Spectroscopy

Infrared and
Nuclear Magnetic Resonance
E le c t r ic
F ie ld
w ave
le n g
th
λ
E le c t r ic
w ave

M a g n e t ic
F ie ld
D ir e c tio n o f
M a g n e tic m o tio n o f th e
w ave lig h t b e a m

Light is an electromagnetic phenomenon.

A beam of light consists of two mutually perpendicular oscillating
fields: an oscillating electric field and an oscillating magnetic field
 Equations
c
c = νλ ν= ν =
1 ν = cν
λ λ
Larger the frequency Larger the frequency
smaller the wavelength wavenumber larger the wavenumber
frequency (ν) → number of cycles per second (units: cycles s-1 = Hertz, Hz)
wavelength (λ) → distance spanned by one cycle (units: meters, m)
Wavenumber → number of cycles in 1 cm or inverse of the wavelength in cm
(units: cm-1)
speed of light (c) → 2.99892458 x 108 m s-1 in a vacuum
Planck’s constant (h) = 6.626076 x 10-34 Joules s
The fundamental mechanism responsible for this radiation is the acceleration of a
charged particle. Whenever a charged particle undergoes acceleration, it must
radiate energy at the speed of light as packets of energy called photons. The energy
of a photon is inversely proportional to the wavelength

hc Smaller the wavelength or larger the

E= or E = hν frequency the larger the energy of the photon
λ
higher energy, greater frequency, smaller wavelength, larger wavenumber

lower energy, smaller frequency, larger wavelength, smaller wavenumber

 Spectroscopy
What is it?
Spectroscopy detects transitions between the quantized energy levels of an
atom or molecule, where the energies are due to some internal motion of the
atom or molecule. In atoms, these motions are due to the changes in the
electronic configuration. In molecules these internal motions arise from
changes in either rotations (microwave spectroscopy) vibrations (infrared
spectroscopy), electronic excitations (uv-visible and photoelectron
spectroscopy) or nuclear spin orientation (nuclear magnetic resonance).

How do we do it?
Transitions are observable by measuring discrete frequencies of electromagnetic
radiation that are absorbed or emitted by atoms or molecules.
Why do we do it?
By characterizing the energy levels of a molecule, we can describe the geometry
of that molecule, including the lengths and strengths of its bonds, the identity
and positions of its constituent atoms, the energies of its molecular orbitals, and
the overall framework and shape of the molecule.
(Chem 129 notes by Dr. B. Power. 1997)
 Regions of the electromagnetic spectrum and the types of molecular motions

C h a n g e in
C hange of C hange of C h a n g e o f E le c tr o n ic
C h a n g e in s p in n u c le a r
o r ie n t a tio n c o n f ig u r a t io n d is tr ib u tio n c o n f ig u r a t io n
N u c le a r M a g n e tic
re s o n a n c e v is ib le a n d X -ra y g a m m a ra y s
E le c tr o n s p in M ic ro w a v e s In fr a r e d u lt r a - -v io le t
re s o n a n c e

V is ib le UV
STD TV IR x -ra y s
b ro a d m ic r o w a v e s
cast g a m m a ra y s
-2
10 -3
10 1 100 104 106 108
w a v e n u m b e r (c m -1 )

10 m 100 cm 1 cm 100 m 1 m 10 nm 100 pm

w a v e le n g t h

6 8 10 12 14
3 x 10 3 x 10 3 x 10 3 x 10
12
3 x 10 3 x 10 3 x 1 0 18
fr e q u e n c y (H z )

10
-3
10
-1
10 10
3
10
5
10
7
10
9

e n e r g y (J /m o l)

lo w e n e rg y h ig h e n e r g y
 Infrared Spectroscopy

All bonds vibrate back and forth about an average bond length. This
vibrational motion is quantized δ
-O
O O

C
δ+

∆E = hν For IR need a change

in the dipole moment

e x c it e d A b s o r p t io n o f I R r a d ia t io n o n ly
s ta te s o c c u r s w h e n e n e r g y is e x a c t ly
Bond e q u a l to th e d iffe r e n c e b e tw e e n
D is s o c ia t io n o n e v ib r a t io n a l s ta t e to a n o t h e r
lo w e s t

I n te r n u c le a r D is ta n c e

For a nonlinear molecule with n atoms there are 3n-6 possible fundamental
vibrations. For example pentane (C5H12) has 45 possible infrared absorptions
 IR Vibrations Almost all inorganic or organic compounds
that have covalent bonds absorbs radiation
in the infrared region of the electromagnetic
spectrum

Only those bonds that have a dipole moment

that changes as a function of time are
Symetrical Symetrical in-plane bending
capable of absorbing infrared radiation.
Stretching (scissoring)
H2, Cl2 or CO2 do not have IR absorptions

zero dipole moment

δ- δ+ δ-
O C O
Asymetrical Asymetrical out-of-plane bending
Stretching
(twisting) no change in dipole
Most Characteristic Easiest - lowest moment and does not
energy absorb energy in the
IR region

Vibrational energies will be different between different atoms because of bond

strengths and atomic masses. Light atoms or stiffer bonds vibrate at a higher
frequency. Triple bonds are stiffer (and vibrate at higher frequencies) than
double bonds, and double bonds are stiffer (and vibrate at a higher frequency)
than single bonds.
 IR Vibrations
We can see some of these effects below. Notice that stretching frequencies of
groups involving hydrogen (a light atom) such as C-H, N-H and O-H all occur at
relatively high frequencies.
≡C-H =C-H -C-H
bond type sp-1s sp2-1s sp3-1s
Bond Frequency
Range (cm-1) length (Å) 1.08 1.11 1.12
C-H 2853-2962 strength (kJ) 506 444 422
N-H 3300-3500
IR (cm-1) 3300 3100 2900
O-H 3590-3650
C-C ~1200
C=C 1620-1680 increasing
In general, triple
bonds are
C=O 1630-1780 energy stronger than
increasing double which are
C≡C 2100-2260 frequency stronger the
C≡N 2220-1680 single bonds

Note: The energy absorbed is directly proportional to the wave number: E = hcν
 Infrared Spectroscopy
The amount of energy that is absorbs depends on the change
in the dipole moment. If there is a large change in the dipole
moment a larger amount of energy is absorbed and exhibits
strong absorption peaks. Nonpolar bonds do not absorb
infrared radiation because there is no change in the dipole
moment. Relatively nonpolar bonds like carbon-carbon bonds
absorb less energy and exhibit weak absorption peaks.
δ- O Larg dipole, strong absorption
large peak
C
δ+ C C
Small dipole weaker absorption

There are other factors that bring about absorption.

Overtones (harmonics) of fundamental absorption bands may
be seen in IR spectra even though these overtones occur with
greatly reduced intensity.
Because IR spectra contain so many peaks, the possibility
that two different compounds will have the same IR spectrum
is exceedingly small. It is because of this that an IR spectrum
has been called the “fingerprint” of the molecule.
 Characteristic Infrared Absorptions

Group Frequency Rang (cm-1) Intensity

Alkane (sp3)
C-H (stretching) 3000-2850 (m-s)
-CH3 (bend) 1450-1375 (m)
-CH2- 1465 (s)
Alkene (sp2)
C-H (stretching) 3100-3000 (m)
C=C (stretching) 1680-1600 (v)
R-CH=CH2 985-1000 (s)
(out of plane and 905-920 (s)
R2C=CH2 880-900 (s)
C-H bendings)
cis-RCH=CHR 675-730 (s)
trans-RCH=CHR 960-975 (s)
Alkyne (sp)
≡C-H (stretching) ≈ 3300 (s)
C≡C 2250-2100 (v)

abbreviations: s = strong, m = medium, w = weak, v = variable

 Characteristic Infrared Absorptions.

Group Frequency Intensity

Rang (cm-1)
Aromatic
Ar-H (stretching) 3150-3050 (very s)
Aromatic substitution type
(C-H out of plane bendings)
Monosubstituted 690-710 (very s)
and 730-770 (very s)
o-Disubstituted 735-770 (s)
m-Disubstituted 680-725 (s)
and 750-810 (very s)
and 860-900 (s)
p-Disubstituted 800-860 (very s)

abbreviations: s = strong, m = medium, w = weak, v = variable

 Characteristic Infrared Absorptions.
Group Frequency Intensity
Rang (cm-1)
Alcohols, Phenols, and Carboxylic acids
O-H (stretching)
Alcohols, phenols (dilute solutions) 3590-3650 (sharp, v)
Alcohols, phenols (hydrogen bonding) 3200-3550 (broad, s)
Carboxylic acids (hydrogen bonding) 2500-3000 (broad, v)
Ethers
C-O (stretching) 1300-1000 (m-s)
Phenyl alky ether 1250 (s)
(make sure no carbonyl peaks) and (s)
Aldehydes
C=O (stretch) 1740-1725 (s)
conjugated of carbonyl with b C=C 1700-1680 (s)
conjugated with phenyl 1700-1660 (s)
C-H 2900-2800 (w)
and 2800-2700 (w)

abbreviations: s = strong, m = medium, w = weak, v = variable

 Characteristic Infrared Absorptions.

Group Frequency Intensity

Rang (cm-1)
Ketones
C=O (stretch) 1720-1708 (s)
conjugated of carbonyl with b C=C 1700-1675 (s)
conjugated with phenyl 1700-1680 (s)
(bending) 1300-1100 (m)
Carboxylic Acids
O-H Stretch 3400-2400 (broad, v)
C=O (stretch) 1730-1700 (s)
C-O (stretch) 1320-1210 (m)
Esters
C=O (stretch) 1750-1735 (s)
conjugated of carbonyl with b C=C 1740-1715 (s)
conjugated with phenyl 1740-1715 (s)
C-O (stretch) (two or more bonds one stronger and 1300-1000 (broad, s)
broader than the other)

abbreviations: s = strong, m = medium, w = weak, v = variable

 Characteristic Infrared Absorptions

Group Frequency Intensity

Rang (cm-1)
Amides
C=O (stretch) 1680-1630 (s, v)
N-H (stretch) primary amide gives two bands near 3350 (broad, m)
and 3180 (broad, m)
N-H (stretch) secondary amide gives one band near 3300 (broad, m)
N-H (bending) 1640-1550 (broad, v)
Acid Chlorides
C=O (stretch) 1810-1775 (s)
conjugated of carbonyl with b C=C 1780-1760 (s)
C-Cl 730-550 (s)

abbreviations: s = strong, m = medium, w = weak, v = variable

 Characteristic Infrared Absorptions

Group Frequency Intensity

Rang (cm-1)
Anhydrides
C=O (stretch) 1820-1750
Amines
N-H (stretch) Primary amines have two bands. 3330-3500 (m)
Secondary amines have one band: a vanishingly
weak one for aliphatic compounds and a stronger
one for aromatic secondary amines. Tertiary
amines have no N-H strectch
N-H (bend) primary 1640-1560 (broad, m)
N-H (bend) secondary near 1500
C-N (stretch) 1350-1000
Nitriles
C≡N 2200-2260 (m)

abbreviations: s = strong, m = medium, w = weak, v = variable

 Pentane
CH3(CH2)3CH3

sp3
sp3 C-C
C-H bending
stretching ~1450

1-Pentene

sp2
sp2 C C
C-H

~3100
~1650
1-hexyne

sp
~2100
C C

~3300
 2-butanol Finger Print Region
Weaker Electro magnetic energy
needed for stretching and bending

-OH broad
hydrogen bonding
weakens the O-H
bond and causes
the absorption to shift
to lower frequency

H O
O
H O

bond strength
variable causes
broad absorption
Cholesterol

~3200
-3600
CH3(CH2)3CH2OH CH3(CH2)2CH2NH2 (CH3CH2)2NH (CH3CH2)2NCH3
1-pentanol N-Butylamine Diethylamine N,N-Diethylmethylamine
primary alcohol primary amine secondary amine tertiary amine

~3600 - 3100 ~3400 and 3300 ~3300

Diethyl ether

~1375

~1100
2-pentanone

~1725
Pentanal

~2700
~1775
~2800
Butanoic acid

~1725
 1 2

A O

ketone

B O
(CH3)2CHCH 3 4

aldehyde

C
(CH3)2C CH
alkyne

D CH3
CH3CH2C OH
CH3

alcohol
CH2 CH(CH2)3CH3 or HC C(CH2)3CH3
(CH3)2CHCH2CH2OH or (CH3)2CHCH2CO2H
CH3CH2CH CH2 or CH3CH2CH2OH
Aromatic or vinyl

Asymmetric stretch C-O-C

approx. 1200

Symmetric stretch C-O-C

approx. 1040
O 1123

Conjugation shifts
asymmetric stretch to Major peaks - 1466, 1378, 1123 cm-1
higher frequency

O O
+

Increase in double
bond character
strengthens bond O

1248
Major Peaks – 1041, 1248, 1498, 1601 cm-1
Aldehyde C-H
2860-2800 and
2760-2700 cm-1 carbonyl
overtone

Aliphatic carbonyl
1740 – 1725 cm-1 C O O
1728
Conjugated carbonyl H
1700-1660 cm-1

Major Peaks – 1728, 2716 cm-1

O
O

H H
+

More single
bond character

Lengthens bond
weaker bond H C C
less energy C O
lower wave # O 1691

Major Peaks – 1691, 2733, 2814 cm-1

 Ketone

Aliphatic carbonyl
1720 – 1708

Conjugated carbonyl C O O
1700 – 1675
1718
O
O
Major Peaks – 1718, 1359, 1169 cm-1
+

More single
bond character

Lengthens bond
weaker bond O
less energy
lower wave # C C
C O 1621
1692

Major Peaks – 1692, 1621 cm-1

 O

O
C O C O C
1739 1188 stretch

O
stronger
- shift to
higher O
energy C O
O C C
+ 1762 C O C
1649
1217 1138
O

O
weaker
- shift to
lower O
C C
energy 1639
O 1726 C O C
+ C O
1164
 O
A NH2 B
OH
O O

C H D O
1711

1461 1739 1188

2716
2817

1730

1364 1468
3290
1364
 O O
CH2 CH2 C O CH2 CH3 CH CH C O CH2 CH3

O O
CH2 CH2 C CH2 CH3 O C CH2 CH CH CH3