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Postcombustion CO2 Capture Solvent Characterization Employing

the Explicit Solvation Shell Model and Continuum Solvation Models
Mayuri Gupta,*, Eirik F. da Silva,, and Hallvard F. Svendsen

Department of Chemical Engineering, Norwegian University of Science and Technology, Trondheim 7491, Norway

Department of Process Technology, SINTEF Materials and Chemistry, Trondheim 7034, Norway
S Supporting Information

ABSTRACT: A study on the explicit and implicit solvation models for calculation of
solvation free energy of ions and pKa of amino acids presented recently [Gupta, M.; et al. J.
Chem. Theory. Comput. 2013, 9, 50215031] is extended for the study of amines and
alkanolamines. Solvation free energies and pKas of a data set of 25 amines and
alkanolamines are calculated using the explicit solvation shell (ESS) model given by da Silva
et al. [J. Phys. Chem. A 2009, 113, 6404] and continuum solvation models (polarized
continuum solvation model (PCM), SM8T, and DivCon). An extensive overview involving
the gas-phase basicity and proton anity, calculated using density functional methods
(B3LYP/6-311++G(d,p)) and composite methods (G3MP2B3, G3MP2, CBS-QB3,
G4MP2) and compared with corresponding experimental results for amines and
alkanolamines, is also included in the present work. This data set was selected based on
the components potential as solvents for postcombustion CO2 capture (PCC) processes.
Results of gaseous-phase thermochemistry and pKa obtained from dierent models
employed in this work are analyzed against experimental results for obtaining error
estimates involved in each theoretical model. The ESS model for the calculation of the solvation free energy of ions combined
with composite methods for gaseous-phase thermochemistry is found to give reasonable accuracy for pKa calculations of amines
and alkanolamines and thereby constitutes a method for validation of pKa for new potential PCC solvents.

1. INTRODUCTION (pressure and temperature), the pKa of amines and alkanol-

Postcombustion CO2 capture (PCC) by reactive absorption is amines is considered as an important variable.11,13,16 Reliable
one of the most mature technologies available today for prediction of pKa by incorporating quantum chemical
combating global warming.1 Amines and amino acids are approaches is cheap and is of crucial importance to dene
commonly used solvents for CO2 capture in this technology.2 the biological and chemical behavior of any molecule.17,18
The pKa of the solvent is one of the most crucial properties, pKa determination from computational chemistry requires
which has to be taken into consideration when evaluating the gaseous-phase and solution-phase free-energy calculations.
performance of a solvent.35 Depending upon the pKa of a Reliable gaseous-phase basicities can be calculated using
solvent, the reaction equilibria, kinetics, absorption capacity, density functional theory (DFT) and advanced composite
reaction rate, heat of absorption of CO2, and temperature- methods within similar or lower experimental error bars.19,20
dependent properties of the system vary.68 As explained by Experimental error bars for the calculation of gaseous-phase
Svendsen et al.,9 the energy required in a typical amine-based basicity and proton anity (PA) are around 48 kJ/mol.19
CO2 capture solvent is used to heat the solvent, to reverse the On the other hand, determination of the acidity or basicity in
absorption process, and to dilute the recovered CO2, and the a solution within reasonable accuracy is still dicult and
pKa of the solvent governs the extent and heat of reaction of demanding approaches are required to calculate these
bicarbonate formation (mainly in tertiary amines),10 which meticulously.21,22 Solvation models range from implicit2330
successively inuences the rate of CO2 transport in the to explicit solvent models;31,32 some molecules are studied
system. Versteeg et al.11 have found a linear relationship employing quantum mechanical treatment3335 of the system.
between the basicity of the solvent and the logarithm of the Despite various eorts,3538 capturing solvation eects in a
reaction rate constant of solvent molecules for their data set system accurately is still challenging39 and contributes the
of molecules. Aronu et al.12 have demonstrated that the rate largest error in the theoretical determination of pKa. To
of CO2 absorption in the solvent increases with the increase attend to this issue, various theoretical models such as
in pKa of the solvent. Additionally, the temperature swing supermolecule-style calculations, variants of dielectric con-
PCC process benets from the solvent having a high-
temperature-sensitive pKa, which helps in reversing the Received: April 21, 2016
reaction equilibrium with low energy requirements.1315 Revised: July 26, 2016
Also, to measure the inuence of operating conditions

XXXX American Chemical Society A DOI: 10.1021/acs.jpcb.6b04049

J. Phys. Chem. B XXXX, XXX, XXXXXX
The Journal of Physical Chemistry B Article

tinuum theory, and clustercontinuum approaches are Gaussian 03 in water. PCM model56 calculations are
employed. Calculation of solvation free energy using performed using DFT at the PCM/B3LYP/6-311++G-
continuum solvation models for the ionic species involved (d,p)//SM8/B3LYP-6-311++G(d,p) level. Self-consistent re-
in the calculation of pKa induces large errors. These models action eld (SCRF) and keyword read were added in the
have neutral species in their training set and do not account input le for invoking PCM calculations and adding dierent
for explicit solutesolvent interactions such as hydrogen specications of the solute cavity along with PCM-specic
bonding.40 Explicit solvation methods are considered to be modiers, respectively. The united atom for HartreeFock
more promising, as presented in our recent41 and present (UAHF) model was employed in the PCM to create the
works. Tomasi et al.42 have outlined a comprehensive review cavity using the RADII = UAHF and GEPOL algorithm of
of state-of-the-art computational solvation models. The Nilsson et al.57 The united atom approach constructs the van
considerable ongoing interest in the determination of der Waals surface using spheres that are based on non-
theoretical dissociation constants has given rise to huge hydrogen atoms. For the calculation of free energy of
number of research publications in this area.4350 solvation Gsolv using the PCM, both electrostatic and
The objective of the present study is twofold. First, the nonelectrostatic (i.e., cavitation, repulsion, and dispersion)
pKas of amines and alkanolamines are calculated by contributions are retained. Aqueous-phase SM8T calcula-
employing various gaseous-phase composite methods and tions58 are performed using DFT at the SM8T/B3LYP/6-
DFT levels of theory along with various solvation models viz. 311++G(d,p)//SM8/B3LYP-6-311++G(d,p) level in Game-
the explicit solvation shell (ESS) model introduced by da Silva ssplus,59 using optimized geometries obtained earlier. The
et al.51 and various continuum solvation models. This SM8T model is not parameterized for ionic molecules and has
provides an opportunity to benchmark the outcome and an unsigned mean error (UME) of 0.08 kcal/mol for N-
compare the performance of various gaseous-phase and containing compounds (i.e., neutral amines in the present
aqueous-phase methods of theory against experimental results. work); however, it is expected to give good qualitative results
In other words, the present work exploits the theoretical for ions.58
limits of calculating pKa to obtain reasonable accuracy using The ESS model extracts solvation shell geometries from
various gaseous- and aqueous-phase computational chemistry molecular simulations of the solute in the bulk solvent as
calculations. Second, this study helps in the initial screening given in da Silva et al.51 Quantum mechanical calculations are
and determination of the potential of amine or alkanolamine used to fully optimize cluster geometries, and cluster solvation
molecules as PCC solvents which are not commercially free energies are calculated employing the Poisson
available and thereby can save much time and resources in the Boltzmann (PB)-based model in the DivCon code.2 The
development of the carbon capture and storage (CCS) physical insights into the PB continuum solvation model have
industry. The calculated gaseous and aqueous thermochem- been given in the Supporting Information of da Silva et al.51
istry data would also provide an opportunity to compare the The PB model calculations were performed for the
thermochemistry data of these potential CCS solvents to determination of the free energy of solvation as single-point
those of new suggested solvents in the future. calculations at the AM1 level on the optimized HF/6-
The present work comprises benchmarking of quantum 31+G(d) clusters. The results of Gsolv for a single solute
electronic structure methods against experiments for calcu- obtained using the DivCon model are also estimated for
lation of PAs and gas-phase basicities (GBs), calculation of analyzing the results obtained using the ESS and DivCon
free energy of solvation of amines and their ionic counter- models. All quantum mechanical calculations were carried out
parts, and calculation of amino group pKa at 298 K using in Gaussian 03 software, and all simulations were carried out
various continuum and ESS models. The results from gaseous- using Sander from the AMBER 12 suite.60 A detailed overview
phase PA, GB, and pKa are compared against experimental of molecular dynamics simulations and the PB model is given
results, where available. in the Supporting Information.


The gas-phase geometries of amines and alkanolamines (Am) 3.1. Gas-Phase Thermochemical Properties of
and their protonated counterparts (AmH+) have been fully Amines and Alkanolamines. The standard enthalpy and
optimized using the functional B3LYP and the 6-311+ standard free energy of reaction given in eq 1 can be dened
+G(d,p) basis sets as compiled in Spartan 08 and Gaussian as the gas-phase thermochemical properties related to the
03.52 (The optimized molecular geometries in Cartesian basicity and acidity of an amine or alkanolamine molecule
coordinates are given in the Supporting Information.) (M) at 298 K as follows61,62
Frequency calculations were used to characterize the
minimum-energy structure for all of the molecules. MH+2 MH + H+ PA(MH) = H10 and GB(M)
Gaussian-n theories (G3MP2B3, G3MP2, G4MP2, CBS-
= G10 (1)
QB3) and DFT at a B3LYP/6-311++G(d,p) level are used
to calculate GB and PA. G3MP2B3, G3MP2, CBS-QB3, and GB and PA for amines and alkanolamines are calculated from
DFT calculations are performed using Gaussian 03.52 G4MP2 eqs 2 and 3 below, following the reaction in eq 1.
thermochemical calculations were done in Gaussian 09.53
For the calculations of the polarized continuum solvation GB = [G 0(MH) G 0(MH+2 )] + G 0(H+) (2)
model (PCM) and SM8T, all molecules were optimized in
the aqueous phase at HF and B3LYP54 levels using the 6- PA = [H 0(MH) H 0(MH+2 )] + H 0(H+) (3)
311++G(d,p) basis set,55 employing solvent model SM8 in
Spartan 08 in equilibrium calculations. Solvation free energies Using an ideal gas expression, the enthalpy of a proton is
are obtained using PCM calculations and default settings in calculated as
B DOI: 10.1021/acs.jpcb.6b04049
J. Phys. Chem. B XXXX, XXX, XXXXXX
The Journal of Physical Chemistry B Article

H(H+) = U + PV = 5 2 RT (4)

where U is the internal energy, P is the pressure, V is the

volume, and R and T are the universal gas constant and
absolute temperature, respectively. Obeying the Sackur
Tetrode equation,63 the entropy of the proton is given as

e5/2k T
S(H+) = R ln B
Figure 1. Thermodynamic cycle for computing solvation free
p (5) energies with the ESS model.

Here, kB represents the Boltzmann constant, is the thermal

de Broglie wavelength [ = (h2/2mkBT)1/2, where h is The solvation free energies, Gsolv
* (A), of the solute
Planks constant, m denotes the mass of the proton], and T molecules, A, were computed according to eq 7, using the
thermodynamic cycle shown in Figure 1, as
and p represent the temperature and pressure, respectively.
The values of gas-phase free energy and enthalpy for a proton * (A) = Gclust,g
Gsolv * (A(H 2O)n ) + Gsolv
* (A(H 2O)n )
are G0(H+) = 26.28 kJ/mol and H0(H+) = 6.19 kJ/mol
at 298 K, respectively, under standard-state conditions. * ((H 2O)n ) G 0 * G* l
Gsolv (7)
3.2. Thermodynamic Cycle for ESS Model Solvation
This is the sum of the free energies of forming the gas-phase
Energy Calculation. Many cluster/continuum calculations
solutewater cluster (G*clust,g(A(H2O)n)) with n explicit
employing various thermodynamic cycles for estimating water molecules and the dierence between the hydration
solvation free energy of ions have been published in the * (A(H2O)n))
free energies of the solutewater cluster (Gsolv
literature.6473 The ESS model overcomes the drawbacks of and the water cluster, G*solv((H2O)n). The standard-state
continuum solvation models to calculate the accurate free corrections adjust the gas-phase concentrations (G0* = RT
energy of solvation of ions by introducing a part of the ln(24.46)) from 1 mol/24.46 L to 1 M and the water cluster
solvent explicitly. The ESS model combines the continuum concentration from 1 M to 55.34/n M75,76 (G*1 = RT
models with explicit solvent representation, unlike a conven- ln([H2O]/n)). The gas-phase standard-state correction
tional continuum model or classical simulation, and to some (G0*) is 1.89 kcal/mol at room temperature. The above
extent take account of all contributions to the solvation cycle was used to study the solvation of a large series of
energy. Continuum solvation models account for long-range cations and anions with clusters containing ve explicit water
electrostatics, solute polarization, and cavitation energy molecules.51
contributions, whereas solutesolvent hydrogen bonding and 3.3. pKa Determination. The fundamental equation of
entropy contributions are taken into consideration during the thermodynamics relating dissociation constant pKa to the free
calculation of cluster formation energy. The results for the energy of protonation in solution (Gaq * ) is
solvation energy from the DivCon model used in the present *
work correspond to those for the solvation free energy of a Gaq
pK a =
single solute from the DivCon model, which is further RT ln(10) (8)
optimized with explicit water clusters in the ESS model. The
where R is the universal gas constant and T is the
DivCon model implements SCRF calculation combining the
temperature. The deprotonation reaction in the system can
linear-scaling divide-and-conquer semiempirical algorithm with
be shown as
the PB equation. The free energy of solvation calculated by
the DivCon model is the SCRF solvation energy for a single *

solute, and the ESS solvation free energy is obtained by taking AH+S A S + H+S (9)
an optimized single molecule of solute from DivCon and An error of 1 pKa unit is introduced in the calculation with a
adding explicit water molecules to it for the best possible variation of 1.36 kcal/mol in the Gaq
* value. The free energy
representation of solutesolvent interactions. The expected of protonation in solution (Gaq * ) corresponds to the
improvement of ESS solvation free energies over the DivCon summation of the gaseous-phase and solvation free energies
results is easily understandable based on the inclusion of all of for the deprotonation reaction given in eq 9, using a
the solutesolvent interactions. The comprehensive descrip- thermodynamic cycle described in our previous work.45
tion of the thermodynamic cycle used to calculate solvation Nproducts Nreactants
free energies using clustercontinuum models has been * = Ggas
Gsol * + * i
niGsolv, * j
explained earlier.41,51,74 Thus, the thermodynamic cycle used i=1 j=1 (10)
is only briey outlined in the present work. In the present
work, the solvation free energy of the solute, G*solv(A), is Here * indicates the standard state of 1 mol/L. Assuming
calculated by the thermodynamic cycle shown in Figure 1. ideal gas behavior, a correction corresponding to nRT
The gas-phase reaction between solute molecules, A, and ln(R*T) must be added to the gas-phase reaction energy,
clusters of water molecules (specied as(H2O)n) is depicted which is denoted Ggas * . This is typically calculated for a
by the upper horizontal leg, given in eq 6, of the water cluster standard state of 1 atm. n refers to the change in the
cycle (Figure 1). number of species in the reaction and R and R* are the gas
constants in units of J/mol K and L atm/mol K, respectively.
Gclust,g Absolute pKa calculations in the present work are based on
A(g) + (H 2O)n (g) A(H 2O)n (g) (6) the thermodynamic cycle shown in Figure 2.
C DOI: 10.1021/acs.jpcb.6b04049
J. Phys. Chem. B XXXX, XXX, XXXXXX
The Journal of Physical Chemistry B Article

by not compromising the reasonable solvation of relatively

small amine molecules studied in the present work. Although
there are many views on the issue of the number of solvent
molecules to be added to exactly represent solutesolvent
interactions, recent studies74 have shown that methods like
adding solvent molecules until the calculated solvation
energies converge could be more reliable than methods that
are based on the size and polarization of ionic molecules. But
these methods would be computationally expensive and would
possibly not result in complete cancelation of errors within
one studied data set of molecules. No convergence of free
energy of solvation is observed in case of 2-aminoethanol
Figure 2. Thermodynamic cycle employed for the calculation of pKa (MEA) by increasing the number of explicit water molecules.
values. From Figure S3, it can be suggested that the additional
explicit water molecules are not involved at the important
The full method describing the calculation of free energy of interaction site with the molecule, which would mean that
protonation in solution as a summation of aqueous and additional water molecules would not help in lowering the
gaseous solvation free energies is described in our previous energy of the molecule. The free energies of solvation
study.45 obtained for the MEA cluster using 5, 6, and 7 explicit water
3.4. Cluster Congurations. The ESS model comprises a molecules are given in Table S4, and they remain similar
cluster containing ve explicit water molecules. The without having any visible trends on increasing the explicit
encouraging results obtained in the studies by da Silva et water molecules in the solvation shell. Therefore, we believe
al.51 and Gupta et al.41 on a similar set of molecules that the molecules studied in this work are small and they can
motivated us to continue our present study with similar be reasonably solvated with ve explicit water molecules.
cluster congurations. The underlying motivation for having
ve explicit water molecules is the greater opportunity of
cancelation of consistent errors in the calculation of Gsolv
emerging from gaseous-phase free-energy, entropy, and Table 1 lists the data set of 25 amines and alkanolamines
continuum solvation free-energy calculations for dierent examined in the current work, including the experimental pKa
molecules and maintenance of optimum computational cost values. The choice of this data set was based on the possibility

Table 1. Amines and Alkanolamines Studied in This Work and Their Experimental pKa Data at 298 K
exp pKab (298 K)
no. amine and alkanolamine abbreviation type
1. 2-aminoethanol MEA p 9.50
2. 3-amino-1-propanol 3-AP p 10.0
3. ethylenediamine EDA p 9.9
4. propanamine PA p 10.6
5. 2-methyl-1-propanamine 2-MPA p 10.5
6. 2-amino-2-methylpropanol AMP p, sh 9.7
7. 2-amino-2-methyl-1,3-propanediol AMPD p, sh 8.8
8. 2-amino-2-ethyl-1,3-propanediol AEPD p, sh 8.8
9. 2-amino-1-propanol 2-AP p 9.4
10. diethanolamine DEA s 9.0
11. monomethylethanolamine MMEA s 9.8
12. morpholine MOR s, c 8.33
13. piperazine PZ s, c 9.83 (1), 5.55 (2)
14. piperidine PIP s, c 11.10
15. 3-amino-1-methylaminopropane MAPA s, p 9.89
16. thiomorpholine TMOR s, c 8.7
17. 1-methylpiperazine 1-methylPZ c 9.14
18. 4-piperidinemethanol 4-PIPM s, c 10.56
19. 4-piperidineethanol 4-PIPE s, c 10.62
20. aminoethylpiperazine AEP p, s, t, c 9.48 (1), 8.45 (2)
21. dimethylethylenediamine DMEDA s 10.03
22. 2-methylpiperazine 2-methylPZ c 9.57
23. 1-ethylpiperazine 1-ethylPZ c 9.20
24. ammonia NH3 p 9.24
25. diethylenetriamine DETA p, s 9.94

In the type of amines studied, p, s, t, sh, and c stand for primary, secondary, tertiary, sterically hindered, and cyclic amines and alkanolamines,
respectively. bPerrin 196592 and Perrin 1972.92

D DOI: 10.1021/acs.jpcb.6b04049
J. Phys. Chem. B XXXX, XXX, XXXXXX
The Journal of Physical Chemistry B Article

Table 2. GBsa of the Data Set of Amines and Alkanolamines Studied in This Work at 298 Kb
amines and alkanolamines G3MP2B3 G3MP2 G4MP2 CBS-QB3 DFT(B3LYP/6-311++G(d,p)) experimental
MEA 893 894 894 896 895 896.8c
3-AP 919 919 919 917 920 917.3c, 912.5d
EDA 913 915 914 913 917 912.5c
PA 889 889 889 887 888 883.9c
2-MPA 892 893 892 891 891 890.8c
AMP 928 929 927 926 932
AMPD 925 924 925 922 925
AEPD 931 930 931 928 932
2-AP 901 901 901 899 902
DEA 949 947 950 945 950 920c, 920.48e
MMEA 920 920 920 917 918
MOR 894 895 895 891 892 891.2c
PZ 919 920 919 916 919 914.7c
PIP 925 926 925 923 925 921c
MAPA 889 889 889 887 888
TMOR 897 899 899 896 897
1-methylPZ 919 918 919 916 919
4-PIPM 931 931 931 928 930
4-PIPE 922 922 922 919 921
AEP 884 883 885 883 886
DMEDA 887 887 887 885 887
2-methylPZ 927 927 927 924 928
1-ethylPZ 920 921 920 917 921
NH3 820 821 820 820 818 819c
DETA 883 883 884 882 884
The GBs are calculated using eq 2. bAll values are in kJ/mol. cHunter et al.79 dBouchoux et al.80 eSunner et al.81

Table 3. Gas-Phase PAsa of the Data Set of Amines and Alkanolamines Studied in This Work at 298 Kb
amines and alkanolamines G3MP2B3 G3MP2 G4MP2 CBS-QB3 DFT(B3LYP/6-311++G(d,p)) experimental
MEA 926 927 925 931 926 930.3c
3-AP 951 951 951 949 951 962.5c, 945.3d
EDA 947 948 948 947 951 951.6c, 941.8e, 951.4f
PA 919 920 920 918 920 917.8c, 907.5f
2-MPA 923 924 924 922 922 924.8c
AMP 961 962 961 961 967
AMPD 956 955 956 953 959
AEPD 962 962 963 959 962
2-AP 931 932 932 930 930
DEA 976 976 977 972 978 953c, 953.9g
MMEA 951 951 951 948 949
MOR 919 920 921 923 922 924.3c
PZ 951 951 951 948 949 943.7c
PIP 957 958 957 955 957 954c
MAPA 920 920 921 918 920
TMOR 930 931 931 928 928
1-methylPZ 950 948 950 947 951
4-PIPM 962 963 963 960 962
4-PIPE 953 953 953 951 951
AEP 914 914 915 913 915
DMEDA 917 918 918 916 917
2-methylPZ 958 959 959 956 959
1-ethylPZ 951 952 951 948 954
NH3 855 855 854 854 853 853.6c
DETA 913 913 914 912 912
The gas-phase PAs are calculated using eq 3. bAll values are in kJ/mol. cHunter et al.79 dBouchoux et al.80 eHahn et al.82 fWang et al.83 gSunner et

for these amines and alkanolamine molecules being energy- GBs and PAs of amine and alkanolamine molecules were
ecient solvents for PCC processes.15 calculated using dierent theoretical methods. Tables 2 and 3
E DOI: 10.1021/acs.jpcb.6b04049
J. Phys. Chem. B XXXX, XXX, XXXXXX
The Journal of Physical Chemistry B Article

Table 4. Free Energy of Solvation of Amines and Alkanolamines Calculated by the ESS Modela
amines and alkanolamines (neutral) Gsolv (calcd)b Ecluster
* c TScluster
* d Gs(A(S)n)e areaf
MEA 3.4 6.0 9.7 19.48 215.52
3-AP 0.0 6.4 10.7 16.71 225.70
EDA 2.2 7.3 10.7 17.91 212.94
PA 2.4 6.3 10.9 14.51 220.46
2-MPA 1.4 7.3 10.7 14.34 239.05
AMP 4.4 13.3 12.2 15.72 233.35
AMPD 3.1 10.4 12.2 17.29 234.76
AEPD 3.3 9.1 11.4 18.00 255.48
2-AP 1.0 6.9 10.3 16.74 223.81
DEA 1.7 6.0 11.0 19.05 246.71
MMEA 0.0 7.3 11.0 15.93 223.18
MOR 1.9 5.5 9.1 17.84 233.07
PZ 3.0 5.4 8.5 18.43 239.06
PIP 0.3 8.9 10.3 13.44 237.24
MAPA 1.0 5.3 10.5 18.63 255.70
TMOR 0.9 2.1 8.7 18.10 242.70
1-methylPZ 2.2 7.9 9.8 16.50 249.49
4-PIPM 4.8 8.5 9.4 17.98 266.00
4-PIPE 4.0 7.8 9.8 18.32 288.30
AEP 5.6 5.9 9.0 21.06 287.24
DMEDA 1.2 7.6 10.6 16.62 251.33
2-methylPZ 2.4 5.3 8.5 17.85 253.43
1-ethylPZ 0.9 6.1 9.6 16.79 266.08
NH3 4.29 13.1 11.9 15.12 232.15
DETA 5.5 3.1 9.0 23.75 272.64
All values are in kcal/mol. bCalculated free energy of solvation; all values shifted by 2.41 kcal/mol to remove systematic errors relative to
experimental values as in the ESS model presented by da Silva et al.51 Estimated sampling standard deviation is 1 kcal/mol. cEnergy of formation of
the cluster at the HF/6-31+G(d) level, converted from a standard state of 1 atm to 1 mol/L. Thermal corrections to the energy and zero-point
energies not included. dTemperature (298 K) multiplied by the entropy of formation of the cluster at the HF/6-31+G(d) level. eFree energy of
solvation of the cluster calculated with the PB continuum model. fArea of clusters calculated with the PB continuum model.

give GBs and PAs using G3MP2B3, G3MP2, G4MP2, CBS- with the ESS model, presented by da Silva et al.,51 are given
QB3, and DFT methods, respectively. in Tables 4 and 5, respectively. The ESS model is
We evaluated the performance of various composite and parameterized for ionic molecules. The cluster formation
DFT methods from the results given in Tables 2 and 3 for energies, entropies and cluster solvation energies for a set of
gas-phase thermochemical properties. From Tables 2 and 3, it 25 amines and alkanolamines and their corresponding
can be seen that all composite and DFT methods estimate protonated counterparts calculated in the present study are
GBs and PAs within experimental error bars. However, in the presented in Table 4 and 5, respectively. A PB continuum
case of DEA, the errors encountered are relatively high. The solvation model is used to calculate cluster solvation free
detailed discussion on the results and errors in gas-phase energies, which are also given in Tables 4 and 5. All of the
thermochemical properties is given in Section 5 below. In this results were combined to get free energy of solvation of
work, we have found that the errors obtained from the CBS- molecules as explained in the model presented by da Silva et
QB3 method are lower in comparison to those in other al.51
methods. Pokon et al.77 have studied various gas-phase In the present work, the cluster geometries of some
deprotonation reactions using the G3, CBS-QB3, and CBS-
molecules would not converge to a minimum-energy structure
APNO methods and also concluded that CBS-QB3 is the best
and had imaginary frequencies. These geometries resulted in a
choice because of its high accuracy and relatively low
breakdown of such clusters and could have been initiated
computational cost amongst all three methods. Ruusuvuori
et al.78 have also concluded in their recent work that the CBS- from poor initial geometries retrieved from molecular
QB3 method is reliable for studying nitrogen-containing bases dynamics simulations as also observed by da Silva et al.51 in
similar to the amines and alkanolamines that we have in our their work. Some vibration frequency calculations were also
present study. Therefore, as the CBS-QB3 results were more accompanied with imaginary frequencies. In pursuance of
accurate and relatively cheaper, this method was employed in identifying and disregarding all unconverged geometries and
the pKa calculations in the present work. The optimized accommodating results from stable cluster geometries, an
structures of gas-phase neutral and protonated amines and energy cuto of 80 kcal/mol from the obtained minimum-
alkanolamines obtained in this work at the CBS-QB3 level of energy structure was applied. Approximately 1015 cluster
theory are given in the Supporting Information (Figures S1 geometries resulted in breakdown and could not converge to
and S2). a stable structure from a set of 100 submitted cluster
The free energies of solvation of amines and alkanolamines geometries for each molecule. The most stable cluster
and their corresponding protonated counterparts, calculated geometries obtained in the present work for neutral and
F DOI: 10.1021/acs.jpcb.6b04049
J. Phys. Chem. B XXXX, XXX, XXXXXX
The Journal of Physical Chemistry B Article

Table 5. Free Energy of Solvation of Protonated Amines and Alkanolamines Calculated by the ESS Modela
protonated amines and alkanolamines (cation) Gsolv (calcd)b Ecluster
* c TScluster
* d Gs(A(S)n)e areaf
MEA 74.3 36.9 9.0 58.84 219.81
3-AP 62.0 29.9 8.9 53.41 230.34
EDA 64.5 29.1 7.8 55.52 221.37
PA 66.4 35.3 9.6 53.12 226.76
2-MPA 63.1 34.2 10.5 51.77 237.87
AMP 60.2 29.7 9.8 52.70 242.94
AMPD 59.1 26.7 9.5 54.21 249.35
AEPD 57.4 25.6 9.2 53.23 263.71
2-AP 63.4 31.1 9.4 54.16 228.42
DEA 55.7 24.6 10.2 53.62 249.37
MMEA 59.4 29.9 10.5 52.37 225.99
MOR 61.9 31.0 9.6 52.81 232.34
PZ 59.1 25.4 7.7 53.82 242.62
PIP 56.3 29.9 10.1 48.77 238.22
MAPA 69.0 34.0 9.3 56.63 261.11
TMOR 62.2 31.5 9.3 52.39 239.33
1-methylPZ 56.9 28.3 10.1 51.11 250.33
4-PIPM 57.9 24.5 9.1 54.83 267.92
4-PIPE 60.8 26.3 9.0 55.90 285.40
AEP 71.5 30.8 8.1 61.11 289.88
DMEDA 65.7 34.5 10.4 53.97 253.79
2-methylPZ 55.3 23.5 8.2 52.38 255.99
1-ethylPZ 57.9 29.7 9.8 50.31 267.55
NH3 76.3 35.3 8.8 62.18 175.40
DETA 71.1 28.1 9.0 64.29 276.26
All values are in kcal/mol. bCalculated free energy of solvation; all values shifted by 2.41 kcal/mol to remove systematic errors relative to
experimental values as in the ESS model presented by da Silva et al.51 Estimated sampling standard deviation is 1 kcal/mol. cEnergy of formation of
the cluster at the HF/6-31+G(d) level, converted from a standard state of 1 atm to 1 mol/L. Thermal corrections to the energy and zero-point
energies not included. dTemperature (298 K) multiplied by the entropy of formation of the cluster at the HF/6-31+G(d) level. eFree energy of
solvation of the cluster calculated with the PB continuum model. fArea of clusters calculated with the PB continuum model.

protonated amines and alkanolamines, respectively, are shown alkanolamines.61,7983 The experimental sources from the
in Figures 3 and 4. literature for GBs and PAs of amines and alkanolamines are
Tables 6 and 7 list the free energy of solvation of neutral reported in Tables 2 and 3. The error bars in the GBs and
and protonated amines and alkanolamines calculated with the PAs obtained in the present work, using dierent theoretical
ESS method, respectively. Free energies of solvation calculated models, are plotted in Figure 5.
from the continuum solvation shell models, that is, PCM, It can be seen from Figure 5 that the dierences between
SM8T, and DivCon, are also presented in Tables 6 and 7 experimental and calculated gas-phase thermochemical proper-
along with the results of ESS solvation free energies for the ties using the B3LYP/6-311++G(d,p) level of theory and
molecules studied in the present work. Results given in Tables Gaussian-n theories are within 5 kJ/mol. In the case of
6 and 7 provide us with the possibility of a thorough DEA, the dierences are relatively large. DEA and protonated
comparison between the values of free energies of solvation DEA molecules form cyclized lowest-energy conformers in the
obtained from dierent solvation models and from explicit gas phase and involve hydrogen bonding, as shown in Figures
and implicit solvation models. S1 and S2, respectively, in the Supporting Information. The
The results for the pKa determined employing the ESS experimental values were determined by Sunner et al.81 using
model and the various implicit solvation models, that is, PCM, pulsed high ion source pressure mass spectrometry with
SM8T, and DivCon, are presented in Table 8. The respective binary mixtures. The probable reason for the dierence
experimental pKa values at 298 K are also tabulated in this between the theoretical and experimental results can be
table for estimating the accuracy of each model for the suggested as the possibility of formulation of proton-bridged
determination of the dissociation constants. For each model, dimers upon ionization, and the experimental methods do not
the resulting UMEs in the calculated pKa values against the consider entropy changes combined with cyclization during
respective experimental pKa for all amine and alkanolamine
protonation. A second explanation could be the low volatility
molecules are also given in this table.
of DEA because of the presence of two OH groups taking
part in hydrogen bonding. Similar results were obtained by da
5. DISCUSSION Silva et al. in their study of basicity of alkanolamine
The GBs and gas-phase PAs for amines and alkanolamines molecules.84 They concluded that there are uncertainties in
calculated in the present work using various composite and the experimental determination of the basicity of alkanolamine
DFT methods are given in Tables 2 and 3 and are compared molecules because of alkanolamine dimer formation and their
against experimental results. There exist some studies in the low volatility. Thus, the results presented for GBs and PAs of
literature for gas-phase thermochemistry of amines and amine and alkanolamine molecules in this work give
G DOI: 10.1021/acs.jpcb.6b04049
J. Phys. Chem. B XXXX, XXX, XXXXXX
The Journal of Physical Chemistry B Article

Figure 3. continued

H DOI: 10.1021/acs.jpcb.6b04049
J. Phys. Chem. B XXXX, XXX, XXXXXX
The Journal of Physical Chemistry B Article

Figure 3. (a), (b) Optimized most stable ESS clusters of protonated amines and alkanolamines obtained in this work. (Dotted lines show
hydrogen bonds, and the bond length of hydrogen bonds is given in angstrom.)

benchmark values from computational chemistry for these (G3MP2, G3MP2B3, G4MP2, and CBS-QB3) and DFT in
thermodynamic properties. The results obtained for GB and this work varied by 1% or less in terms of relative dierence
PA using the calculations based on CBS-QB3 theory have a (5 kJ/mol), and dierent experimental results mostly have a
discrepancy of 3 kJ/mol relative to the experimental results deviation of approximately 2% relative to each other.85 In
for most of the molecules. The gas-phase thermochemical this view, the results for gas-phase thermochemistry presented
properties determined using dierent Gaussian-n theories in this work have errors which are in the range of
I DOI: 10.1021/acs.jpcb.6b04049
J. Phys. Chem. B XXXX, XXX, XXXXXX
The Journal of Physical Chemistry B Article

Figure 4. continued

J DOI: 10.1021/acs.jpcb.6b04049
J. Phys. Chem. B XXXX, XXX, XXXXXX
The Journal of Physical Chemistry B Article

Figure 4. (a) (b) Optimized most stable ESS clusters of protonated amines and alkanolamines obtained in this work. (Dotted lines show
hydrogen bonds, and the bond length of hydrogen bonds is given in angstrom.)

experimental uncertainties and are regarded as contingent in The results for free energies of solvation of amines and
nature. alkanolamines using the explicit and implicit solvation models
K DOI: 10.1021/acs.jpcb.6b04049
J. Phys. Chem. B XXXX, XXX, XXXXXX
The Journal of Physical Chemistry B Article

Table 6. Comparison of Free Energies of Solvation of Table 7. Comparison of Free Energies of Solvation of
Amines and Alkanolamines Calculated Using the ESS Protonated Amines and Alkanolamines Calculated Using
Model and Implicit Solvation Models (PCM, SM8T, and the ESS Model and Implicit Solvation Models (PCM,
DivCon)a SM8T, and DivCon)a
Gsolv (calcd) Gsolv (calcd)
ESS model implicit solvation shell models ESS
model implicit solvation shell models
amine and alkanolamine Gsolv
(neutral) (calcd)b PCM SM8T DivCon protonated amines and Gsolv
alkanolamines (cation) (calcd)b PCM SM8T DivCon
MEA 3.42 11.65 9.144 6.23
3-AP 4.01 9.28 8.192 4.36 MEA 74.33 76.70 81.94 77.66
EDA 5.22 10.38 7.823 6.14 3-AP 62.02 63.00 65.99 66.01
PA 2.38 4.14 3.294 2.09 EDA 64.47 65.81 67.89 68.2
2-MPA 1.39 3.03 2.564 1.83 PA 66.40 65.75 73.79 71.36
AMP 4.43 6.64 6.27 7.28 2-MPA 63.09 62.69 71.29 69.32
AMPD 3.09 12.22 10.011 6.36 AMP 60.22 65.64 66.26 63.98
AEPD 3.34 10.46 9.137 7.35 AMPD 59.07 61.40 63.07 62.64
2-AP 1.04 8.67 7.051 4.32 AEPD 57.35 59.20 61.69 61.43
DEA 5.75 13.43 11.255 5.83 2-AP 63.41 64.67 68.18 67.47
MMEA 0.04 8.44 6.672 3.79 DEA 55.69 62.16 59.74 57.81
MOR 1.90 12.67 9.414 4.01 MMEA 59.42 63.16 63.43 61.92
PZ 3.00 13.06 10.061 4.92 MOR 61.90 72.7 70.21 65.69
PIP 0.34 6.17 4.201 1.27 PZ 59.12 71.42 67.52 63.44
MAPA 1.02 9.74 7.239 5.8 PIP 56.28 62.46 63.35 60.36
TMOR 0.86 9.37 5.4 3.6 MAPA 69.04 70.62 76.54 73.91
1-methylPZ 2.25 10.25 8.296 4.17 TMOR 62.21 69.89 68.52 65.46
4-PIPM 4.79 11.69 8.513 5.26 1-methylPZ 56.92 69.59 66.76 62.35
4-PIPE 3.98 11.99 8.599 5.16 4-PIPM 57.91 65.81 65.67 62.93
AEP 5.65 13.82 9.649 7.5 4-PIPE 60.82 68.72 68.31 64.8
DMEDA 1.19 10.64 7.57 4.42 AEP 71.46 74.63 69.66 75.55
2-methylPZ 2.37 11.29 8.055 4.78 DMEDA 65.72 68.39 68.02 72.39
1-ethylPZ 0.91 9.79 7.626 3.45 2-methylPZ 55.28 68.96 65.15 59.84
NH3 4.29 4.09 4.609 3.11 1-ethylPZ 57.85 67.4 65.11 61.43
DETA 5.49 14.76 10.483 9.38 NH3 85.40 80.35 92.30 88.17
a DETA 71.07 75.35 78.26 77.24
All values are in kcal/mol. bCalculated free energy of solvation; all a
values shifted by 2.41 kcal/mol to remove systematic errors relative All values are in kcal/mol. bCalculated free energy of solvation; all
to experimental values as in the ESS model presented by da Silva et values shifted by 2.41 kcal/mol to remove systematic errors relative
al.51 Estimated sampling standard deviation is 1 kcal/mol. to experimental values as in the ESS model presented by da Silva et
al.51 Estimated sampling standard deviation is 1 kcal/mol.

are presented in Tables 6 and 7. Examining the results, we

can say that ESS solvation free energies for neutral amines resulting from pKa determinations employing the ESS model
and alkanolamine molecules are overestimated in comparison and continuum solvation models (PCM, SM8T, and DivCon),
to those from continuum solvation models. This is also true the better accuracy observed in pKa calculations from the EES
for protonated amine and alkanolamine molecules, but the model over that from implicit models is clearly observed. The
dierence between the ESS and continuum solvation models UME of 0.99 pKa units for ESS against 2.70, 1.65, and 1.05
for solvation free energy is relatively small. The ESS model pKa units for PCM, SM8T, and DivCon, respectively,
has been developed to study accurately the solvation free reassures that the ESS model provides signicantly better
energy of ionic molecules, so solvation free energies predicted results for pKa calculations compared to the pKa calculations
by ESS for protonated amines and alkanolamines are from implicit solvation models. Furthermore, as the ESS
considered to be more reliable compared to those by model has no parametrization for molecules in the present
continuum solvation models. data set, the absolute RMSE of 1.26 pKa units obtained from
Absolute and relative errors in pKa values obtained from the the ESS pKa calculations becomes very encouraging. Based on
explicit and implicit solvation models studied in the present the present study, the performance of the ESS model for the
work, for the data set of 25 amines and alkanolamines, are determination of solvation free energy of ions and dissociation
shown in Tables 9 and S5, respectively. The dierence constants is found to be satisfactory. The computational
between the calculated pKa values and the corresponding calculation of pKa is very demanding, and an error of 1.36
experimental pKa values is referred to as absolute error, kcal/mol in the deprotonation reaction would introduce an
whereas relative error corresponds to the error given by error of 1 pKa unit.46,47 This error can be minimized on the
primarily adding a signed mean error (SME) for each model basis of the choice of thermodynamic cycle and methods used
to its calculated pKa value and later subtracting the calculated for gas-phase and aqueous-phase calculations. The main error
pKa value from the corresponding experimental pKa value. in pKa calculations comes from solvation free energies, as
SME, UME, and RMSEs for the present data set of continuum models are parametrized to experimental free
molecules are listed in Table 9. On comparison of errors energy of solvation for ions, which have error bars of
L DOI: 10.1021/acs.jpcb.6b04049
J. Phys. Chem. B XXXX, XXX, XXXXXX
The Journal of Physical Chemistry B Article

Table 8. Comparison of pKa Calculated from the ESS Model and Implicit Solvation Shell Models with the Experimental pKa
at 298 K
pKa at 298 K UME
amine and alkanolamines expa ESS PCM SM8T DivCon ESS PCM SM8T DivCon
MEA 9.50 10.51 6.19 11.89 10.89 1.01 3.31 2.39 1.39
3-AP 9.96 9.71 6.56 9.56 12.39 0.25 3.40 0.40 2.43
EDA 9.93 9.97 7.15 10.57 12.03 0.04 2.78 0.63 2.10
PA 10.60 12.38 7.10 13.64 12.74 1.78 3.50 3.04 2.14
2-MPA 10.50 9.85 6.31 12.98 12.07 0.65 4.19 2.48 1.57
AMP 9.72 9.68 12.04 12.77 10.35 0.04 2.32 3.05 0.63
AMPD 8.80 9.00 3.99 6.85 9.22 0.20 4.81 1.95 0.42
AEPD 8.80 8.72 4.84 7.64 8.77 0.08 3.96 1.16 0.03
2-AP 9.40 9.75 5.07 8.84 10.33 0.35 4.33 0.56 0.93
DEA 8.96 8.67 7.78 7.60 10.17 0.29 1.18 1.36 1.21
MMEA 9.77 10.74 7.25 8.76 9.76 0.97 2.52 1.01 0.01
MOR 8.33 6.63 6.66 7.22 7.87 1.70 1.67 1.11 0.46
PZ 9.83 8.16 9.81 9.14 9.93 1.67 0.02 0.69 0.10
PIP 11.12 9.66 9.41 11.52 11.48 1.46 1.71 0.40 0.36
MAPA 9.89 11.83 6.58 12.77 11.90 1.94 3.31 2.88 2.01
TMOR 8.70 9.73 7.85 9.76 8.84 1.03 0.85 1.06 0.14
1-methylPZ 9.14 7.05 10.48 9.84 9.63 2.09 1.34 0.70 0.49
4-PIPM 10.56 7.99 8.72 10.96 11.34 2.57 1.84 0.40 0.78
4-PIPE 10.62 9.22 9.14 11.34 11.28 1.40 1.48 0.72 0.66
AEP 9.48 9.40 5.72 5.13 11.05 0.08 3.76 4.35 1.57
DMEDA 10.03 8.90 3.91 5.89 11.43 1.13 6.12 4.14 1.40
2-methylPZ 9.57 7.14 10.64 10.21 8.72 2.43 1.07 0.64 0.85
1-ethylPZ 9.20 8.88 9.38 9.29 9.65 0.32 0.18 0.09 0.45
NH3 9.24 9.61 6.04 14.45 12.52 0.37 3.20 5.21 3.27
DETA 9.94 9.03 5.36 10.65 10.71 0.91 4.58 0.71 0.77
average error 0.99 2.70 1.65 1.05
Experimental data from Perrin 196592 and Perrin 1972.92

approximately 25 kcal/mol.58 On the other hand, explicit alkanolamines and provides the possibility of substantially
solvation methods take specic solutesolvent interactions cheaper calculations than DFTMD.
into consideration and do not include uncertainty due to
experimental errors.86 Pliego et al.,69 in a similar work 6. CONCLUSIONS
involving calculation of pKa using explicit and implicit
solvation models, have obtained an RMSE of 2.2 pKa units The comprehensive study of the gas-phase thermochemical
with an explicit model compared to that of 7 pKa units using properties of the 25 molecules shows that the calculated
implicit solvation models. In other words, we can say that in gaseous-phase PA and basicity computational results are
the challenging realm of calculating computational pKa, the within experimental error bars and could serve as benchmark
present results can be helpful in the initial screening of PCC results for the molecules for which experimental results are
solvents and in identifying promising PCC solvents, which are not available or are dicult to obtain. The calculated GBs and
not yet available or are very expensive. PAs provide reliable thermochemical results for the molecules
In the literature, many references are found for a DFT-
and could be employed for evaluating the consistency within
based explicit solvent approach for pKa calculation.8790 The
transferability to heterogeneous redox reactions at electro- various experimental sources reported in the NIST database.91
chemical interfaces is a main advantage of the DFT-based However, poor agreement between experimental and
molecular dynamics (DFTMD) method. However, the huge calculated GB and PA for DEA is observed, and in this
computational cost of the DFTMD method imposes a serious case, the experimental results are suggested to be more
drawback. Clustercontinuum or quantum mechanics/molec- uncertain than computational results. As experimental
ular mechanics methods are relatively cheaper for computa- determination of solvation free energies is challenging, the
tions of pKa and redox free energies.88 results for solvation free energy for protonated amines and
DFTMD and clustercontinuum methods are comparable alkanolamines could help as guiding values for future advances
in terms of errors observed in the calculation of pKa. Mangold in this demanding domain of computational chemistry. The
et al.87 in their DFTMD simulation study containing six
better performance and lower RMSE for the ESS model
amino acids report a UME of 2.1 pKa units with a maximum
error of 4.0 pKa units. In DFTMD, approximations in DFT compared to those of various implicit models for the
can be the main source of error in the results, and these calculation of pKa are reported in the present work. Hence,
calculations also have limitations of time scales and model the explicit solvation model provides a potential approach for
system size. The explicit solvation model used in the present calculating solvation energies of ions and thermochemical
work gives very encouraging results for pKas of amines and properties with relatively high degree of accuracy.
M DOI: 10.1021/acs.jpcb.6b04049
J. Phys. Chem. B XXXX, XXX, XXXXXX
The Journal of Physical Chemistry B Article

Figure 5. Plots of GB dierences (GB = GBexp GBcalcd) and gas-phase PA dierences (PA = PAexp PAcalcd) of G3MP2B3, G3MP2,
G4MP2, CBS-QB3, and DFT (B3LYP/6-311++G(d,p)) in kJ/mol for the amines and alkanolamines studied in this work.

Table 9. Comparison of Absolute Errors for pKa from the

ESS Model and Continuum Solvation Models (PCM,

S Supporting Information
SM8T, and DivCon)a
The Supporting Information is available free of charge on the
Absolute Errors ACS Publications website at DOI: 10.1021/acs.jpcb.6b04049.
errors ESS PCM SM8T DivCon Constant terms utilized in calculations for the ESS
SME 0.38 2.30 0.31 0.94 model. Underlying data for Tables 4 and 5, energy of
UME 0.99 2.70 1.65 1.05 the solute and cluster in gas phase, thermal corrections
RMSE 1.26 3.10 2.15 1.33 to the energy and entropy of the solute and cluster.
Dierent errors are abbreviated as SME (signed mean error), UME Optimized structures of gas-phase neutral and proto-
(unsigned mean error), and root-mean-square error (RMSE). nated amines and alkanolamines studied in the present
work at the CBS-QB3 level of theory. Simulation
N DOI: 10.1021/acs.jpcb.6b04049
J. Phys. Chem. B XXXX, XXX, XXXXXX
The Journal of Physical Chemistry B Article

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