LAPORAN PRAKTIKUM KIMIA FISIKA II

PERCOBAAN VII
SIFAT IKATAN, MUATAN, DAN VIBRASI BEBERAPA STRUKTUR SENYAWA
ORGANIK SEDERHANA

Oleh :

Nama : Alfani Mahmudah

NIM : M0318009

Hari/Tgl. Praktikum : Senin/9 November 2020

Asisten Pembimbing : Isni Trisnawati

LABORATORIUM KIMIA
PROGRAM STUDI KIMIA
FAKULTAS MATEMATIKA DAN ILMU PENGETAHUAN ALAM
UNIVERSITAS SEBELAS MARET
SURAKARTA
2020
 LAMPIRAN
GAMBAR PERCOBAAN

1. Senyawa Etanol

Gambar 1.1 Struktur Etanol Gambar 1.2 Struktur Etanol

dengan muatannya
2. Senyawa Etenol

Gambar 1.1 Struktur Etenol Gambar 1.1 Struktur Etenol

dan muatannya
3. Senyawa Asetaldehid

Gambar 1.1 Struktur Asetaldehid Gambar 1.1 Struktur

Asetaldehid dan muatannya
 Jurnal Teknologi Kimia Unimal 5:1 (2016) 57-65

Jurnal
Jurnal Teknologi Kimia Unimal Teknologi
homepage jurnal: jtk@unimal.ac.id Kimia
Unimal

PROSES PEMBUATAN BIOETANOL DARI KULIT PISANG

KEPOK (Musa acuminata B.C) SECARA FERMENTASI

Wusnah, Samsul Bahri, Dwi Hartono

Jurusan Teknik Kimia, Fakultas Teknik, Universitas Malikussaleh Lhokseumawe
Email: wusnah@yahoo.com

Abstrak
Kulit pisang kepok selama ini hanya dianggap sebagai salah satu limbah industri
rumah tangga yang belum termanfaatkan dengan baik. Komposisi terbanyak
kedua kulit pisang kepok adalah karbohidrat 18,50% dimana karbohidrat dapat
dikonversi menjadi glukosa yang selanjutnya dapat digunakan sebagai bahan baku
pembuatan bioetanol.Penelitian ini bertujuan membuat bioethanol dari kulit
pisang kepok dengan variasi waktu fermentasi dan penambahan starter. Pada
penelitian ini kulit pisang kepok dihidrolisis dengan mengunakan HCl 5% pada
suhu 100oC selama 60 menit. Hasil penelitian menunjukkan bahwa semakin lama
waktu fermentasi maka semakin banyak etanol yang dihasilkan.Pada variasi
waktu fermentasi diperoleh waktu terbaik fermentasi pada waktu 7 hari dengan
kadar etanol 40 % sebanyak 34ml.

Kata kunci : kulit pisang kepok, bioetanol, fermentasi

1. Pendahuluan
Sumber daya energi konvensional bahan bakar fosil (minyak/gas bumi dan
batu bara) sebagai sumber energi yang tidak terbarukan dengan segala
permasalahannya, terutama kenaikan harga (price escalation) secara global setiap
terjadinya krisis energi akibat dari faktor-faktor seperti cadangan yang berkurang
sesuai dengan umur eksploitasinya, permintaan yang meningkat, jaminan pasokan
(supply security) yang terbatas dan pembatasan produksi serta penilaian dampak
lingkungan yang ketat terhadap pemanasan global (global warming), harus
dikurangi ketergantungannya denganmenggunakan sumber-sumber energi lainnya
sebagai bahan bakar alternatif.
Bioetanol merupakansalah satu sumber bahan bakar alternatif yang diolah
dari tumbuhan, dimana memiliki keunggulan mampu menurunkan emisi CO2
 Wusnah, dkk / Jurnal Teknologi Kimia Unimal 5:1 (2016) 57–65

13,5406%. Pada variasi penambahan berat ragi diperoleh kadar etanol 13,5353%
dengan berat ragi 0,0624 gram.

Bioetanol adalah sebuah bahan bakar alternatif yang diolah dari tumbuhan,
dimana memiliki keunggulan mampu menurunkan emisi CO2 hingga 18 %. Ada 3
kelompok tanaman sumber bioetanol: tanaman yang mengandung pati (seperti
singkong, kelapa sawit, tengkawang, kelapa, kapuk, jarak pagar, rambutan, sirsak,
malapari, dan nyamplung), bergula (seperti tetes tebu atau molase, nira aren, nira
tebu, dan nira surgum manis) dan serat selulosa (seperti batang sorgum, batang
pisang, jerami, kayu, dan bagas). Bahan yang mengandung pati, glukosa, dan serat
selulosa ini bisa dimanfaatkan sebagai bahan bakar (Arif, 2011).

Tidak ada perbedaan antara etanol biasa dengan bioetanol yang

membedakannya hanyalah bahan baku pembuatan dan proses pembuatannya.
Etanol adalah sejenis cairan yang mudah menguap, mudah terbakar, tak berwarna,
dan merupakan alkohol yang paling sering digunakan dalam kehidupan sehari-
hari. Senyawa ini merupakan obat psikoaktif dan dapat ditemukan pada minuman
beralkohol dan termometer modern. Etanol termasuk ke dalam alkohol rantai
tunggal, dengan rumus kimia C2H5OH dan rumus empiris C2H6O. Ia merupakan
isomer konstitusional dari dimetil eter.

Gambar 1 Struktur Molekul Etanol

Bioetanol yang digunakan sebagai campuran bahan bakar merupakan

etanol (etil alcohol) dengan jenis yang sama dengan yang ditemukanpada
minuman beralkohol. Etanol seringkali dijadikan bahan tambahan bensin sehingga
menjadi biofuel. Produksi etanol dunia untuk bahan bakar transportasi meningkat
3 kali lipat dalam kurun waktu 7 tahun, dari 17 miliar liter pada tahun 2000

59
 Jurnal Kimia Sains dan Aplikasi 14 (3) (2011) : 94 – 99 94

Jurnal Kimia Sains dan Aplikasi 14 (3) (2011) : 94 – 99

ISSN: 1410-8917
Jurnal Kimia Sains dan Aplikasi
Journal of Scientific and Applied Chemistry
Journal homepage: http://ejournal.undip.ac.id/index.php/ksa

Studi Kemampuan Adsorpsi Zeolit Alam Terdealuminasi terhadap

Senyawa Fenol dan 2-Metoksifenol pada Asap Cair Sekam Padi:
Eksperimen dan Komputasi AB Initio
Wempie Gressanggaa, Suhartanab, Parsaoran Siahaana*

a Inorganic Chemistry Laboratory, Chemistry Department, Faculty of Sciences and Mathematics, Diponegoro University, Jalan Prof.
Soedarto, Tembalang, Semarang

* Corresponding author: siahaan.parsaoran@live.undip.ac.id

Article Info Abstract

Study of dealuminated natural zeolite ability to adsorb phenol and 2-methoxyphenol on

Keywords: rice hull liquid smoke have been done. This research was conducted through two
zeolite, approaches of experiments and ab initio computation. Zeolite dealumination did by
dealumination, acidification using HCl and H2SO4. Natural zeolite before and after dealumination was
adsorption, ab
analyzed by Atomic Absorption Spectroscopy (AAS). Liquid smoke before and after
initio, computing
adsorption was analyzed by GC-MS. Modelling was carried out at HF/6-31G** level of
theory obtained the lowest interaction energy between dimer tetrahedral segments of
zeolite ratio Si-Al 2-0 with phenol with amount -19.3313 kkal/mol and with 2-
metoksifenol with amount -22.1246 kkal/mol. Natural zeolite dealumination using 6N
hydrochloric acid obtained highest ratio Si/Al with amount 19,2432. The result of liquid
smoke adsorption obtained phenol and 2-metoxyphenol content with amount of 0,52%
and 28,4%. From this result concluded that higher ratio Si/Al was able to improve
adsorption phenol and 2-methoxyphenol on rice hull liquid smoke, result of ab initio
computational also proved that dimer tetrahedral segmen of zeolite with highest ratio
Si-Al had lowest interaction energy when it interacted with phenol and 2-
methoxyphenol.

Abstrak
Kata kunci:
Telah dilakukan penelitian tentang studi kemampuan adsorpsi zeolit alam
zeolit, dealuminasi,
adsorpsi, ab initio, terdealuminasi terhadap senyawa fenol dan 2-metoksifenol pada asap cair sekam padi.
komputasi Penelitian ini dilakukan melalui dua pendekatan yaitu eksperimen dan komputasi ab
initio. Dealuminasi zeolit dilakukan dengan pengasaman menggunakan asam HCl dan
H2SO4. Zeolit alam sebelum dan sesudah didealuminasi dianalisis menggunakan
Spektroskopi Serapan Atom (SSA). Asap cair sebelum dan sesudah adsorpsi dianalisis
menggunakan GC-MS. Pemodelan dilakukan pada tingkat teori HF/6-31G** diperoleh
energi interaksi terendah antara segmen dimer tetrahedral zeolit rasio Si-Al 2-0 dengan
fenol sebesar -19,3313 kkal/mol dan dengan 2-metoksifenol sebesar -22,1246 kkal/mol.
Dealuminasi zeolit alam menggunakan asam HCl 6N diperoleh rasio Si/Al tertinggi
sebesar 19,2432. Hasil adsorpsi asap cair diperoleh kadar fenol dan 2-metoksifenol
terendah ketika diadsorpsi menggunakan zeolit alam dengan rasio Si/Al tertinggi
dengan kadar masing-masing 0,52% dan 28,4%. Dari data tersebut dapat disimpulkan
bahwa semakin tinggi rasio Si/Al mampu meningkatkan kemampuan adsorpsi senyawa
fenol dan 2-metoksifenol pada asap cair sekam padi, melalui hasil pemodelan juga
dibuktikan bahwa segmen tetrahedral zeolit rasio Si-Al tertinggi memiliki energi
interaksi terendah terhadap molekul fenol dan 2-metoksifenol.
 Jurnal Kimia Sains dan Aplikasi 14 (3) (2011) : 94 – 99 97

mengadsorpsi senyawa-senyawa aromatik kususnya
fenol dan 2-metoksifenol.
Asap cair AC-2b, AC-1b dan AC-2a masing-masing
di adsorpsi menggunakan zeolit terdealuminasi dengan
hasil rasio Si/Al sebesar 11,5277; 14.0071 dan 14.3304.
Hasil analisis GC-MS menunjukkan penurunan
kandungan senyawa fenol semakin besar pada
penggunaan adsorben dengan rasio Si/Al semakin
tinggi. Kandungan senyawa fenol asap cair AC-2b, AC-
1b, dan AC-2a masing-masing sebesar 6,78%, 6,45%
dan 4,93%, sedangkan kandungan senyawa 2-
metokifenol nya sebesar 33,47%, 31,84% dan 31,46%.
Keluarnya alumunium dari kerangka zeolit
menyebabkan permukaan zeolit alam menjadi bersifat
lebih non polar daripada sebelumnya, sehingga
kemampuan adsoprsi zeolit alam terhadap fenol yang
cenderung bersifat non polar meningkat.
Kemampuan adsorpsi terbaik terjadi pada zeolit
ZAH-1a dengan rasio Si/Al tertinggi sebesar 19,2432
yang digunakan untuk mengadsorpsi asap cair AC-1a
menghasilkan kandungan fenol sebesar 0,52% dan 2-
metoksifenol sebesar 28,4%. Kromatogran asap cair AC-
1a dapat dilihat pada gambar 3.
teliti. Perhitungan dilakukan dengan metode ab initio
pada tingkat teori HF dengan basis set 6-31G**
menggunakan program Gaussian03, dengan
mengasumsikan molekul pada fasa gas. Informasi yang
bisa didapat dari hasil perhitungan antara lain energi
molekul, muatan masing-masing atom, muatan total,
momen dipol, frekuensi vibrasi molekul dan lain-lain
[10-12].
Zeolit terdiri dari monomer-monomer tetrahedral
(SiO4)4- dan (AlO4)5-. Pemodelan struktur dimer zeolit
dilakukan dengan memunculkan adanya situs asam
Brownsted di dalamnya, karena transfer proton dari
situs asam Brownsted merupakan tahapan penting pada
proses adsorbsi [7]. Tahap awal dari studi komputasi
perhitungan ab initio adalah optimasi geometri molekul
tunggal antara lain senyawa fenol, 2-metoksifenol dan
segmen dimer zeolit dengan variasi Rasio Si/Al 2-0, 1-1
dan 0-2. Hasil optimasi molekul tunggal diperoleh
geometri dan beberapa parameter yang ditunjukkan
pada tabel 3.
Optimasi geometri bertujuan untuk mendapatkan
struktur molekul tiga dimensi dengan energi minimum
global (keadaan paling stabil). Penentuan optimasi
geometri molekul diawali dengan perkiraan awal
struktur yang dinyatakan dalam matrik-Z.

Tabel 3. Tabel struktur geometri dan beebrapa

parameter hasil optimasi molekul tunggal

Gambar 3. Kromatogram asap cair setelah di adsorpsi

dengan zeolit ZAH-1a (AC-1a)

Dari Kromatogram asap cair AC-1a pada gambar 3

juga menunjukkan bahwa pada asap cair AC-1a lebih
banyak senyawa yang teradsorpsi, hal ini dapat dilihat
dengan melihat jumlah peak pada grafik kromatogram
asap cair AC-S pada gambar II terdapat 41 peak
sedangkan pada hasil kromatogram asap cair AC-1a
gambar 3 menunjukkan hanya terdapat 18 peak.

Dari hasil penelitian ini menunjukkan bahwa

kemampuan adsorpsi tertinggi pada zeolit ZAH-1a
dengan rasio Si/Al sebesar 19.2432 yaitu dengan hasil
asap cair AC-1a sebasar senyawa fenol 0,52% dan
senyawa 2-metoksifenol 28,4%. Hal ini sesuai dengan
penelitian sebelumnya yang pernah dilakukan,
permukaan zeolit akan semakin bersifat hidrofobik jika
rasio Si/Al meningkat sehingga kemampuan adsorpsi
zeolit terhadap senyawa-senyawa non polar semakin
meningkat.

Fenomena molekular pengaruh zeolit alam

terdealuminasi menjadi penting untuk mengetahui nilai
kuantitatif yang terjadi pada tingkat molekular dengan
melihat pengaruh perubahan rasio Si/Al terhadap energi
interaksi yang terjadi terhadap adsorbat. Kimia
komputasi memungkinkan penentuan struktur/
geometri dan energi interaksi berbagai molekul secara
Hindawi
International Journal of Corrosion
Volume 2017, Article ID 8915967, 10 pages
https://doi.org/10.1155/2017/8915967

Research Article
Semiempirical Theoretical Studies of 1,3-Benzodioxole
Derivatives as Corrosion Inhibitors

Omnia A. A. El-Shamy
Egyptian Petroleum Research Institute, Nasr City, Cairo 11727, Egypt

Correspondence should be addressed to Omnia A. A. El-Shamy; omniaelshamy@yahoo.com

Received 31 December 2016; Revised 28 February 2017; Accepted 7 March 2017; Published 20 March 2017

Academic Editor: Flavio Deflorian

Copyright © 2017 Omnia A. A. El-Shamy. This is an open access article distributed under the Creative Commons Attribution
License, which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly
cited.

The efficiency of 1,3-benzodioxole derivatives as corrosion inhibitors is theoretically studied using quantum chemical calculation
and Quantitative Structure Activity Relationship (QSAR). Different semiempirical methods (AM1, PM3, MNDO, MINDO/3, and
INDO) are applied in order to determine the relationship between molecular structure and their corrosion protection efficiencies.
Different quantum parameters are obtained as the energy of highest occupied molecular orbital 𝐸HOMO , the energy of the lowest
unoccupied molecular orbital 𝐸LUMO , energy gap Δ𝐸𝑔 , dipole moment 𝜇, and Mulliken charge on the atom. QSAR approach is
applied to elucidate some important parameters as the hydrophobicity (Log P), surface area (S.A), polarization (𝑃), and hydration
energy (𝐸Hyd ).

1. Introduction
The widths involved for different metals, especially iron with
its various grades, are widely used in many industrial fields,
such as petrochemical industries, petroleum oil production,
transportation, and others. That has led to conducting more
research into the metal surface protection in various aggres-
sive media, especially acid medium. The most essential aim of
corrosion research papers is to determine the best protection
compounds for metal and metal alloys in different aggressive
corroded media. However, these research papers do not only
cost a lot of money, but they also take so much time to detect
the most effective inhibitors [1–4].
Among numerous corrosion inhibitors, organic com-
pounds are considered as powerful inhibitors, especially
hetero organic compounds [5, 6] that possess active centers
as oxygen, nitrogen, and sulphur. The inhibiting mechanism
of corrosion inhibitors occurs via physical and/or chemical
adsorption of the inhibitors on the metal surfaces. The
adsorption of these compounds occurred via transferring the
e’s from the high electron atoms to the metal surface, resulting
in that coordinate covalent bond between the inhibitor
compound and metal surface [7]. Most researchers see that
adsorption does not only depend on the physicochemical
properties of the inhibitor molecules but also depend on the
nature of the metal surface and that of media. Since they are
usually perfect, the corrosion inhibiting compounds should
not only donate electrons to the metal d-orbital but also
accept the e’s from them through antibonding orbital to form
feedback donation [8, 9].
Recently, in the presence of sophisticated hardware and
with the development of theoretical chemistry programs,
quantum chemical calculation methods are looked upon as
some of the most effective tools not only for the molecular
structure but also for elucidating the active center of the
studied molecules [10, 11]. Semiempirical calculations are rec-
ommended as more accurate methods, but not for all of the
e’s-e’s interaction processes, compared to an extended Hückel
method that neglects all the e’s-e’s interaction processes to
become less accurate [12, 13].
The applications of 1,3-benzodioxole derivatives as cor-
rosion inhibitors are not dealt widely with. The efficiency
of 5-(1,3-benzodioxol-5-yl)-1-(piperidin-1-yl)penta-2,4-dien-
1-one and 5-(1,3-benzodioxol-5-yl)-1-(piperidin-1-yl)pent-2-
en-1-one as corrosion inhibitors was experimentally/theoret-
ically studied. Good agreement is obtained between experi-
mental results and quantum parameters [14].
The aim of this paper is to study the dependence of inhi-
bition efficiencies for different substitutes of 1,3-benzodioxole
2 International Journal of Corrosion

O
O O O

− O
O Cl O
O

1,3-Benzodioxole (I) 1,3-Benzodioxole, 5-ethenyl (II) 1,3-Benzodioxole, 5-(chloromethyl)- (III) 1,3-Benzodioxole, 5-(2-propenyl)- (IV)

O O O O
O O O O
O O
O O
O O
1,3-Benzodioxole, 4-
1,3-Benzodioxole, 4,7- 1,3-Benzodioxole, 4,7-dimethoxy-5-(1- 1,3-Benzodioxole-5-carboxaldehyde
methoxy-6-(2-
dimethoxy-5-(2-propenyl)- (VI) propenyl)-, (E)- (VII) (VIII)
propenyl)- (V)

O
O O O N
O
O
O O O
O O
O O
O

1,3-Benzodioxole-5- 1,3-Benzodioxole-5-carboxylic 1,3-Benzodioxole-5-acetic acid, 1,3-Benzodioxole-5-methanamine

carboxylic acid (IX) acid, methyl ester (X) methyl ester (XI) (XII)

Figure 1: The molecular structure of the studied 1,3-benzodioxole derivatives.

on their molecular and electronic structures using some
semiempirical methods (AM1, PM3, MNDO, MNDO/3, and
INDO). The inhibition efficiencies are obtained by different
quantum chemical parameters as the energy of the frontier
orbital, charge densities, Dipole moment 𝜇, and so forth. The
QSAR is used to investigate hydrophobicity, polarization, and
other important parameters. The investigation performed in
this study will be helpful in producing new 1,3-benzodioxole
substitutes, such as corrosion inhibitors, where the appli-
cation of these compounds like corrosion inhibitors is not
widely dealt with. The molecular structures of the studied 1,3-
benzodioxole derivatives are listed in Figure 1.
2. Theoretical Calculation
All the Quantum chemical calculations are carried out at
Restricted Hartree-Fock (RHF), by spin pairing case using
AM1, PM3, MNDO, MINDO/3, and INDO semiempirical
methods and SCF (iteration limit = 50) using Hyperchem 8.0.10
windows program implemented on the Intel core i7 laptop.
The energy of highest occupied molecular orbital, 𝐸HOMO ,
and the energy of lowest unoccupied molecular orbital,
𝐸LUMO , are used for indicating the adsorption ability of the
investigated organic compounds. With regard to the Hartree-
Fock theorem [15], the ionization potential, 𝐼, and electron
affinity and 𝐴 are obtained from the following:
𝐼 = −𝐸HOMO
(1)
𝐴 = −𝐸LUMO .
The electronegativity (𝑋) and absolute hardness (𝜂) of the
investigated molecule are related to the electron affinity and
the ionization potential as follows:
1 are calculated using different semiempirical methods (AM1,
𝑋 = (𝐼 + 𝐴)
2 (2)
1 Table 1. The applied methods show some differences in the
𝜂 = (𝐼 − 𝐴) .
2
The hydration energy, 𝐸Hyd , hydrophobicity Log, P, sur-
face area, SA, and the polarizability, 𝑃, of the investigated
molecules are obtained from QSAR calculations.
3. Discussion
The quantum chemistry computing method is often used to
study the simple systems taking into account that (i) the effect
depends only on the inhibitor molecule properties and (ii)
everything else in its vicinity is uninvolved either with respect
to competition for the surface or with respect to itself. Several
researches confirmed that there is little effect of the media on
these parameters [16–20]. Since, all metals are characterized
by the presence of vacant d orbital which is ready to accept e’s
from donors (inhibitor molecules), the computing method is
suitable for most metals.
Different 1,3-benzodioxole derivatives are selected to
study the effect of molecular electronic properties based on
the nature of a substitute. The optimized geometry of the
investigated molecules possesses minimum total energy (the
net result of the electronic kinetic energy and the interactions
between atomic cores and all e’s) is shown in Figure 2. The
cyan color corresponds to carbon, red color to oxygen, white
color to hydrogen, and dark blue color to nitrogen atoms.
In adsorption process, frontier orbital (HOMO and
LUMO) should be taken into account in order to predict the
adsorption site of the studied molecules. The higher 𝐸HOMO
is, the higher electron donating tendency of a molecule to
the metal is. However, the lower 𝐸LUMO becomes, the lower
tendency of the molecule to accept e’s from metal is. Thus,
the molecule’s binding to the metal surfaces increases with
higher 𝐸HOMO and lower 𝐸LUMO [21, 22]. 𝐸HOMO and 𝐸LUMO
PM3, MINDO/3, MNDO, and INDO) and the data listed in
calculated values of frontier orbital.
Journal of Molecular Structure, 43 (1978) 267-271
OElsevier Scientific Publishing Company, Amsterdam - Printed in The Netherlands

THE STRUCI’URE OF VINYL ALCOHOL

WILLEM J. BOUMA and LEO RADOM

Research School of Chemistry, Australian National University, Canberra, A.C.T. 2600
(Australia)
(First received 21 June 1977; in revised form 19 September 1977)

ABSTRACT

Theoretical structures for vinyl alcohol are obtained using ab initio molecular orbital
theory and the minimal STO-3G and split-valence 4-31G basis sets. The preferred con-
formation has HOCC syn. Correction for the systematic deficiencies of both basis sets
and use of experimental rotational constants leads to a prediction of the complete r,,
structure for vinyl alcohol.

INTRODUCTION

Vinyl alcohol, the enol isomer of acetaldehyde, although proposed as a

reaction intermediate nearly 100 years ago El], has until very recently eluded
experimental identification. Blank and Fischer [2] in 1973 observed the
CIDNP enhanced NMR spectrum of vinyl alcohol in the liquid phase but it
was not until recently (1976) that the first gas-phase identification of
vinyl alcohol was reported. Saito [ 31 was able to generate vinyl alcohol by
thermal dehydration of ethylene glycol and to observe its microwave spectrum.
From the derived rotational constants and assuming the values of the other
nine parameters, Saito calculated r0 values for two of the structural parameters
in vinyl alcohol. In this paper, ab initio molecular orbital theory is used to
predict the complete structure of vinyl alcohol. It should be noted that
ab initio calculations on vinyl alcohol with standard geometries [4, 51 or
partial (three out of eleven parameters) geometW-optimization [6] have
been reported previously.

METHODS AND RESULTS

Standard LCAO- SCF-MO calculations were carried out using the Gaussian
70 system of programs [ 71 and the STO-3G [S] and 4-31G [9] basis sets.
All geometric parameters* in syn (IA) and anti (IB) isomers of vinyl alcohol
were optimized with both basis sets yielding the results in Table 1.

*Bond lengths throughout this paper are in A, bond angles in degrees.

270

TABLE 3

Comparison of theoretical and experimental O-H bond lengths (r. A)

Molecule Exptl. STO-3G 4-3 1G

r Ara r Ara

HO-H 0.957 0.990 +0.033 0.951 -0.006

CH,O-H 0.956 0.991 +0.035 0.951 -0.005
Mean + 0.034 -0.006

aAr = r (theoretical) -r (experimental).

type of system are approximately 0.034 A too long while 4-31G estimates
are approximately 0.006 A too short. The optimized STO-3G and 4-31G
values of-the O--H length in syn vinyl alcohol (Table 1) then lead to corrected
values of 0.956 A and 0.958 A, respectively, and hence our “best”value of
0.957 A.
The structural parameters with the greatest uncertainties resulting from
the application of this procedure are the C-O length and the CC0 and CCH,
bond angles. We believe that the remaining eight geometric parameters are
predicted to an accuracy well within 0.01 A in lengths and 1” in angles.
We were able to use the experimental rotational constants [3] to decide on
the best values of the C-O length and the CC0 angle within the theoretically
acceptable range. However, the calculated rotational constants are quite
insensitive to the value of the CCH, angle and it was not possible to refine
our value for this parameter which consequently has a somewhat greater
uncertainty of approximately + 2”.
The resultant best structure for syn vinyl alcohol, i.e. our prediction of
the r, structure, is shown in Fig. 1. Our CC0 angle (126.0”) is the same but
the C-O length (1.364 A) somewhat shorter than the values (126.0” and
1.373 A, respectively) derived in the microwave study 131, though it
must be recalled that, in the latter, all the other geometrical parameters
were assigned assumed values on the basis of experimental structures for

Fig. 1. Predicted structure for vinyl alcohol.

 Journal of Molecular Structure 985 (2011) 202–210

Contents lists available at ScienceDirect

Journal of Molecular Structure

journal homepage: www.elsevier.com/locate/molstruc

The r0 structural parameters, conformational stability, barriers to internal

rotation, and vibrational assignments for trans and gauche ethanol
James R. Durig ⇑, Hamoudeh Deeb, Ikhlas D. Darkhalil, Joshua J. Klaassen, Todor K. Gounev,
Arindam Ganguly
Department of Chemistry, University of Missouri – Kansas City, Kansas City, MO 64110, USA

a r t i c l e i n f o a b s t r a c t

Article history: The infrared spectrum (4000–400 cm1) of the gas and variable temperature (55 to 100 °C) spectra of
Received 30 July 2010 xenon solutions of ethanol (ethyl alcohol), CH3CH2OH, have been recorded. From these data complete
Received in revised form 24 October 2010 vibrational assignments have been made for both the trans (anti) and gauche conformers. By utilizing
Accepted 25 October 2010
the conformer pair of the CH3 rock fundamental modes in the xenon solution the enthalpy difference
Available online 13 November 2010
has been determined to be 62 ± 12 cm1 (0.75 ± 0.14 kJ mol1) with the trans form the more stable con-
former from variable temperature spectra of xenon solutions. It is estimated that there is approximately
Keywords:
40 ± 1% of the trans form present at ambient temperature. By using the previously reported fifteen
Xenon solutions
r0 Structural parameters
rational constants of the five heavy atom isotopomers for the trans conformer and the three rotational
ab initio calculations constants for the gauche form combined with the structural parameters predicted from the MP2(full)/
Barriers to internal rotation 6-311+G(d,p) calculations, the adjusted-r0 parameters have been obtained. The heavy atom structural
Ethanol parameters for the trans [gauche] are: the distance (Å), C–O = 1.433(3) [1.430(3)], C–C = 1.518(3)
[1.523(3)]; and angle (°), CCO = 107.6(5) [112.5(5)], HOCC = 180.0 [56.9(5)]. The DJ, DJK, DK, dJ, dK centrif-
ugal distortion constants have been predicted from ab initio and density functional theory calculations
which are compared to the corresponding experimentally determined values. The harmonic force field,
infrared intensities, band contours, and vibrational frequencies have been obtained for both conformers
from ab initio MP2 (full)/6-31G(d) calculations and the results are compared to the experimental values
when appropriate. The results are discussed and compared to the corresponding quantities of some sim-
ilar molecules.
Ó 2010 Elsevier B.V. All rights reserved.

1. Introduction Gallagher that determined the CC and CO bond distances, the CH

The conformational stabilities and barriers to internal rotation
of alcohols in the gas phase or in solution have provided significant
challenges to structural scientist for years for a variety of reasons.
The O–H barriers for those that have been determined are about
one third or less than those obtained for methyl barriers so there
is usually only the fundamental vibration and one excited state
in the potential well which makes it difficult to obtain the barriers
to internal rotation from the torsional frequencies. Also the deter-
mination of the conformational stability has been difficult to deter-
mine because of the association due to hydrogen bonding which is
significant in the gas phase where vibrations due to the dimer as
well as trimers can be observed.
The determination of the structural parameters for ethanol has
not been without some serious problems. The first structural deter-
mination was an electron diffraction study [1] by Rouault and
⇑ Corresponding author. Tel.: +1 816 235 6038; fax: +1 816 235 2290.
E-mail address: durigj@umkc.edu (J.R. Durig).
bond distances as one set, and the CCO angle. The first complete
structural determination was a microwave study [2] where
Kadzhar et al. used the principal moments of inertia obtained for
ethanol and seven isotopomers to determine the structural param-
eters. This structural determination suffered from the assumption
that the methyl hydrogens were all equivalent and the difference
between the secondary moments of inertia P cc —Pcc not being equal
to zero. The next complete structural determination was another
microwave study [3] by Culot where the rotational spectra of thir-
teen isotopomers of ethanol were used to determine the rs struc-
tural parameters. In this study [3] it was concluded that the
structural determination by the substitution method was unfavor-
able and the structural parameters obtained were not accurate, this
conclusion was based on the finding that the effect of zero-point
vibrations is rather large. This effect is even larger when the substi-
tution is done on the in-plane hydrogen atom of the methyl group
and the hydrogen atom of the OH group. Culot was aware that the
zero-point vibrational effects due to the torsional oscillation of the
methyl group resulted in less accurate structural parameters
especially those involving the H7 coordinates, Fig. 4. This was

0022-2860/$ - see front matter Ó 2010 Elsevier B.V. All rights reserved.
doi:10.1016/j.molstruc.2010.10.043
 J.R. Durig et al. / Journal of Molecular Structure 985 (2011) 202–210 205

Table 4
Structural parametersa, rotational constants, and dipole moments for trans and gauche ethanol.

Parameter Int. coor. Trans Gauche

b c d e
MP2(full)/ B3LYP/ ED MW MW rs MW rs Adjusted r0f,g MP2(full)/ B3LYP/ Adjusted r0f,g
6-311+G(d,p) 6-311+G(d,p) 6-311+G(d,p) 6-311+G(d,p)
r(O3–H4) R1 0.960 0.962 0.936 0.956 0.9710 (6) 0.962 (3) 0.961 0.963 0.963 (3)
r(C2–O3) R2 1.426 1.431 1.40 1.426 1.428 1.431(3) 1.432(3) 1.424 1.429 1.430(3)
r(C1–C2) R3 1.513 1.517 1.50 1.533 1.524 1.512(3) 1.519(3) 1.519 1.524 1.523(3)
r(C1–H7)ip r1 1.093 1.093 1.08 1.092 1.093 1.0878(3) 1.095(2) 1.094 1.095 1.096(2)
r(C1–H8)op r2 1.092 1.093 1.08 1.092 1.093 1.0908(2) 1.094(2) 1.095 1.095 1.097(2)
r(C1–H9)op r3 1.092 1.093 1.08 1.092 1.093 1.0908(2) 1.094(2) 1.092 1.093 1.094(2)
r(C2–H5) r4 1.097 1.099 1.08 1.092 1.100 1.0980(4) 1.099(2) 1.098 1.099 1.100(2)
r(C2–H6) r5 1.097 1.099 1.08 1.092 1.100 1.0980(4) 1.099(2) 1.091 1.092 1.093(2)
\C2O3H4 p1 107.7 109.0 106.0 104.8 105.4(1) 107.5(5) 107.0 108.6 107.0(5)
\O3C2H5 p2 110.6 110.4 109.8(2) 110.8(5) 110.6 110.4 110.4(5)
\O3C2H6 p3 110.6 110.4 109.8(2) 110.8(5) 105.3 105.1 105.2(5)
\C1C2O3 a 107.6 107.9 109.5 107.4 107.6 107.77(2) 107.6(5) 112.3 113.0 112.5(5)
\C1C2H5 q1 110.1 110.2 109.8 109.5 110.7(2) 109.6(5) 110.3 110.4 110.2(5)
\C1C2H6 q2 110.1 110.2 109.8 109.5 110.7(2) 109.6(5) 110.5 110.4 110.5(5)
\H5C2H6 b 108.1 107.8 108.0(2) 108.5(5) 107.7 107.3 107.7(5)
\H7C1C2 d1 110.4 110.4 109.8 110.7 110.5(1) 110.0(5) 110.7 110.6 110.7(5)
\H8C1C2 d2 110.2 110.5 109.8 110.7 110.5(1) 109.7(5) 110.8 111.2 110.8(5)
\H9C1C2 d3 110.2 110.5 109.8 110.7 110.5(1) 109.7(5) 110.3 110.7 110.2(5)
\H8C1H9 l1 108.6 108.3 108.8(2) 109.0(5) 108.3 108.2 108.4(5)
\H7C1H8 l2 108.6 108.3 108.8(2) 109.0(5) 107.8 107.6 107.9(5)
\H7C1H9 l3 108.7 108.5 108.8(2) 109.2(5) 108.8 108.5 108.8(5)
sH4O3C2C1 s1 180.0 180.0 180.0 180.0 180.0 180.0 180.0 56.9 60.8 56.9(5)
sH7C1C2O3 s2 180.0 180.0 180.0 180.0 180.0 180.0 180.0 177.4 177.2 177.4(5)
A 35060 35097 34890.8 34890.8 34891.73(7) 34898.282 34252 34417 34173.8
B 9421 9320 9350.8 9350.8 9350.65(2) 9352.933 9270 9122 9191.5
C 8189 8113 8135.0 8135.0 8135.22(2) 8136.169 8161 8063 8100.4
|la| 0.014 0.043 0.058(100) 1.597 1.419
|lb| 1.903 1.772 1.473(100) 0.024 0.076
|lc| 0.000 0.000 0.000 1.338 1.233
|lt| 1.903 1.773 1.474(100) 2.084 2.660
a
Bond distances in Å, bond angles in degrees, rotational constants in MHz, and dipole moments in Debye.
b
Ref. [1].
c
Assumed structural parameters, Ref. [24].
d
Ref. [2].
e
Ref. [3].
f
This study.
g
Adjusted structural parameters with experimental rotational constants taken from Ref. [4].

with the 6-31G(d) basis set. The internal coordinates used to calcu-
late the G and B matrices are given for the trans and gauche con-
formers in Table 4 with the atomic numbering shown in Fig. 2.

Table 5
Symmetry coordinates for trans ethanol.

Species Description Symmetry coordinate*

0
A OH stretch S1 = R1
CH3 antisymmetric stretch S2 = 2r1  r2  r3
CH3 symmetric stretch S3 = r1 + r2 + r3
CH2 symmetric stretch S4 = r4 + r5
CH2 symmetric deformation S5 = 4b  q1  q2  p2  p3
CH3 antisymmetric deformation S6 = 2l1  l2  l3
CH2 wag S7 = p2 + p3  q1  q2
CH3 symmetric deformation S8 = l1 + l2 + l3  d1  d2  d3
COH bend S9 = p1
CO stretch S10 = R2
CC stretch S11 = R3
CH3 rock S12 = 2d1  d2  d3
CCO bend S13 = a
A00 CH3 antisymmetric stretch S14 = r2  r3
CH2 antisymmetric stretch S15 = r4  r5
CH3 antisymmetric deformation S16 = l2  l3
CH2 twist S17 = p2  p3  q1 + q2
CH2 rock S18 = p2  p2 + q1  q2
CH3 rock S19 = d2  d3
OH torsion S20 = s1
CH3 torsion S21 = s2
*
Not normalized. Fig. 1. Mid-infrared spectra of ethanol (A) gas; (B) Xe solution at 60 °C.
Int. J. Mol. Sci. 2012, 13, 15360-15372; doi:10.3390/ijms131115360
OPEN ACCESS
International Journal of
Molecular Sciences
ISSN 1422-0067
www.mdpi.com/journal/ijms
Article

Eclipsed Acetaldehyde as a Precursor for Producing

Vinyl Alcohol
Osman I. Osman *, Abdulrahman O. Alyoubi, Shabaan A. K. Elroby, Rifaat H. Hilal and
Saadullah G. Aziz

Chemistry Department, Faculty of Science, King Abdulaziz University, P.O. Box 80203,
Jeddah 21589, Saudi Arabia; E-Mails: aalyoubi@kau.edu.sa (A.O.A.);
Skamel@kau.edu.sa (S.A.K.E.); rhilal@kau.edu.sa (R.H.H.); saziz@kau.edu.sa (S.G.A.)

* Author to whom correspondence should be addressed; E-Mail: oabdelkarim@kau.edu.sa;

Tel.: +966-2-6952000 (ext. 69315); Fax: +966-2-6952709.

Received: 24 September 2012; in revised form: 29 October 2012 / Accepted: 29 October 2012 /
Published: 20 November 2012

Abstract: The MP2 and DFT/B3LYP methods at 6-311++G(d,p) and aug-cc-pdz basis sets
have been used to probe the origin of relative stability preference for eclipsed acetaldehyde
over its bisected counterpart. A relative energy stability range of 1.02 to 1.20 kcal/mol, in
favor of the eclipsed conformer, was found and discussed. An NBO study at these
chemistry levels complemented these findings and assigned the eclipsed acetaldehyde
preference mainly to the vicinal antiperiplanar hyperconjugative interactions. The
tautomeric interconversion between the more stable eclipsed acetaldehyde and vinyl
alcohol has been achieved through a four-membered ring transition state (TS). The
obtained barrier heights and relative stabilities of eclipsed acetaldehyde and the two
conformers of vinyl alchol at these model chemistries have been estimated and discussed.

Keywords: acetaldehyde; eclipsed; bisected; vinyl alcohol; tautomerization;

hyperconjugation; MP2; B3LYP; NBO

1. Introduction

Acetaldehyde (CH3CHO) was first synthesized by Scheele in 1774 [1]. The importance of
acetaldehyde lies in its usage as an intermediate in many organic reactions [2]. To understand the
mechanisms of how acetaldehyde works as an intermediate in these organic reactions; the relative
Int. J. Mol. Sci. 2012, 13 15365

Table 3. Optimized geometry a, bond lengths in Å and angles in degrees, of acetaldehyde,

Transition State (TS) and syn and anti vinyl alcohol which were obtained by using
B3LYP/aug-cc-pvdz level of theory.
Definition CH3CHO TS Syn CH2CHOH Anti CH2CHOH
C1–H1 1.102 (1.086) b 1.093 1.088 (1.070) c 1.087 (1.073) d
C1–H3 1.103 (1.086) 1.098 1.092(1.079) 1.089 (1.078)
C1–H2 1.096 (1.079) 1.507 - -
C–C 1.504 (1.501) 1.415 1.337 (1.326) 1.335 (1.315)
C2–H4 1.118 (1.114) 1.099 1.090 (1.086) 1.093 (1.075)
C–O 1.212 (1.216) 1.285 1.366 (1.372) 1.372 (1.352)
OH - 1.302 0.967 (0.969) 0.963 (0.941)
H1C1H3 109.57 (108.3) 113.78 117.89 (118.8) 118.85 (119.9)
H1C1C2 109.32 (109.2) 122.22 119.74 (119.5) 119.55 (119.9)
CCO 124.71 (123.9) 110.51 126.94 (126.2) 122.15 (122.7)
H4C2O 119.97 (117.5) 119.12 110.47 (110.7) 115.73 (115.7)
H1CCO −121.85 −152.96 180.00 180.00
H3CCO 121.85 66.50 0.00 0.00
H2CCH4 −179.99 168.17 180.00 180.00
H2CCO 0.002 −9.09 180.00 180.00
a
The optimized geometry obtained by this work. The values between brackets are the experimental
geometries of: b acetaldehyde taken from References [3,21]; c syn vinyl alcohol taken from Reference [22] and
d
anti vinyl alcohol obtained from Reference [23].

The main geometrical features of the TS that manifested the interconversion between eclipsed
acetaldehyde and vinyl alcohol are: (i) the elongation of the C1–H2 from 1.096 Å in acetaldehyde to
become 1.507 Å in the TS and to disappear completely in vinyl alcohol (ii) the shortening of C–C bond
of 1.504 Å in acetaldehyde to become 1.415 Å in the TS and to finally settling at 1.337 Å in vinyl
alcohol as a C=C bond (iii) the elongation of acetaldehyde C=O bond of 1.212 Å by about 0.073 Å in
the TS and to attain a typical length of a C–O bond length of 1.366 Å in vinyl alcohol (iv) the
emergence of a weakly bonded (H–O) bond of 1.302 Å in the TS that eventually reached a normal HO
bond length of 0.967 Å in vinyl alcohol (v) the typical sp3 HCH angles of ca. 109.6° in acetaldehyde
opened up by about 4.2° in the TS and flattened up more by ca. 4.1° in vinyl alcohol (vi) the
three-dimensional dihedral angles of acetaldehyde have worked out their path nicely toward a flat
vinyl alcohol through the TS.

2.2.2. Activation Energies and Relative Stabilities

Table 4 lists the zero-point corrected total electronic energies and activation energies of eclipsed
acetaldehyde, the Transition State (TS) and syn and anti vinyl alcohol which were computed by using
MP2 and B3LYP methods at 6-311++G(d,p) and aug-cc-pvdz basis sets. Figure 3 depicts the Intrinsic
Reaction Coordinate (IRC) plot that connects eclipsed acetaldehyde to vinyl alcohol through the TS by
using B3LYP/aug-cc-pvdz model chemistry. The analysis of the TS imaginary frequency showed
variations in the C1–H2 bond length that were in line with the anticipated interconversion between the
eclipsed acetaldehyde and vinyl alcohol which were connected by a saddle point.
Indian Journal of Pure & Applied Physics
Vol. 48, March 2010, pp. 183-191

Vibrational spectroscopy study of diethyl carbamazine using

semi-empirical calculations
S Gunasekarana, B Anitab & S Seshadric
aRegistrar, Periyar Univeristy, Salem
bDepartment of Physics, D G Vaishnav College, Chennai 600 106
cDepartment of Physics, Sir Chandrasekharendra Saraswathi Viswa Mahavidyalaya, Kanchipuram 631 561
E-mail: anitabharathan@yahoo.com
Received 30 June 2008; revised 7 December 2009; accepted 15 January 2010

The study of vibrational spectra of diethyl carbamazine is difficult to interpret by normal coordinate analysis because of
the complex structure and low symmetry of the molecule. The vibrational spectra of the molecule have been studied
completely and various normal modes with great wave number accuracy have been identified. The equilibrium geometries
and harmonic frequencies of the compounds diethyl carbamazine are determined and analysed using the semi-empirical
methods AM1 and PM3. The differences between the observed and calculated wavenumber values in the molecule are
marginal. Thermodynamic properties like entropy, heat capacity, zero point energy have been calculated for the molecule.
Since the structure of the diethyl carbamazine is very complex, it is very difficult to calculate the above mentioned
parameters using empirical techniques HR and DFT. Therefore, in the present study, the semi-empirical techniques are only
applied to the compound to study its molecular parameters.
Keywords: Diethyl carbamazine, FTIR spectra, FT Raman spectra, Semi-empirical method

1 Introduction moderately large molecules1-5. For diethyl

Predicting and understanding the properties and
behaviour of real material systems is of great
importance both from technological and academic
points of view. The theoretical problems associated
with these systems are quite complex. Computational
chemistry uses the results of theoretical chemistry,
incorporated into efficient computer programs, to
calculate the structure and properties of molecules and
solids. The methods are based on theories which
range from highly accurate, but suitable for small
systems, to very approximate, but suitable for large
systems. The accurate methods are called ab initio
methods, as they are based entirely on theory from
first principles. The less accurate methods, like MM1-
4 methods are called empirical or semi- empirical,
because some experimental results, often from atoms
or related molecules are used with the theory.
Semi-empirical methods represent a middle road
between the qualitative results available from
molecular mechanics and the computationally time-
consuming quantitative results available from ab
initio methods. When used judiciously, semi-
empirical methods like AM1, PM3, MNDO can give
great insight into structure and reactivity of even
carbamazine, vibrational spectral studies (Fourier
transform infrared and Raman spectral studies) and
normal coordinate analysis calculations using the
Wilson’s F-G matrix method have been carried out
earlier6. At the completion of the work, it was
observed that it is very difficult to interpret the spectra
of this molecule because of its complex structure and
low symmetry. In the present paper the vibrational
spectra of the molecule diethyl carbamazine has been
studied to identify the various normal modes with
greater wave number accuracy. For the analysis of the
molecule, semi-empirical methods AM1 and PM3
implemented in GAUSSIAN program have been used.
Ab initio programs such as ATMOL, GAUSSIAN,
IBMOL, POLYATOM, Cache are being used to
speed up calculations of molecular orbitals. The
commercial package GAUSSIAN is considered by
most to be the industry standard, although other
packages like Spartan, Hyperchem are challenging
Gaussian for computational performance, and used by
the research community. Gaussian is the benchmark
by which all other ab-initio methods are measured.
The primary advantage of ab-initio methods is the
accuracy with which calculations are performed.
Fundamentally, it is the most accurate and precise of
 Prosiding Seminar Hilirisasi Penelitian Untuk Kesejahteraan Masyarakat
Lembaga Penelitian Universitas Negeri Medan, 28 September 2017

PERHITUNGAN Ab INITIO PADA REAKSI ASETALISASI 2-HIDROKSIBENZALDEHIDA DILINDUNGI

OLEH GUGUS PELINDUNG MEM MENGGUNAKAN KATALIS ASAM KLORIDA

Muhammad Yusuf* dan Ahmad Kamil Nasution

Jurusan Kimia, Universitas Negeri Medan
Jl. Willem Iskandar Psr V Medan, Indonesia
Email : yusuf.6423@gmail.com

Abstrak

Perhitungan ab initio menggunakan basis set 6-31G * dan 3-21G telah diterapkan pada
model reaksi asetalisasi 2-hidroksibenzaldehid yang dilindungi oleh gugus pelindung MEM dengan
adanya katalis HCl. Perhitungan ini menyangkut perubahan energi pada setiap tahap mekanisme
reaksi meliputi pengaruh gugus pelindung MEM, pembentukan keadaan antara hemiasetal, dan
pembentukan produk asetal.
Berdasarkan hasil perhitungan, pengaruh gugus pelindung MEM dan juga pengaruh gugus
pelindung MEM dalam kondisi ionik menunjukkan energi tertinggi (1021,44 kJ/mol dan 1709,12
kJ/mol) dibandingkan dengan tanpa adanya MEM (512.93 kJ/mol) dan juga jika dibandingkan
dengan molekul lainnya karena ketidakstabilannya. Hasil perhitungan ini menunjukkan bahwa
tahap pertama mekanisme reaksi dimulai dari protonasi karbonil oleh katalis HCl. Sedangkan,
pengaruh gugus pelindung MEM dalam mekanisme ini adalah untuk mencegah terjadinya serangan
gugus hidroksi pada katalis HCl. Akan tetapi, tahap ini membutuhkan katalis Natrium Hidrida
sehingga sulit untuk dilakukan. Selain itu, setelah terbentuk produk asetal juga diperlukan katalis
untuk melepaskan gugus pelindung MEM dari produk asetal.

Kata kunci: Ab initio, asetalisasi, dan gugus pelindung

Ab INITIO CALCULATION ON THE ACETALIZATION OF 2-HYDROXYBENZALDEHYDE REACTION

PROTECTED BY MEM PROTECTIVE GROUP USING HYDROCHLORIC ACID CATALYST

Abstract

Ab initio calculation using the 6-31G* and 3-21G basis set has been applied to the reaction
model the acetalization of 2-hydroxybenzaldehyde protected by MEM protective group in the
presence of HCl catalyst. This calculation concern on the energy changes in the each step of
reaction mechanism includes protective group effects of MEM, the formation of hemiacetal
intermediate, and the formation of acetal product.
Based on the calculation results, the protective group effect of MEM as well as the
protective group effect of MEM in ionic condition showed the highest energy (1021. 44 kJ/mol and
1709.12 kJ/mol) compared to without the presence of MEM (512.93 kJ/mol) and also if compared
to among the other molecule due to its instability. These calculation results indicate that the first
possible step of the reaction mechanism is started from protonation of carbonyl by the HCl
catalyst. Whereas, the protective group effect of MEM in this mechanism is to prevent the attack of
the hydroxyl group on the HCl catalyst. However, this step needs the Natrium Hydride catalyst so
that difficult to follow this step. Besides that, after 2-hydroxybenzaldehyde converted to acetal
product also need a catalyst to remove the protective group of MEM from acetal product.

Keyword: Ab initio, acetalization, and protective group

418
 Prosiding Seminar Hilirisasi Penelitian Untuk Kesejahteraan Masyarakat
Lembaga Penelitian Universitas Negeri Medan, 28 September 2017

Tujuan dari penelitian ini adalah untuk mengkaji mekanisme reaksi asetalisasi 2-
hidroksibenzaldehida yang dilindungi oleh gugus MEM menggunakan katalis asam klorida dengan
metode ab initio. Metode ab initio adalah metode komputasi yang diperoleh langsung dari hasil
perhitungan tanpa adanya data percobaan. Mekanisme reaksi yang diperoleh akan
menggambarkan bagaimana interaksi molekul substrtat, metanol, katalis HCl, dan gugus MEM
serta perubahan energi yang terjadi selama reaksi berlangsung. Selain itu kajian mekanisme reaksi
dapat memberikan usulan tahapan reaksi yang paling mungkin berdasarkan perhitungan energi
teroptimasinya.

Metode Penelitian
Bahan dan alat
Bahan yang digunakan pada perhitungan ini adalah software HyperChem versi 8.0 untuk Windows
7 professional 64-bit. Basis set yang digunakan untuk menghitung adalah 3-21G dan 6-31G* untuk
semua atom C, O, H, dan Cl. Algoritma yang digunakan adalah Polak-Ribiere (Conjugate Gradient)
dengan 32767 maximum cycles. Visualisasi hasil perhitungan dilakukan menggunakan perangkat
lunak HyperChem versi 8.0 dan ChemDraw versi 8.0. Sedangkan alat yang digunakan adalah
seperangkat komputer dengan spesifikasi Intel (R) core (TM) i3-6100T, CPU 3.20 GHz, Random
Acces Memory 4.00 GB dengan System type 64-bit Operating System.
Perhitungan komputasi mekanisme reaksi
Perhitungan komputasi dilakukan untuk menghitung optimasi geometri dari molekul sehingga
diperoleh energi minimumnya. Perhitungan optimasi geometri dilakukan melalui beberapa tahapan
yaitu:
1. Molekul sampel dimodelkan melalui toolbar draw. Kemudian dipilih dua kali atau memilih
default element pada menubar build untuk memunculkan SPU. Selanjutnya dipilih atom-
atom yang diinginkan dan menghubungkannya satu per satu untuk membentuk molekul.
2. Diubah gambar molekul dari 2D menjadi 3D dengan memilih menu invoke model builder.
Setelah itu dihitung energi molekul dengan memilih menu Setup, Ab-Initio dan memilih
basis set small (3-21G) atau medium (6-31G*).
3. Menu compute dipilih, kemudian geometry optimization untuk menghitung optimasi
geometri. Nominal 32767 ditulis pada kotak dialog maximum cycles, dipilih OK dan
ditunggu hingga converged = yes (tertera pada status bar).
4. Energi hasil optimasi yang diperoleh dikonversi dalam satuan kJ/mol. Persamaan berikut
digunakan untuk menentukan perubahan energi pada tiap tahapan reaksi: E produk – E Substrat
5. Setelah semua energi hasil optimasi molekul diperoleh, grafik koordinat reaksi vs energi
digambar menggunakan software ChemDraw.

Hasil Penelitian dan Pembahasan

Usulan Mekanisme reaksi asetalisasi 2-hidroksi benzaldehida dengan proteksi gugus MEM
(methoxy-ethoxy-methyl)
Perhitungan mekanisme reaksi asetalisasi 2-hidroksibenzaldehida yang dilindungi oleh
gugus MEM dilakukan untuk memperoleh usulan tahapan mekanisme reaksi yang paling mungkin
berdasarkan hasil perhitungan energi optimasinya. Hasil perhitungan mekanisme reaksi keadaan
antara disajikan pada Tabel 1, dimana setiap molekul memiliki jumlah molekul yang sama sehingga
energi totalnya dapat dibandingkan.

Tabel 1. ∆E Mekanisme reaksi asetalisasi 2-hidroksi benzaldehida menggunakan gugus pelindung

methoxy-ethoxy-methyl.
No Nama ∆E
3-21G (kJ/mol) 6-31G* (kJ/mol)
0 Titik Nol (2-OH Bz + HCl + 2MeOH + MEM-Cl + 0 0

420
 chemosensors

Review
Nanostructured Semiconducting Metal Oxide Gas
Sensors for Acetaldehyde Detection
Ali Mirzaei 1, * , Hyoun Woo Kim 2,3, *, Sang Sub Kim 4, * and Giovanni Neri 5, *
1 Department of Materials Science and Engineering, Shiraz University of Technology, Shiraz 71557-13876, Iran
2 The Research Institute of Industrial Science, Hanyang University, Seoul 04763, Korea
3 Division of Materials Science and Engineering, Hanyang University, Seoul 04763, Korea
4 Department of Materials Science and Engineering, Inha University, Incheon 22212, Korea
5 Department of Engineering, University of Messina, 98166 Messina, Italy
* Correspondence: mirzaei@sutech.ac.ir (A.M.); hyounwoo@hanyang.ac.kr (H.W.K.); sangsub@inha.ac.kr
(S.S.K.); gneri@unime.it (G.N.)




Received: 26 August 2019; Accepted: 8 November 2019; Published: 13 November 2019


Abstract: Volatile organic compounds (VOCs) are among the most abundant air pollutants. Their
high concentrations can adversely affect the human body, and therefore, early detection of VOCs is of
outmost importance. Among the different VOCs, in this review paper we have focused our attention
to the monitoring of acetaldehyde by chemiresistive gas sensors fabricated from nanostructured
semiconducting metal oxides. These sensors can not only provide a high sensing signal for detection
of acetaldehyde but also high thermal and mechanical stability along with a low price. This review
paper is divided into three major sections. First, we will introduce acetaldehyde as an important VOC
and the importance of its detection. Then, the fundamentals of chemiresistive gas sensors will be
briefly presented, and in the last section, a survey of the literature on acetaldehyde gas sensors will be
presented. The working mechanism of acetaldehyde sensors, their structures, and configurations are
reviewed. Finally, the future development outlook and potential applications are discussed, giving
a complete panoramic view for researchers working and interested in acetaldehyde detection for
different purposes in many fundamental and applicative fields.

Keywords: acetaldehyde; chemiresistive gas sensor; nanostructured metal oxide; sensing mechanism

1. Introduction
By definition, volatile organic compounds (VOCs) are organic compounds with a low boiling
point, (50–100 ◦ C to 240–260 ◦ C) and with saturation vapor pressures higher than 102 kPa at 25 ◦ C [1].
They are air pollutants and mostly are emitted from industrial factories and vehicles. They accelerate
the formation of secondary organic aerosols, and under oxidized conditions, they will convert them
to particles [2]. Accordingly, they cause different environmental problems and also have detrimental
effects on human health [3].
Aldehydes are a class of VOCs that are highly reactive and odorous. They are one of the most
common sources of pollution in air because they are not only used in many chemical adhesives
such as cigarette adhesives [4] but also are produced in many industrial processes or incomplete
combustions [5]. In particular, they can be formed as a product of incomplete wood combustion in
fireplaces and woodstoves, pulp and paper factories, internal combustion engines and turbines, and
vehicle exhaust fumes [6]. Formaldehyde (HCHO) and acetaldehyde (CH3 CHO) are considered two of
the most important aldehydes [7,8]. They are known as carcinogenic and probably carcinogenic agents,
respectively [9,10].

Chemosensors 2019, 7, 56; doi:10.3390/chemosensors7040056 www.mdpi.com/journal/chemosensors

 Chemosensors 2019, 7, x FOR PEER REVIEW  2  of  16 
Chemosensors 2019, 7, 56 2 of 16
of the most important aldehydes [7,8]. They are known as carcinogenic and probably carcinogenic 
agents, respectively [9,10]. 
Acetaldehyde, with the systematic name of ethanal [11], is a small molecule comprising of
Acetaldehyde, with the systematic name of ethanal [11], is a small molecule comprising of only 
only four hydrogen atoms, two carbon atoms and one oxygen atom with a low molecular weight
four hydrogen atoms, two carbon atoms and one oxygen atom with a low molecular weight (44.05 
(44.05 g/mol) [12], as shown in Figure 1. It has an aroma like oranges, low boiling point (20.2 ◦ C),
g/mol) [12], as shown in Figure 1. It has an aroma like oranges, low boiling point (20.2 °C), and high 
and high solubility in water and lipids [13]. The indoor sources of acetaldehyde include laminates,
solubility in water and lipids [13]. The indoor sources of acetaldehyde include laminates, building 
building materials, wood ceilings, wooden varnished, etc., while its outdoor sources include power
materials, wood ceilings, wooden varnished, etc., while its outdoor sources include power plants, 
plants, wood, trash, oil and gas extraction, cement kilns, refineries, and automobile exhausts [14]. It
wood, trash, oil and gas extraction, cement kilns, refineries, and automobile exhausts [14]. It is also 
isthe most abundant carcinogen of tobacco smoke [15]. Acetaldehyde is widely employed to produce 
also the most abundant carcinogen of tobacco smoke [15]. Acetaldehyde is widely employed to
produce acetic acid, acetate esters, pentaerythritol, and pyridine bases [16]. In addition, it is used in
acetic acid, acetate esters, pentaerythritol, and pyridine bases [16]. In addition, it is used in the dairy 
the dairy industry as a synthetic flavoring component and food additive [17].
industry as a synthetic flavoring component and food additive [17]. 

 
Figure 1. Structure of acetaldehyde. 
Figure 1. Structure of acetaldehyde.

Acetaldehyde is also a highly toxic compound [18]. The

Acetaldehyde is also a highly toxic compound [18]. effects of acetaldehyde on the human
The effects of acetaldehyde on the human 
body include eye irritation, headache, vomiting, liver diseases, and detrimental effects on the throat,
body include eye irritation, headache, vomiting, liver diseases, and detrimental effects on the throat, 
skin, and the respiratory tract [19–21]. In particular, because of the pungent odor of acetaldehyde,
skin, and the respiratory tract [19–21]. In particular, because of the pungent odor of acetaldehyde, it 
itis isextremely 
extremelyirritating 
irritatingat 
atconcentrations 
concentrationsabove 
above50  50 ppm 
ppm [14]. 
[14]. In 
In addition, 
addition, it 
it can 
can be
be  aa cause
cause ofof sick
sick 
building syndrome, so-called SBS, even at ppb levels [22,23]. Acetaldehyde has a strong electrophilic
building syndrome, so‐called SBS, even at ppb levels [22,23]. Acetaldehyde has a strong electrophilic 
nature and can damage DNA in humans, and it is considered as a possible human carcinogen [24,25].
nature and can damage DNA in humans, and it is considered as a possible human carcinogen [24,25]. 
Furthermore, it can easily react with Vitamin B1, leading to B1 deficiency. Accordingly, it can cause
Furthermore, it can easily react with Vitamin B1, leading to B1 deficiency. Accordingly, it can cause 
mental illness, visual disturbances, and poor memory in human beings. To avoid such problems,
mental illness, visual disturbances, and poor memory in human beings. To avoid such problems, 100 
100 ppm as a permissible exposure limit of acetaldehyde has been proposed [26].
ppm as a permissible exposure limit of acetaldehyde has been proposed [26]. 
Acetaldehyde is present in both indoor and outdoor environment and its detection is therefore
Acetaldehyde is present in both indoor and outdoor environment and its detection is therefore 
very important for monitoring environmental and domestic pollution. For monitoring acetaldehyde,
very important for monitoring environmental and domestic pollution. For monitoring acetaldehyde, 
conventional analytical techniques, such as gas chromatography, are widely used but they are bulky,
conventional analytical techniques, such as gas chromatography, are widely used but they are bulky, 
time
time consuming
consuming  and expensive.
and  Accordingly,
expensive.  Accordingly, compact, robust,
compact,  and inexpensive
robust,  solid-state
and  inexpensive  gas sensors
solid‐state  gas 
are required. Among the others, conductometric solid-state gas sensors represent an effective alternative.
sensors are required. Among the others, conductometric solid‐state gas sensors represent an effective 
Although
alternative.  semiconducting oxide-based chemoresistors
Although  semiconducting  oxide‐based are characterized by
chemoresistors  are high-sensitivity,
characterized  often the
by  high‐
low selectivity
sensitivity,  limits
often  the their
low practical use.
selectivity  Then,
limits  duepractical 
their  to scientific
use. and practical
Then,  importance,
due  to  a survey
scientific  and  of
practical 
literature on acetaldehyde chemoresistive gas sensors will be presented and discussed.
importance, a survey of literature on acetaldehyde chemoresistive gas sensors will be presented and 
discussed. 
2. Chemiresistive Gas Sensors
2. Chemiresistive Gas Sensors 
Nowadays, gas sensors are widely utilized in different areas including public safety, industrial
processes, domestic safety, underground mining, and monitoring of environmental pollution and
Nowadays, gas sensors are widely utilized in different areas including public safety, industrial 
air quality in vehicles [27]. So far, different types of gas sensors such as surface acoustic wave [28],
processes, domestic safety, underground mining, and monitoring of environmental pollution and air 
optical [29], gasochromic [30], thermoelectric [31], electrochemical [32]. and chemiresistive [33–35] gas
quality in vehicles [27]. So far, different types of gas sensors such as surface acoustic wave [28], optical 
sensors for detection[30], 
[29],  gasochromic  of VOCs have been[31], 
thermoelectric  introduced. Among them,
electrochemical  chemiresistive
[32].  and  chemiresistive gas sensors
[33–35] are
gas 
very popular owing to their high sensitivity, short response time, high stability, reproducibility, simple
sensors for detection of VOCs have been introduced. Among them, chemiresistive gas sensors are 
fabrication and owing 
very  popular  operation, and low
to  their  cost
high  [36–38]. Chemiresistive
sensitivity,  short  response gas sensors,
time,  high in which the
stability,  resistance of
reproducibility, 
the sensing layer changes upon exposure to the target gas, were introduced for the
simple  fabrication  and  operation,  and  low  cost  [36–38].  Chemiresistive  gas  sensors,  in  first time about
which  the 
sixty years ago [39]. Depending on the increase or decrease of the resistance and the magnitude of
resistance of the sensing layer changes upon exposure to the target gas, were introduced for the first 
the resistance
time  change,
about  sixty  the
years  gas[39]. 
ago  typeDepending 
and its concentration can beor 
on  the  increase  estimated
decrease [40,41]. In chemiresistive
of  the  resistance  and  the 
gas sensors, surface area, morphology, chemical composition, and sensing temperature
magnitude of the resistance change, the gas type and its concentration can be estimated [40,41]. In  are the main
factors affecting the
chemiresistive  gas gas responsesurface 
sensors,  [42,43]. area,  morphology,  chemical  composition,  and  sensing 
temperature are the main factors affecting the gas response [42,43]. 
ARTICLE
Received 12 May 2015 | Accepted 23 Jun 2015 | Published 6 Aug 2015 DOI: 10.1038/ncomms8880 OPEN

Mode-selective vibrational modulation of charge

transport in organic electronic devices
Artem A. Bakulin1,2,*, Robert Lovrincic3,4,*, Xi Yu3,*, Oleg Selig1, Huib J. Bakker1, Yves L.A. Rezus1,
Pabitra K. Nayak3,w, Alexandr Fonari5, Veaceslav Coropceanu5, Jean-Luc Brédas6 & David Cahen3

The soft character of organic materials leads to strong coupling between molecular, nuclear
and electronic dynamics. This coupling opens the way to influence charge transport in organic
electronic devices by exciting molecular vibrational motions. However, despite encouraging
theoretical predictions, experimental realization of such approach has remained elusive. Here
we demonstrate experimentally that photoconductivity in a model organic optoelectronic
device can be modulated by the selective excitation of molecular vibrations. Using an ultrafast
infrared laser source to create a coherent superposition of vibrational motions in a
pentacene/C60 photoresistor, we observe that excitation of certain modes in the
1,500–1,700 cm  1 region leads to photocurrent enhancement. Excited vibrations affect
predominantly trapped carriers. The effect depends on the nature of the vibration and its
mode-specific character can be well described by the vibrational modulation of intermolecular
electronic couplings. This presents a new tool for studying electron–phonon coupling and
charge dynamics in (bio)molecular materials.

1 FOM Institute AMOLF, Science Park 104, 1098 XG Amsterdam, The Netherlands. 2 Cavendish Laboratory, University of Cambridge, JJ Thomson Avenue,

Cambridge CB3OHE, UK. 3 Department of Materials and Interfaces, Weizmann Institute of Science, Rehovot 76100, Israel. 4 IHF, TU Braunschweig, and
Innovationlab, Speyerer Strasse 4, 69115 Heidelberg, Germany. 5 School of Chemistry and Biochemistry, and Center for Organic Photonics and Electronics,
Georgia Institute of Technology, 901 Atlantic Drive NW, Atlanta, Georgia 30332-0400, USA. 6 Solar & Photovoltaics Engineering Research Center, King
Abdullah University of Science and Technology, Thuwal 23955-6900, Kingdom of Saudi Arabia. * These authors contributed equally to this work. w Present
address: Clarendon Laboratory, University of Oxford, Oxford OX1 3PU, UK. Correspondence and requests for materials should be addressed to A.A.B.
(email: aab58@cam.ac.uk) or to D.C. (email: david.cahen@weizmann.ac.il).

NATURE COMMUNICATIONS | 6:7880 | DOI: 10.1038/ncomms8880 | www.nature.com/naturecommunications 1

& 2015 Macmillan Publishers Limited. All rights reserved.
ARTICLE
T
he soft character of organic materials strongly influences
their electronic functionality1,2. In these systems charge
hopping and electronic delocalization are determined by
the overlap of the molecular orbitals and, therefore, is highly
sensitive to minor changes in molecular geometry. Hence, the
electronic properties of organic materials are largely determined
by the interplay between the electronic and nuclear dynamics
of the molecules, referred to as vibronic coupling phenomena.
A growing number of interdisciplinary studies show that
vibronic effects lie at the heart of a diverse class of effects in
physics, chemistry and biology—from nonlinear behaviour of
molecular junctions2 to photophysics of vision3, conformational
reorganization4 and even olfactory reception5. Vibrational
motions have been postulated to regulate the interaction
between different molecular electronic states by modulating
inter- and intra-molecular couplings, by donating or accepting
extra energy quanta5,6, and by suppressing7 or promoting8
quantum interference phenomena.
Vibronic effects were also shown to be fundamentally
important for the conductivity of organic materials.
Vibrational motions influence intermolecular electron tunnelling
probabilities9–11 and govern a variety of non-equilibrium
phenomena such as local heating12, switching2, hysteresis and
electronic decoherence7,13. This makes vibrational excitation a
promising tool for spectroscopy of molecular junctions12,14,
tracking charge transfer processes in organic and bio-electronic
systems, and, more generally, for the development of electronic
devices. For example, remarkable opportunities for organic
electronics would arise from the possibility to control charge
transport, and, thus, affect device performance by coherently
driving nuclear motions along a pre-selected reaction coordinate
trajectory. However, despite many encouraging theoretical
predictions15–17, the experimental realization of vibrationally
driven electronics is still elusive due to the complexity of selective
control of nuclear motions in an actual electronic junction.
Until now, vibration-associated charge dynamics in organic
electronic devices has been only engaged with approaches that do
not include mode selectivity. For example, the density and the
equilibrium population of vibrational states have been varied via
chemical synthesis of molecules with different bond structures13
and via thermal population of low-frequency vibrations7.
However, in principle, it should be possible to access
particular non-equilibrium nuclear or vibronic states by using
instrumentation of optical time-resolved techniques, such as
visible pump–probe3,6,18, time-resolved stimulated/impulsive
Raman19,20 or transient infrared absorption21. For example, for
inorganic perovskite materials, molecular Mott insulators22 and
organometallic donor–bridge–acceptor systems23,24 it has been
reported that selective infrared excitation can lead to strong
modulation of the electronic properties. Sophisticated all-optical
two-dimensional photon echo techniques are even capable of
guiding a molecular system through a desired quantum
superposition of vibronic/vibrational states8,25–28. Although
such spectroscopic methods provide a comprehensive approach
for probing and controlling molecular motions, and have been
applied to model systems such as molecular thin films or
solutions, they have not yet been employed to influence charge
transport in functional electronic (nano)devices.
In this work, we combine device characterization and ultrafast
spectroscopy methods to experimentally demonstrate that the
performance of an organic optoelectronic system can be
modulated by selectively exciting vibrational modes of the
molecules involved in charge transport. As model system we
use pentacene/C60 bilayer photoresistors. Our experimental
approach is based on the interferometric extension of the
pump–push photocurrent (PPP) technique. In this work,
2 NATURE COMMUNICATIONS | 6:7880 | DOI: 10.1038/ncomms8880 | www.nature.com/naturecommunications
& 2015 Macmillan Publishers Limited. All rights reserved.
NATURE COMMUNICATIONS | DOI: 10.1038/ncomms8880
we extend the PPP method, using the recent progress in ultrafast
interferometry28,29 that allows for a precise control over the
time/frequency-domain structure of the infrared optical pulses.
We apply a sequence of ultrafast mid-infrared laser pulses to
create a coherent superposition of molecular vibrational motions
inside the active layer of a device and correlate this excitation with
the device performance.
Results
Optoelectronic characterization of model device. Figure 1a–c
describes the organic bilayer photoresistor model system. The
active layer of the device consists of polycrystalline pentacene
(70 nm) and fullerene C60 (15 nm) films (Fig. 1a, Supplementary
Fig. 1), thermally evaporated on top of 3-, 5- or 10-mm spaced
electrodes arranged in a comb-like geometry on a SiO2 substrate
(Fig. 1b). We chose this geometry rather than a sandwich-like
structure, typical for photodiodes or solar cells, to improve the
access of mid-infrared pump pulses to the active layer. Adding
the C60 layer was critical to enhance the photocarrier generation
in the film30.
Figure 1d compares the absorption spectra of pentacene and
C60 in the infrared vibrational fingerprint region and in the region
of the optical electronic transitions. C60 shows several distinct
vibrational modes at 1,180, 1,430 and 1,540 cm  1 and has a
comparably low optical density in the visible. Pentacene has a rich
spectrum of vibrational lines in the infrared and also shows
strong excitonic absorption features at frequencies above
14,500 cm  1 (690 nm). According to the density functional
theory calculations, the strong infrared peaks at 1,300 and
1,345 cm  1 are mostly associated with C ¼ C stretching
vibrations along the short axis of pentacene, while the weaker
high-frequency vibrations correspond to atomic motions mostly
aligned with the long axis of the molecule (see Supplementary
Fig. 2).
The dark I–V curves of the devices are symmetric and roughly
linear, indicating good hole injection from the gold electrodes to
the pentacene layer (see Supplementary Fig. 3). On exposure to
visible light, the current flow through the devices strongly
increases (approximately three times under 10 mW cm  2
illumination). Devices without a C60 layer demonstrated only
negligible photoconductivity, which indicates that singlet (and
triplet)30 excitons generated after pentacene excitation are
dissociating at the pentacene/C60 interface and that the charge
generation proceeds through the interfacial charge transfer
states31. Owing to the large electron injection barrier at the
pentacene/Au interface, the dark current is mostly provided by
holes, while under illumination both holes and electrons
contribute to the photocurrent. Unlike in a typical solar cell,
both electrodes are placed below the pentacene films. Therefore,
electrons and holes have to pass through the pentacene, which is
known to lead to extremely long (up to seconds) extraction times
of electrons residing in low-lying trap states in pentacene32. This
notion is confirmed by the dependence of the photocurrent on
the light-modulation frequency (Fig. 1e). Cole–Cole analysis of
this dependence shows a typical time constant 42 ms, which we
interpret as the lifetime of long-lived electronic charge carriers.
Pump–push photocurrent measurements. In a PPP experiment,
an optoelectronic device is illuminated by a sequence of laser
pulses interacting with the active material in the device. The result
of these interactions is detected by observing the variations in the
current flow through the device as a function of time delay
T between the pump and push pulses and their spectra. Thus,
PPP combines the sensitivity and device relevance of electronic
methods with the excitation selectivity and ultrafast time
Semi empirical insights into the electronic structure of an isatin
derived bis Schiff base

Zahid Khan1*, Zahida Tasneem Maqsood1 and Asad Tanoli1

1
Department of Chemistry, University of Karachi, Karachi, Pakistan

Abstract: Schiff bases are versatile organic compounds and are widely studied for their broad range of biological
applications. Extensive experimental data is available on these compounds but theoretical aspects are not
comprehensively studied so far. This paper reports quantum mechanical calculation of a Schiff base to theoretically
explore the electronic structure. Semi empirical (Austin Model 1, and Parametric Method 3) methods were employed to
predict the optimized geometry and calculate various electronic properties e.g. IR vibrations, frontier molecular energy
levels, total energies, dipole moments and some thermo chemical properties.

Keywords: Computational Chemistry, semi empirical calculation, Schiff base.

INTRODUCTION accurate results when applied to chemical species similar

Schiff bases are remarkable organic compounds and
frequently reported for variety of important biological
properties including anticancer, antibacterial, antifungal,
enzyme inhibition and herbicidal activities (Khan et al.,
2009). The azomethine group, rich in electron density
render these compounds to be promising ligands from
coordination chemistry standpoint and a number of
coordination complexes have also been reported with
broad range of biological applications (Papishet al., 2006;
Patel, Parekh, & Patel, 2005; Raman, Kulandaisamy,
Thangaraja, & Jeyasubramanian, 2003). A theoretical
analysis of the candidate compound can so become
valuable to predict certain properties and potential
binding sites to give supplementary insights into the
electronic structures of the candidate compound.
Substantial experimental data is available for these
compounds i.e. Schiff bases, but theoretical perspectives
are not much explored yet. This fact prompted us to
conduct theoretical exploration of the electronic structure
of these compounds. In present communication we report
the quantum mechanical AM1 and PM3 electronic
structure calculations of an isatin derived bis Schiff base,
“2-hydroxybenzaldehyde-N-(2-oxo-1,2-dihydro-3H-
indol-3-ylidene) hydrazone”.
to those used in the process of parameterization (Stewart,
1989a, 1989b). Although semi empirical methods are
based upon approximations, yet they are efficiently used
to calculate the wave function and energy to predict other
properties like heats of formation, force constant,
molecular geometry, population analysis, conformational
analysis, chemical reaction pathways, prediction of
spectral information and transition states etc. (Krossing &
Slattery, 2006; McIver & Komornicki, 1971; Stewart,
1989a).
Latest semi empirical models like AM1 and PM3 are
based on NDDO (neglect diatomic differential overlap)
method which allow the use of a simpler HF equation |H-
E|=0 in replacement of secular Hartree-Fock equation |H-
ES|=0. These methods are very popular and used by
various workers for rapid estimation of molecular
properties and have been recently extended to embrace
many elements, including some transition metals. The
Austin Model 1 (AM1 by Dewar and co-workers) was
largely parameterized based on a small number of atomic
data, while Parametric Method 3, (PM3 by James
Stewart) is parameterized in such a way that it can
reproduce a large number of molecular properties
(Krossing & Slattery, 2006; McIver & Komornicki,
1971).

The ab-Initio methods are computationally very MATERIALS AND METHODS

expensive in their application for medium to large sized
chemical systems. Semi empirical approach effectively
address this limitation of the Hartree-Fock calculation
either by omitting or parameter zing some integrals
centered on experimental data, such as dipole moments or
ionization energies(Arora & Kumar, 2001). Therefore
semi empirical calculations are exceedingly fast,
applicable to large molecules and often come up with near
*Corresponding author: e-mail: zahid@chemuok.edu.pk
Pak. J. Pharm. Sci., Vol.29, No.6, November 2016, pp.2059-2063
All computations were performed on a 64 bit Intel based
computer with 1.7 GHz Quad Core 4005U CPU and 4.0
GB of physical memory. Molecular modeling of six
slightly different starting geometries and MM (using
Merck Force Field - MMFF94) conformational search
was performed using Avogadro version 1.1.1 program
(Hanwell et al., 2012). The lowest energy conformations
for each starting geometry was optimized by semi-
empirical AM1 and PM3 Hamiltonians implemented by
2059
 THE JOURNAL OF CHEMICAL PHYSICS 122, 234509 !2005"

Hydrogen bonding in ethanol under shear

Janka Petravica!
Research School of Chemistry, Australian National University, Canberra ACT 0200, Australia
Jerome Delhommelle
Department of Chemical Engineering, Vanderbilt University, Nashville Tennessee 37235-1604
!Received 14 March 2005; accepted 29 April 2005; published online 22 June 2005"

We study the dependence of viscosity of ethanol on shear rate using constant volume and constant
pressure nonequilibrium molecular dynamics simulations, with the emphasis of the interrelationship
between breaking, stability, and alignment of hydrogen bonds and shear thinning at high shear rates.
We find that although the majority of hydrogen bond breakings occur at low shear rates, we do not
observe shear thinning until there is some shear-induced alignment of the hydrogen bonds with the
direction of shear. © 2005 American Institute of Physics. #DOI: 10.1063/1.1940050$

INTRODUCTION between the experimental and simulation viscosities are only

quantitative, with the correct qualitative trends resulting
In hydrogen-bonding liquids, the structures formed by a from correct description of structural changes, we calculate
hydrogen bond network determine, to a large part, their dy- viscosity under a range of shear rates ! !from 0.0025 to
namics and transport properties. The influence of hydrogen 0.2 ps−1" at ambient conditions. We relate the observed
bonds on the diffusion coefficient of simple polar liquids like trends to the dependence of hydrogen-bonded structures and
monohydric alcohols has been studied in depth both in their lifetimes on shear rate.
experiments1,2 and in simulations.3–6 The molecular simula-
tion studies of their behavior under shear have been more
scarce, with the observance of shear thinning in water7,8 and I. MODEL AND SIMULATION DETAILS
methanol8 for shear rates exceeding 0.01 ps−1. In the one
simulation study that addressed hydrogen bonding,7 the The OPLS potential for ethanol9 is a united atom model
three-dimensional tetrahedral hydrogen-bond network of wa- in which methyl and methylene groups are treated as single
ter was found to weaken and disrupt by shearing, with some Lennard-Jones !LJ" sites. The hydroxyl group is represented
shear-induced alignment at increased shear rates. The degree by a single LJ site located on the oxygen atom and two
of alignment was weaker and occurred at higher shear rates partial charges located on the oxygen and hydrogen atoms.
than in long-chain alkanes. The reason for this was assumed An additional charge is placed on the carbon bonded to the
to be that the existence of the hydrogen bonding sites op- hydroxyl group in order to satisfy the neutrality of the mol-
posed the partial ordering of molecules in the shear plane ecule. Interactions between unlike LJ sites are described by
responsible for shear thinning. geometric combining rules for both LJ parameters " and #.
Equilibrium monohydric alcohols form hydrogen Nonbonded interaction parameters are given in Table I.
bonded chains with a small amount of branching, i.e., essen- Bond lengths and bond angles are fixed !dCH3-CH2
tially one-dimensional structures.9,10 We investigate the im- = 1.53 Å , dCH2-O = 1.43 Å, and dO-H = 0.945 Å". From the me-
pact of the structure of the chains and the dynamics of the chanical point of view, the ethanol molecule in this model
hydrogen bond formation on the rheology of ethanol. consists of two fixed triangles, a LJ C–C–O triangle and an
We use the OPLS model of ethanol9 because of its abil- electrostatic C–O–H triangle, where the dihedral angle $ be-
ity to accurately predict the thermodynamic properties of tween them can change according to the torsion potential,
pure ethanol under a wide range of conditions, and a satis- V!$" = 21 #V1!1 + cos $" + V2!1 − cos 2$"
factory description of structural properties and hydrogen
bonding in liquid ethanol,9–12 all at a favorable balance be- + V3!1 + cos 3$"$, !1"
tween atomic detail and computational cost. The main defi- −1
with V1 = 3.489 kJ mol , V2 = −0.4853 kJ mol , −1
and V3
ciency of the model is that it underestimates the experimental = 3.125 kJ mol−1.
liquid densities at temperatures and pressures close to ambi-
ent, which is the main reason why it overestimates the diffu- TABLE I. OPLS parameters for ethanol.
sion coefficient.10
We first evaluate its ability to reproduce experimental "!Å" # !kJ/ mol" q !e"
values of equilibrium viscosity at different temperatures
CH3 3.905 0.7322 0.0
along the ambient 0.1 MPa isobar. Assuming the differences
CH2 3.905 0.4937 0.265
O 3.070 0.7113 −0.700
a"
Present address: School of Chemistry, The University of Sydney, Australia. H 0.0 0.0 0.435
Electronic address: janka@chem.usyd.edu.au

0021-9606/2005/122"23!/234509/5/$22.50 122, 234509-1 © 2005 American Institute of Physics

Downloaded 03 Jul 2006 to 129.94.6.28. Redistribution subject to AIP license or copyright, see http://jcp.aip.org/jcp/copyright.jsp
 World Journal of Pharmaceutical Research
Rao. SJIF Research
World Journal of Pharmaceutical Impact Factor 8.074

Volume 8, Issue 9, 511-531. Review Article ISSN 2277– 7105

A MINI REVIEW ON COMPUTATIONAL STUDY OF

TAUTOMERISM IN BETA- LACTAM ANTIBIOTICS BY AUSTIN
MODEL-1(AM1) METHOD

Dr. Bojja Rajeshwar Rao*

Senior Chemist (Retired), Chemical Division, Kakatiya Thermal Power Project (O&M)
Chelpur-506 170, Telangana State, India.

Article Received on
27 May 2019,
Revised on 18 June 2019,
Accepted on 09 July 2019
DOI: 10.20959/wjpr20199-15475
*Corresponding Author
Dr. Bojja Rajeshwar Rao
Senior Chemist (Retired),
Chemical Division,
Kakatiya Thermal Power
Project (O&M) Chelpur-506
170, Telangana State, India.
KEYWORDS: AM1, lactam, lactim, enol, tautomerism, benzylpenicillin, methicillin,
phenethicillin, cephapirin, induction effect.
ABSTRACT
The geometry, conformation, electronic structure of beta-lactam
antibiotics i.e. benzylpenicillin, methicillin, phenethicillin, cephapirin
and their tautomers have been optimized and calculated in the gas
phase by semi-empirical molecular orbital AM1 method usually
considering an isolated molecule, which is surrounded by vacuum. The
mechanism of tautomerism in beta-lactam antibiotics have been
studied by comparison of the different positions of net charges at
hetero- atoms in the molecule. Further, the heats of formation (∆Hfo),
dipole moment (µ), ionization potential (IP), full atomic charges and
energies of frontier molecular orbitals (EHOMO and ELUMO) have been
performed and their stable conformations have also been evaluated.

1. INTRODUCTION
The importance of β-lactam antibiotics contributes a potent and rapid bactericidal action
against the growth phase of bacteria and also very low toxic adverse reactions in the host.[1,2,3]
Benzylpenicillin has been recognized as first antibiotic in chemotherapy for the treatment of
infections caused by most species of Gram-positive bacteria.[4,5] Methicillin is useful for
treatment of severe staphylococcal infections, such as septicaemia, endocarditis, pneumonia,
meningitis, osteomyelitis and septic arthritis.[6] It inhibits the growth of both penicillin
susceptible and penicillinase-producing staphylococci.[7] Phenethicillin (Broxil) has been
used most widely against gram-positive bacteria and readily absorbed into the blood stream

www.wjpr.net Vol 8, Issue 9, 2019. 511

Rao. World Journal of Pharmaceutical Research

where it is partially bound to plasma proteins in both animals and humans.[8] It has a high
order of selective toxicity to micro-organisms which are pathogenic to human beings without
obvious side effects.[9] Cephapirins were isolated from Cephalosporium spp. or prepared
semi-synthetically. The cultures of C. acremonium inhibited the growth of a wide variety of
gram-positive and gram-negative bacteria.[10] It is assumed that dipolar character of the drug
could improve oral absorption.[11]

Austin Model-1 (AM1) is one of the semi-empirical quantum calculations based on the
neglect of differential diatomic overlap integral approximation[12,13], which includes
experimental parameters and extensive simplification of the Schrodinger’s equation
(HΨ=EΨ) to optimize molecules with a view to predict various properties of molecules and
solve chemical problems.[14] The tautomerism of beta-lactam antibiotics i.e.
benzylpenicillin.[15], methicillin[16], phenethicillin[17], cephapirin[18] were reported, with a
view to investigate their properties.

2. Tautomeric equilibrium of beta-lactam antibiotics

Theoretical investigations on tautomeric equilibrium of heterocyclic tautomerism[19] has been
fascinated much to carry out optimization of conformational analyses and electronic
properties of beta-lactam antibiotics. All tautomers are solvated to form hydrogen bonds with
the polar solvents which would affect the position of the equilibrium. Tautomeric equilibrium
is reported extensively theoretical and statistical-physical approaches.[20] It is predictable for
the study of the processes of both organic chemistry and biochemistry and the stability of
tautomers[21] and equilibrium constants in aqueous solution[22] was reported.

Present review reveals about tautomerism of β-lactam antibiotics, the mechanism of proton
shifting has been studied by comparison of the relative values of net charges at different
atoms of the molecule and evaluated the predominated tautomer. Lactam-lactim tautomerism
is involved by the shifting of hydrogen atom from nitrogen atom of lactam (-HN-C=O) group
to the oxygen atom to form lactim (-N=C-O-H) group. Keto-enol tautomerism is involved by
the shifting of hydrogen atom from α-carbon atom of keto (-HC-C=O) group to the oxygen
atom to form enol (-C=C-O-H) group and both shifts are involved in the formation of lactim-
enol form as shown in Scheme-1 to 4. The molecular geometry, conformations and electronic
properties of β-lactam antibiotics with its enol, lactim and lactim-enol systems in gas phase
usually considering an isolated molecule surrounded by vacuum have been optimized.

www.wjpr.net Vol 8, Issue 9, 2019. 512

 sensors
Review
Probe of Alcohol Structures in the Gas and Liquid
States Using C–H Stretching Raman Spectroscopy
Yuanqin Yu 1 , Wei Fan 2 , Yuxi Wang 2 , Xiaoguo Zhou 2 , Jin Sun 1 and Shilin Liu 2, *
1 Department of Physics, Anhui University, Hefei 230601, China; yyq@ahu.edu.cn (Y.Y.);
sunjin@ahu.edu.cn (J.S.)
2 Hefei National Laboratory for Physical Sciences at the Microscale, iChEM (Collaborative Innovation Center
of Chemistry for Energy Materials), Department of Chemical Physics, University of Science and Technology
of China, Hefei 230026, China; fw1008@mail.ustc.edu.cn (W.F.); wangyuxi@mail.ustc.edu.cn (Y.W.);
xzhou@ustc.edu.cn (X.Z.)
* Correspondence: slliu@ustc.edu.cn




Received: 20 May 2018; Accepted: 26 June 2018; Published: 28 June 2018


Abstract: Vibrational spectroscopy is a powerful tool for probing molecular structures and dynamics
since it offers a unique fingerprint that allows molecular identification. One of important aspects
of applying vibrational spectroscopy is to develop the probes that can characterize the related
properties of molecules such as the conformation and intermolecular interaction. Many examples of
vibrational probes have appeared in the literature, including the azide group (–N3 ), amide group
(–CONH2 ), nitrile groups (–CN), hydroxyl group (–OH), –CH group and so on. Among these
probes, the –CH group is an excellent one since it is ubiquitous in organic and biological molecules
and the C–H stretching vibrational spectrum is extraordinarily sensitive to the local molecular
environment. However, one challenge encountered in the application of C–H probes arises from
the difficulty in the accurate assignment due to spectral congestion in the C–H stretching region.
In this paper, recent advances in the complete assignment of C–H stretching spectra of aliphatic
alcohols and the utility of C–H vibration as a probe of the conformation and weak intermolecular
interaction are outlined. These results fully demonstrated the potential of the –CH chemical group as
a molecular probe.

Keywords: C–H group; vibrational probe; aliphatic alcohols; conformation; hydrogen bond

1. Introduction
Vibrational spectroscopy, including infrared and Raman spectroscopy, plays an important role
in various research fields due to its sensitivity to molecular structure and the changes in response to
external environments. Additionally, vibrational spectroscopy has many attractive characteristics such
as being non-destructive and in-situ analysis. This makes vibrational spectroscopy a valuable tool in
physics, chemistry, biology, material science, food industry, and security control [1–8]. In vibrational
spectra, it is known that the vibrational frequencies are closely correlated with the chemical bonds or
chemical functional groups, which are the fundamental units in all molecules. Therefore, one of the
important aspects of applying vibrational spectroscopy is to develop the appropriate vibrational probes
that can characterize molecular specific information such as the conformation and intermolecular
interaction. Many chemical groups have been established as vibrational probes in the literature,
including the thiocyanate group (–SCN), azide group (–N3 ), diazo group (–N2 ), the alkyne (–C≡C–),
amide group (–CONH2 ), amine group (–NH2 ), carbonyl group (–C=O), hydroxyl group (–OH),
–SH group, –CH group, and so on, as summarized in recent several reviews [9–27]. For example,
using the site-specific nitrile group (–C≡N) as a probe of protein structure, it was shown that –CN

Sensors 2018, 18, 2061; doi:10.3390/s18072061 www.mdpi.com/journal/sensors

 www.nature.com/scientificreports

OPEN Clustering mechanism of ethanol-

water mixtures investigated
with photothermal microfluidic
received: 02 December 2015
accepted: 15 March 2016 cantilever deflection spectroscopy
Published: 05 April 2016
M. S. Ghoraishi, J. E. Hawk, Arindam Phani, M. F. Khan & T. Thundat

The infrared-active (IR) vibrational mode of ethanol (EtOH) associated with the asymmetrical stretching
of the C-C-O bond in pico-liter volumes of EtOH-water binary mixtures is calorimetrically measured
using photothermal microfluidic cantilever deflection spectroscopy (PMCDS). IR absorption by the
confined liquid results in wavelength dependent cantilever deflections, thus providing a complementary
response to IR absorption revealing a complex dipole moment dependence on mixture concentration.
Solvent-induced blue shifts of the C-C-O asymmetric vibrational stretch for both anti and gauche
conformers of EtOH were precisely monitored for EtOH concentrations ranging from 20–100% w/w.
Variations in IR absorption peak maxima show an inverse dependence on induced EtOH dipole moment
(μ) and is attributed to the complex clustering mechanism of EtOH-water mixtures.

Aqueous mixtures of alcohol have been under investigation among biologists, physicists, chemists and engineers
due to its relevance in many areas such as the pharmaceutical industry, biofuels, and protein aggregation1–7.
Alcohol-water mixtures overcome limitations of the poor solubility of pure hydrophobics in water and thus, are
of particular importance in the study of protein folding and stability as well as hydrophobic solvation8–12, where
solute-solute, solvent-solvent and solvent-solute interactions play an important role. As a result, short chain alco-
hols have been used as a simple model that may facilitate understanding of more complex aqueous solutions such
as biomolecules9–13.
Of the short chained alcohols, EtOH is one of the most popular and has been studied with a variety of com-
putational and experimental techniques14–18 to include Raman (Burikov et al.)19 and NMR and FT-IR spectros-
copy (Mizuno et al.)20. EtOH consists of an equilibrium mixture of two conformers, anti and gauche, each of
which exhibits an associated absorption band in IR21,22. C-O stretch in alcohol,more appropriately considered
as C-C-O asymmetric stretch in EtOH, displays two distinguishable peaks in the 1000–1100 cm−1 region with
approximately 40 cm−1 wavenumber difference, each related to the anti and gauche conformers, respectively22,23.
The band around 1045 cm−1, due to the more favorable anti conformer, has the more intense peak among the two
bands and is often the peak referred to in studies22. Here we refer to C-O stretch as C-C-O asymmetric stretch
while investigating the absorption of both the anti and gauche conformer23.
In this letter we report on shifts in the vibrational energy peaks of EtOH water mixture experimentally
observed using micromechanical calorimetric spectroscopy using bimaterial microfluidic cantilevers (BMC). The
experimentally measured shifts in the wavenumber at IR absorption peak maxima show (1/μ) dependence. From
first principles we show that IR absorption wavenumber is proportional to (1/μ), which anticipates a nonlinear
relation between IR absorption wavenumber and concentration of EtOH as observed.
We fabricated microfluidic channels on bimaterial cantilevers (BMC) capable of holding 115 ± 1% pL of liq-
uid. We have used a quantum cascade laser (QCL) as a light source which solves the low spectral power density of
IR spectroscopy. By incorporating QCL and BMC, we were able to obtain nonlinear blue shift of C-C-O vibration
as a result of nonlinear changes in dipole moment of EtOH as predicted by molecular dynamic simulation24.
Photothermal cantilever deflection spectroscopy is based on measuring extremely small changes in thermal
energy due to absorption of infrared energy by molecules. When a molecule is illuminated by IR radiation, it
absorbs the radiation that matches the vibrational energy of the bond. This vibrational energy will be lost as heat

Department of Chemical and Material Engineering, University of Alberta, Edmonton, Canada. Correspondence
and requests for materials should be addressed to M.S.G. (email: ghoraish@ualberta.ca) or T.T. (email: thundat@
ualberta.ca)

Scientific Reports | 6:23966 | DOI: 10.1038/srep23966 1

www.nature.com/scientificreports/

Figure 1. (a) Experimental set-up to collect IR spectrum of EtOH-water mixtures, (b) cross-section of the
microchannel cantilever, (c) top view of the microchannel cantilever and (d) variation in bimaterial microfluidic
cantilevers (BMC) deflection at absorption maxima (vmax) for each concentration.

during the relaxation process. The heat generated during the relaxation process is monitored as bending of a
bimaterial cantilever. Photothermal deflection of the microchannel cantilever as a function of wavenumber pro-
vides the IR spectrum of the samples25,26.
Using Hooke’s law, the vibrational frequency of a chemical bond, where atoms and the connecting bond are
modeled as a simple harmonic oscillator, can be expressed as,

1 k
f=
2π m⁎ (1)
where, f is frequency of oscillation, k is force constant and m* is reduced mass. Frequency of oscillation is related
to wavenumber by v =  f/C, where C is wave velocity. In the presence of an electric field, E, the equilibrium posi-
tion of a molecule carrying charge dq will be shifted by dx =  Edq/k which results in the induced dipole moment
μ =  Edq2/k. As a result of change in the charge separation on the molecule, the force constant associated with
bonds in the molecule will be different. Therefore, IR light with slightly different energy (frequencies) will be
absorbed, matching to the bond stiffness change. Substituting k obtained from the induced dipole relation into
Equation (1), we can relate changes in the IR absorption wavenumber with the internal electric field in the binary
mixture as a result of polar media surrounding the analyte.

ν = (dq /2πC ) E /m⁎ 1/µ (2)

In addition, induction effects and Keesom forces in binary mixtures of water-EtOH is expected to lead to
varying molecular dipole moments of both water and EtOH as concentration changes.

Results
The IR spectra of binary mixtures of EtOH-water as concentration changes from 20–100 wt% were experimentally
collected using a BMC. The experimental setup, device schematic and normalized deflection intensity at differ-
ent concentrations are shown in Fig. 1. Each concentration was tested three times. After deconvolution of each
spectrum, using a Voigt function, the average peak maxima for both anti and gauche conformers were plotted as
a function of concentration (Fig. 2a). Deconvolution of each spectrum is provided in supplementary material,
Figs S1–S3. To compare our results with the reported results of FTIR and Raman studies, the peak maxima for
the anti conformer was normalized and plotted as a function of concentration (Fig. 2b) alongside the normalized

Scientific Reports | 6:23966 | DOI: 10.1038/srep23966 2

 International Journal of ChemTech Research
CODEN( USA): IJCRGG ISSN : 0974-4290
Vol.4, No.3, pp 983-990, July-Sept 2012

Vibrational Spectroscopy Investigation on

Aspirin Using Semi-Empirical Calculations
V Renganayaki1* S Srinivasan2 and S Suriya1
1
PG Department of Physics, D.G. Vaishnav College, Chennai 600 106
2
Department of Physics, Presidency College, Chennai 600 005,India.

*Corres.Author: renganayaki_sri@rediffmail.com

Abstract: Modern spectroscopic techniques are very effective and sensitive tools for the qualitative and
quantitative analysis of many compounds and the results are well employed in the quality control laboratories of
pharmaceutical firms. In the present work, the infrared spectroscopy is employed for the identification and
assignment of the functional groups present in the medicinally important drug namely aspirin. The present
investigation was undertaken to study the vibrational spectrum of the molecule completely and to identify the
various normal modes with great wave number accuracy. The equilibrium geometries and harmonic frequencies
of the compound aspirin were determined and analyzed using the semi-empirical methods AM1 and PM3. The
differences between the observed and calculated wave number values in the molecule were marginal.
Thermodynamic properties like entropy, heat capacity, zero point energy were calculated for the molecule.
Keywords: Aspirin, FTIR spectrum, semi-empirical, AM1, PM3.

INTRODUCTION mechanics and the computationally time-consuming

quantitative results available from ab initio methods.
Predicting and understanding the properties
When used judiciously, semi-empirical methods like
and behavior of real material systems is of great
AM1, PM3 etc. can give great insight into structure
importance both from technological and academic
and reactivity of even moderately large molecules1-5.
points of view. The theoretical problems associated
Modern spectroscopic techniques are very
with these systems are quite complex.
effective and sensitive tools for the qualitative and
Computational chemistry uses the results of
quantitative analysis of many compounds and the
theoretical chemistry, incorporated into efficient
results are well employed in the quality control
computer programs, to calculate the structure and
laboratories of pharmaceutical firms. The infrared
properties of molecules and solids. The methods are
spectroscopy is employed here for the identification
based on theories which range from highly accurate,
and assignment of the functional groups present in
but suitable for small systems, to very approximate,
medicinally important drug aspirin. Aspirin is used
but suitable for large systems. The accurate methods
in analgesics, anti-inflammatory drugs, antipyretics,
are called ab initio methods, as they are based
anticoagulants and anti-rheumatics. Acetylsalicylic
entirely on theory from first principles. The less
Acid is also known by trade name aspirin is
accurate methods, like MM1-4 methods are called
introduced in the year 1899. It has attained a leading
empirical or semi-empirical, because some
position world-wide in the prescription-free therapy
experimental results, often from atoms or related
of painful, inflammatory and feverish conditions.
molecules are used with the theory. Semi-empirical
The origin of aspirin lies in the use of the bark of the
methods represent a “middle road” between the
willow tree. The acetyl derivative of salicylic acid is
mostly qualitative results available from molecular
a white, crystalline, weakly acidic substance, with