Structural Chemistry (2019) 30:185–194

https://doi.org/10.1007/s11224-018-1192-3

ORIGINAL RESEARCH

C–H···O interaction between cation and anion in amino acid-based ionic

liquids—A DFT study in gas and solvent phase
Muraledharan Shyama 1 & Senthilkumar Lakshmipathi 1

Received: 15 August 2018 / Accepted: 19 September 2018 / Published online: 28 September 2018
# Springer Science+Business Media, LLC, part of Springer Nature 2018

Abstract
The interaction between anions and cations within amino acid-based ionic liquids (AAILs) are studied in the gas phase and in
three different solvents (DMSO, water, and formamide). Structural and topological analyses of ion pairs signify that they interact
via C–H···O hydrogen bond. In gas and solvent phase, the aliphatic amino acids (anions) interact strongly with EMIM (1-ethyl-3-
methylimidazolium) and BMIM (1-butyl-3-methylimidazolium) cations. Further, the interaction between amino acid and EMIM
cation is stronger due to large charge transfer from the electronegative oxygen atoms (carbonyl group) of the amino acids to the
C–H bond of the imidazole ring. All the C-H···O bonds observed between the ions are red shifted and strong due to large
interaction energy. The major contribution to the interaction energy is from electrostatic and orbital energies. The implicit
solvents tend to increase the H···O distance of the AAILs. The increase in the chain length of cations irrespective of phase
meagerly decreases the interaction between the ions. From the solvation energy, the reaction between solvents and AAILs are
exothermic. AAILs possess higher solvation energy in DMSO. Overall, ionic liquids are highly stable in the gas phase and
moderately stable in the solvents due to C-H···O bonds.

Keywords C-H···O . Hydrogen bond . Amino acid based ionic liquids

Introduction
Hydrogen bonding [1–14] interactions are of keen interest to
researchers due to their importance in the chemical and biolog-
ical process for both theoretical and practical reasons. Besides,
they are found to be responsible for the physical and chemical
properties of different liquid systems other than water. Several
experimental and theoretical studies have established that hy-
drogen bond is a major force in governing the chemical activity
taking place in liquids [15]. Hydrogen bonds are convention-
ally represented as X-H···Y where both X and Y electronega-
tive atoms share the hydrogen atom. Several intermolecular
hydrogen bonds are observed in tradition like C–H···O, O–
H···O, and N–H···O in organic as well as biological molecules.
Electronic supplementary material The online version of this article
(https://doi.org/10.1007/s11224-018-1192-3) contains supplementary
material, which is available to authorized users.
* Senthilkumar Lakshmipathi
lsenthilkumar@buc.edu.in
1
Department of Physics, Bharathiar University, Coimbatore, Tamil
Nadu 641046, India
Among these bonds, C–H···O [4, 13, 16, 17] hydrogen bond is
peculiar and interesting because several studies in organic mo-
lecular and crystal systems have observed and classified these
bonds as a weak non-conventional hydrogen bond. These C–
H···O bonds mostly reinforce with other conventional hydro-
gen bonds and aid in the stability of the chemical system.
However, in ionic liquids, C–H···O bond is vital as being the
primary source of interaction between cation and anion, which
is responsible for the liquid state.
Ionic liquids (ILs) [18–25], a class of liquids made of a large
organic cation and an inorganic anion, have been extensively
studied due to their low volatility and higher thermal and chem-
ical stabilities. A variety of ILs have been developed and stud-
ied according to the specificity and practical applications, like
room temperature ionic liquids (RTILs) [26–28], task-specific
ILs (TSILs) [29], and polyionic liquids (PILs) [30, 31]. A new
class of IL derived from amino acids has gained interest these
days due to easy availability and their environmentally benign
nature. These are amino acid-based ionic liquids [32, 33]
formed via C–H···O hydrogen bonding wherein amino acids
are anions and alkyl imidazolium as cations. Previous theoret-
ical studies [32, 34–39] suggest that the C–H···O hydrogen
bonding [37] between cation-anion of IL are found to stabilize
186
the system. Vibrational and other spectroscopic [34, 40] tech-
niques have confirmed the presence of red-shifted C–H···O
hydrogen bonds as a result of the interactions between the ionic
pairs. However, all these studies restrict themselves to gas
phase results. In the industry, these AAILs are subjected to
additives to alter their viscosity to suit the applications, for
example as an electrolyte in batteries [41], solvents [19, 27,
28, 42] for organic synthesis and as separation enhancers [31,
33, 43, 44]. Presumably, these additives affect cation-anion
interaction. Hence, the nature of C–H···O hydrogen bonds pres-
ent in AAILs in the solvent is questioned and needs thorough
investigation. Most studies also reveal the change in behavioral
properties of AAILs when immersed in a solvent phase [7, 15,
29, 45–52]. The aim of this paper is to learn the structural
parameters and energetics of C–H···O hydrogen bonding inter-
actions of AAILs in gas and solvent phase.
This paper reports the interactions of 64 AAILs, with two
cations (1-ethyl-3-methylimidazolium and 1-butyl-3-
methylimidazolium) with increasing chain length [53] and
eight hydrophobic amino acid-derived anions in the gas phase
and solvent phase in the increasing order of their dielectric
constant (dimethyl sulfoxide, water, and formamide). Nature
of the C–H···O hydrogen bond is analyzed using topological
analysis, natural bonding orbital analysis, and energy decom-
position analysis.
Computational details
Density functional theory (DFT) [16] calculation was
employed to investigate the interactions between various pos-
sible conformers of a cation-anion pair of AAILs, in the gas
phase and solvent phases. The gas-phase geometries with low-
est energies along with their frequencies were calculated at
PBEPBE/6-311++G (d, p) [16] level of theory. The structures
have been studied in liquid phases using Tomasi’s Polarizable
Continuum Model (PCM) [54]. Stable configurations of gas
phase were used as initial geometries in solvents viz. dimethyl
sulfoxide (DMSO), water, and formamide. Single-point cal-
culations for energy distributions using SM12 [55] solvation
model were carried out with GGA-PBE [56] (generalized gra-
dient approximation-Perdew-Burke-Ernzerhof) functional
and QZ4P set with Grimme’s dispersion corrections [57]
using ADF [58] (Amsterdam density functional). All optimi-
zation calculations (gas and solvent phase) were performed
using the Gaussian 09 Package [59]. Topological properties
were calculated using atoms in molecules analysis (AIM) [60]
using the MORPHY98 [60, 61] program package.
Result and discussion
1-ethyl-3-methylimidazolium [EMIM] and 1-butyl-3-
methylimidazolium [BMIM] as cation and aliphatic amino
Struct Chem (2019) 30:185–194
acids like alanine [ALA], leucine [LEU], isoleucine [ILE],
methionine [MET], valine [VAL], and aromatic amino acids
like phenylalanine [PHE], tryptophan [TRP], and tyrosine
[TYR] as anions were combined to form AAILs. Though
the interaction was carried out at different sites on cation,
ortho site in cation emerged as a strong binding site.
Subsequently considering ortho site, we have obtained 16
structures each in gas and solvent phase with an aggregate
of 64 structures.
Structural parameters
Figure 1 exhibits the optimized geometries of amino acid-
based ionic liquid [62] structures in the gas phase with their
atom numbering and bond length. The interactions of EMIM+
and BMIM+ with all anions are through two intermolecular
C–H···O bonds. Besides, the two C–H···O bonds are common
between cation and anion among all the AAILs considered.
All the C–H···O bonds are formed between the carbonyl
oxygen (negative) atoms in amino acids anions, and the hy-
drogen atom attached to the ortho-positioned carbon (positive
charge) of the imidazole ring, forming C–H···O bonds [52,
63]. Based on the Lewis acid-base concept, the electronega-
tive oxygen atoms (carbonyl group) of the amino acids act as
the electron donor while the C–H bond of the imidazole ring
acts as the electron acceptor. Table 1 provides the bond length,
electron density, and Laplacian of the electric density of C–
H···O bonds formed between cation-anion in the gas phase.
In gas phase among EMIM-based AAILs, the short and
strong, C–H···O, a hydrogen bond is formed between
[EMIM-ALA] with a bond length of 1.56 Å (C1–H5···O23).
However, the weak bond is observed between [EMIM-TRP]
with a bond length of 2.03 Å. Likewise, among BMIM-based
AAILs, [BMIM-ALA] has a strong bond of 1.57 Å (C1-H5···
O29), while [BMIM-LEU] has a weak bond of length, 2.06 Å,
in the gas phase. The bond lengths observed agree with pre-
vious studies reported by Wu and Zhang [37] for EMIM-
based ILs. In case of the liquid phase, two C–H···O bonds
are observed in all the AAILs. Tables S1, S2, and S3 of
supporting information presents the bond length and electron
density and Laplacian of electron density of the C–H···O
bonds observed in the solvents. The difference in C–H···O
bond lengths pertaining to BMIM and EMIM in all the sol-
vents are 0.09~0.1 Å. However, by comparing the gas phase,
the C–H···O bond lengths in the solvent phase has increased in
length in the order of 0.2~0.3 Å for BMIM and EMIM com-
plexes. The stable configurations of EMIM-AAILs and
BMIM-AAILs in solvents with hydrogen bonds are indicated
in Fig. S1 of the supporting information. Among the three
solvents, short and strong hydrogen bonds are observed in
DMSO (1.77 Å, [EMIM-ALA]). Overall, on comparing all
the bond length in the gas and solvent phase, we observe that
aliphatic amino acids interact strongly with EMIM and
Struct Chem (2019) 30:185–194 187

BMIM. Further, EMIM AAILs form shorter hydrogen bonds hydrogen bonds are linear. This suggests that an increase in
with amino acids than BMIM, and bond angles of stronger chain length of cations decreases the interactions. The bond

EMIM-ALA EMIM-ILE

EMIM-LEU EMIM-MET

EMIM-PHE EMIM-TRP

EMIM-TYR EMIM-VAL

BMIM-ALA BMIM-ILE
Fig. 1 The stable configurations of EMIM-AAILs and BMIM-AAILs at and degree (°), respectively. Color code: carbon—green, hydrogen—
PBEPBE/6–311++G (d, p) level. Dotted lines represent hydrogen bonds blue, oxygen—red and nitrogen—pink, sulfur—yellow
and the corresponding bond lengths and bond angles are in angstrom (Å)
188
BMIM-LEU
BMIM-PHE
BMIM-TYR
Fig. 1 (continued)
angles range from 163.37° to 167.73° for EMIM-based
AAILs and 159.89° to 171.40° for BMIM-based AAILs in
the gas phase. In the solvent phase, the hydrogen bond angles
range for EMIM and BMIM are 167.93° to 177.20° and
160.72° to 177.54°, respectively. These above linear bond
angles indicate strong overlap of orbitals between anion and
cations which reflects in shorter C–H···O bond lengths.
AIM analysis
To provide insight into the nature of the hydrogen bond
[64–66] in the ionic pairs, we employ electron density-based
topological parameters within the framework of Bader’s
atoms in molecule theory using MORPHY 98 Program.
Generally, a large value of the electron density and a positive
value of the Laplacian of electron density confirm that stron-
ger bonds are formed and that the electrostatic interaction is a
major source of H-bonded systems. The ionic pair, bond, elec-
tron density (ρ), and Laplacian of electron density (∇2ρ) in
atomic units and bond lengths (Å) corresponding to the bond
Struct Chem (2019) 30:185–194
BMIM-MET
BMIM-TRP
BMIM-VAL
critical points (BCPs) of C–H···O intermolecular bonds be-
tween EMIM- and BMIM-based AAILs in gas phase is given
in Table 1. The electron density, Laplacian of electron density,
and the bond lengths of the hydrogen bonds formed at bond
critical points between the cation-anion in solvents are report-
ed in the supporting information Tables S1, S2, and S3. Here,
the electron density and the Laplacian of electron density of
C–H···O bond among the ionic pairs range from 0.02 to
0.07 a.u. and 0.07 to 0.13 a.u., respectively in the gas phase;
therefore, the nature of the interaction is electrostatic.
Topological parameters, electron density and the Laplacian
of electron density of C–H···O bond in solvents range from
0.01 to 0.04 a.u. and from 0.04 to 0.13 a.u., respectively,
which is slightly less than the gas phase due to the weaker
interaction between the ions. Further, we have established a
correlation between the hydrogen bond distances and electron
density for both gas and solvent phase, which is inverse in
nature, indicating an increase in hydrogen bond length corre-
sponding to decrease in electron density. The correlation
graphs for AAILs in gas, DMSO, water, and formamide are
Struct Chem (2019) 30:185–194 189

Table 1 The ionic pair, bond, electron density (ρ), and Laplacian of NBO analysis
electron density (∇2ρ) in atomic units and bond lengths (Å) corresponding
to the bond critical points (BCPs) of C–H···O intermolecular bonds
between EMIM- and BMIM-based AAILs in gas phase Natural bond orbital analysis (NBO) [67] is a reliable tool to
study hydrogen bonds, as it provides good information regard-
Ionic pair Bond Bond ρ(a.u.) ∇2ρ(a.u.) ing the change in charge densities of donor and acceptor ions.
length (Å)
In the present work, strong C–H···O hydrogen bond has been
EMIM-ALA C13–H15···O22 2.03 0.02 0.08 observed; hence, NBO is an appropriate method to explain the
C1–H5···O23 1.56 0.07 0.13 charge delocalization process between a lone pair of oxygen to
EMIM-ILE C1–H5···O20 1.58 0.07 0.13 the antibonding orbital of a C–H proton acceptor. The occu-
C8–H9···O24 2.01 0.02 0.08 pation number of the donor and acceptor ions and their corre-
EMIM-LEU C1–H5···O20 1.58 0.07 0.13 sponding stabilization energies are represented in Tables S8,
C13–H15···O24 2.03 0.02 0.08 S9, S10 and S11 of the supporting information. From the
EMIM-MET C1–H5···O22 1.58 0.07 0.13 above tables, we observe that in general, for EMIM and
C8–H11···O20 2.02 0.02 0.08 BMIM both in gas and solvent phase, charge transfer has
EMIM-PHE C1–H5···O28 1.62 0.06 0.13 occurred from the lone pairs of oxygen atom to the antibond-
C13–H15···O29 2.06 0.02 0.08 ing orbital of the C–H bonds. This is evident from the occu-
EMIM-TRP C1–H5···O24 1.59 0.07 0.13
pation number of proton donor (N(y)) and acceptor (C–H)
C13–H15···O23 2.03 0.02 0.08
which have decreased and increased from their corresponding
EMIM-TYR C1–H5···O22 1.59 0.07 0.13
monomers respectively. The charge transfer is maximum in
gas (0.1–0.002e) and minimum in solvent phase (0.1–0.009e).
C8–H11···-O20 2.02 0.02 0.08
Among solvents, the charge transfer is maximum in DMSO
EMIM-VAL C1–H10···O22 1.57 0.07 0.13
(0.07–0.004e). Besides the above, charge transfer from EMIM
C8–H11···O20 2.01 0.02 0.08
is more than BMIM cation.
BMIM-ALA C13–H15···O28 2.04 0.02 0.07
Further, this charge transfer has increased the C–H bond
C1–H5···O29 1.57 0.07 0.13
length in the range 0.08–0.01/0.04–0.008 Å in gas/solvent
BMIM-ILE C1–H5···O26 1.58 0.07 0.13
respectively, common for both EMIM/BMIM systems. Also,
C8–H11···O30 2.02 0.02 0.08
this has led to a concomitant decrease in the H···O bond
BMIM-LEU C1–H5···O26 1.59 0.07 0.13
length. Apparently, from the above results, it is noticeable that
C13–H16···O30 2.06 0.02 0.07
shorter C–H···O bond has large charge transfer from proton
BMIM-MET C1–H5···O28 1.59 0.07 0.13
donor to acceptor, associated with large stabilization energy
C8–H11···O26 2.01 0.02 0.08
E2. For example, in gas phase, [EMIM-ALA] has the shorter
BMIM-PHE C1–H5···O35 1.61 0.06 0.13
and stronger C–H···O bond (1.56 Å) with lone pair occupancy
C18–H11···O34 2.01 0.02 0.08 of 1.87086 a.u. in monomer which is found to be decreased by
BMIM-TRP C1–H5···O30 1.59 0.07 0.13 an amount of 0.002e, with simultaneous increase in the anti-
C8–H11···O29 2.02 0.02 0.08 bonding orbital (C–H) occupancy to 0.03356 a.u. from the
BMIM-TYR C1–H5···O28 1.59 0.07 0.13 corresponding monomer value of 0. 01289 a.u, with the max-
C13–H15···O26 2.05 0.02 0.07 imum second-order perturbation energy of E2 (40.04 kcal/
BMIM-VAL C1–H5···O28 1.58 0.07 0.13 mol) among all the hydrogen bonds. Overall, these charge
C13–H15···O26 2.04 0.02 0.07 transfers result from NBO validate the strong and short C–
H···O bonds.

Nature of C–H···O hydrogen bond

reported in Figs. S2, S3, S4 and S5 of the supporting informa-
tion. The correlation coefficients obtained for electron density
with hydrogen bond for EMIM- and BMIM-based AAILs are
0.998 a. u and 0.999 a.u. respectively in the gas phase. The
coefficient of correlation for EMIM-based AAILs in DMSO is
found to be 0.994 and BMIM-based AAILs have a correlation
of 0.988. The correlation coefficient is 0.998 for EMIM-based
AAILs and 0.996 in BMIM-based AAILs in water, and the
coefficients are 0.999 and 0.995 in EMIM and BMIM AAILs
in formamide, respectively. All the correlation values above
suggest a strong overlap of orbitals between the ions.
The C–H···O hydrogen bond is found in all the complexes of
this work; it is appropriate to analyze whether the bonds are
proper or improper using vibrational frequency analysis,
henceforth will provide validation of the charge transfer pro-
cess. Comparative table of the C–H stretching frequencies of
AAILs in the gas phase and all solvent phases are summarized
in Table S4 of the supporting information. All the ionic pairs
formed exhibit C–H···O bonds with C and H being sp2 and sp.
hybridized respectively. In general, all the C–H stretching fre-
quencies indicate the bond to red shifted. This is due to the
190 Struct Chem (2019) 30:185–194

large charge transfer from the lone pair of oxygen atom to the
antibonding orbital which induces structural reorganization,
thereby elongating the C–H bond with a concomitant decrease
in the H···O distance. This elongation accounts for the de-
crease in the frequency of C–H bond from their corresponding
monomers. It is found that the C–H bond has elongated ap-
proximately by 0.01–0.08 Å in the gas phase and 0.01–0.1 Å
when solvated in both EMIM- and BMIM-based AAILs. The
C–H stretching frequencies in the gas phase and solvent
phases when compared show a red shift in the range 430–
640 cm−1. Further, the shifts in frequencies increase up to
500 cm−1 in going from the gas phase to the solvent phase.
However, the difference in frequency shifts among the three
solvents is in the range of 2 to 160 cm−1. We compared the C–
H stretching frequencies of the monomers to the C–H
stretching frequencies of the complex in the gas phase and
solvent phase. We observed a shift range of 400–1000 cm−1
for EMIM/BMIM-based AAILs. The abovementioned shift
values confirm that the C–H···O bonds are proper and red shift
in nature.
Energetics
One of the most interesting tools to study the nature of hydro-
gen bond energy is provided by the partitioning of interaction
energy in which energy is decomposed [68] in terms of elec-
trostatic interactions, Pauli’s repulsion, orbital interactions,
and dispersion energy.
In this method, the interaction energy between the two
fragments ΔEint is split up into four components:
ΔE int ¼ ΔE pauli þ ΔE elstat þ ΔE orb: þ ΔE disp: ð1Þ
where ΔEpauli gives the repulsive Pauli interactions between
the occupied orbitals of the two fragments. ΔEelstat. gives the
classical electrostatic interaction between the fragments. Both
ΔEpauli and ΔEelstat combined account for the steric interac-
tion (ΔEsteric). ΔEorb is the interaction between the occupied
molecular orbitals of one fragment with the unoccupied mo-
lecular orbitals of the other fragment as well as mixing of
occupied and virtual orbitals within the same fragment (in-
ner-fragment polarization). ΔEdisp. accounts for the energy
contribution from long-ranged electron correlation effect be-
tween the fragments. ΔEint accounts for the interaction be-
tween the two fragments of the complex. Table 2 provides
the energy decomposition analysis for the gas-phase interac-
tions of the AAILs. Tables S5, S6, and S7 of the supporting
information provide the energy decomposition for AAILs in
the liquid phase. From the results, it is evident that the elec-
trostatic interactions are the most pronounced interactions
among all; orbital interactions play a secondary role in sum-
ming up the total energy followed by dispersion interactions
and Pauli’s repulsion. The most stable complex among all
EMIM- and BMIM-based ILs in gas and solvent phase is
[EMIM-ALA], but for formamide wherein [BMIM-PHE]
has the maximum interaction energy originating from the
strong orbital interaction. A similar contribution from orbital

Table 2 The energy

decomposition analysis (EDA) AAILs EDA of interaction energies(kcal/mol)
for the ionic pairs calculated using
GGA-PBE functional and QZ4P Pauli’s Electrostatic Orbital Dispersion Total interaction
set with dispersion corrections repulsion interactions interactions energy energy

EMIM-ALA 49.51 − 109.93 − 40.20 − 2.43 − 103.06

EMIM-ILE 47.36 − 107.49 − 38.68 − 2.69 − 101.30
EMIM-LEU 47.36 − 107.32 − 38.77 − 2.74 − 101.47
EMIM-MET 46.45 − 106.29 − 37.91 − 2.45 − 100.20
EMIM-PHE 42.95 − 103.28 − 35.86 − 2.51 − 98.70
EMIM-TRP 46.37 − 105.92 − 38.48 − 2.53 − 100.56
EMIM-TYR 46.26 − 105.11 − 38.05 − 2.41 − 99.31
EMIM-VAL 49.31 − 108.97 − 40.04 − 2.54 − 102.24
BMIM-ALA 48.61 − 108.12 − 40.01 − 2.66 − 102.2
BMIM-ILE 47.09 − 106.00 − 39.04 − 3.67 − 101.61
BMIM-LEU 48.16 − 106.73 − 39.47 − 2.67 − 100.72
BMIM-MET 45.73 − 104.60 − 37.61 − 2.51 − 98.99
BMIM-PHE 44.3 − 102.92 − 36.93 − 2.52 − 98.08
BMIM-TRP 45.87 − 104.68 − 38.21 − 2.58 − 99.6
BMIM-TYR 45.07 − 103.00 − 37.68 − 2.74 − 98.35
BMIM-VAL 48.26 − 106.87 − 39.82 − 2 .84 − 101.27
Struct Chem (2019) 30:185–194 191

interactions is observed in [BMIM –MET] which makes it the ΔG⊗conc accounts for the difference in concentrations, if any,
second most stable complex in water. Nevertheless, in the gas-phase standard state and the solution-phase one.
[EMIM/BMIM-ALA] remains the second most stable form The solvation energies obtained from the energy decomposi-
in gas and other solvents. In general, the orbital interaction tion analysis is reported in Table 3.
energy has marginally increased from the gas to solvents in As expected, the addition of the solute expands the ion-ion
all complexes. structure; however, more surprisingly, the long-range interac-
The difference in total interaction energy between most tions are still present in the system. The energy decomposition
stable structure and the second stable structure in EMIM- analysis of AAILs in solvents shows that the electrostatic in-
based AAILs is found to be 0.82 and 0.70 kcal/mol in the teractions play a major role in stabilizing the AAIL in solvents
gas and solvent phase, respectively. Despite the above, the followed by the contributions from orbital interactions.
stability order indicates that aliphatic amino acid IL com- [BMIM-PHE] in formamide has the maximum stability and
plexes are more stable than aromatic amino acid IL complexes [BMIM-PHE] in DMSO is the least stable form obtained. The
in all the phases. Though these complexes are formed with C– reaction between the AAIL and solvent are exothermic in
H···O hydrogen bonds, the interaction energies of these IL nature due to negative solvation energy.
systems are of the order of covalent [37, 40, 69] bond energy From EDA analysis for AAILs in liquid phase provided in
and shows that the AAILs are highly stable. The calculated the supporting information Tables S5, S6, and S7, we infer
interaction energies are in agreement with the results previ- that the cations interact weakly to the solute and have less
ously obtained [37]. The relative order of stability in influence in contributing to solvation energy. Hence, anions
EMIM/BMIM-based ILs in gas phase is [EMIM- appear to play a significant role in determining the solubility
A L A ] > [ E M I M - VA L ] > [ E M I M - L E U ] > [ E M I M - of AAILs in solvent phase. Hydrophobic anions exhibit stron-
ILE] > [EMIM-TRP] > [EMIM-MET] > [EMIM- ger solvation in all the solvents. However, among all solvents,
TYR] > [EMIM-PHE]. Overall, except for DMSO, other sol- AAILs exhibit maxiumum solvation in DMSO. For example,
vents such as water and formamide have perturbed stability [EMIM-TYR] and [BMIM-TYR] show more preferences to-
order. wards dissolving in DMSO with solvation energy of −
27.33 kcal/mol and − 27.73 kcal/mol, respectively.
Meanwhile, [EMIM-ALA] and [BMIM-LEU] showed the
Solvation energy least favorable solvation in DMSO. Ionic pairs in water and
formamide show almost similar values of solvation energy.
A good understanding of solute-solvent interactions is vital to The dielectric constant of the solvents is found to influence
learn about ionic liquids. Continuum solvation models are
efficient tools for studying solvent effects on molecular struc-
ture, spectra, and energetics. The energy of solvation repre- Table 3 The solvation energies (ΔG⊗S) of the ionic pairs in DMSO,
water, and formamide in kcal/mol
sents a very important property for the thermodynamic de-
scription of a solution. Single-point calculations were per- Solvation energy (ΔG⊗S) in kcal/mol
formed using the SM12 model to calculate the solvation en-
Ionic pairs DMSO Water Formamide
ergy of the EMIM- and BMIM-based ILs in three different
solvents, DMSO, water, and formamide of dielectric constants EMIM-ALA − 19.19 − 15.43 − 15.37
46.826, 78.35, and 108.94, respectively. Solvation energy is EMIM-ILE − 19.21 − 14.58 − 14.53
calculated combining both the energy associated with the EMIM-LEU − 19.38 − 14.73 − 14.69
SCRF polarization, post-SCF polarization, and post-SCF sur- EMIM-MET − 20.04 − 15.01 − 15.23
face tension energies. EMIM-PHE − 23.17 − 16.32 − 17.33
The theoretical free energy of solvation is computed ac- EMIM-TRP − 27.28 − 19.59 − 20.52
cording to
EMIM-TYR − 27.33 − 19.49 − 19.48
ΔG⊗ S ¼ ΔEE þ GP þ GCDS þ ΔGN þ ΔG⊗ conc ð2Þ EMIM-VAL − 19.23 − 14.33 − 14.29
BMIM-ALA − 19.47 − 14.51 − 14.67
where the symbol ⊗ denotes an arbitrary choice of standard BMIM-ILE − 19.65 − 13.30 − 13.27
states, ΔEE is the change in the solute’s internal electronic BMIM-LEU − 18.77 − 13.28 − 13.43
energy in transferring from the gas phase to the liquid phase BMIM-MET − 20.39 − 14.21 − 14.50
at the same geometry, GP is the polarization free energy of the BMIM-PHE − 23.13 − 15.21 − 16.19
solute-solvent system when the solute is inserted, GCDS is the BMIM-TRP − 27.34 − 18.68 − 19.66
component of the free energy that is normally associated with BMIM-TYR − 27.73 − 18.88 − 19.03
cavitation, dispersion, and solvent structure, ΔGN is the BMIM-VAL − 19.79 − 13.89 − 13.98
change in ΔG0S due to a change in nuclear coordinates and
192
to an extent, with the increasing order of the dielectric con-
stant, weaker is the solvation.
Conclusion
Systematic investigations on the C–H···O hydrogen bond be-
tween cations EMIM and BMIM and anions amino acid with-
in AAILs were carried out in gas and solvent phases using
density functional theory method. From the energetics, it can
be learned that the cation EMIM/BMIM binds strongly with
hydrophobic anions chosen. The favorable binding site is the
ortho position carbon of the cation. Topological parameters
electron density and Laplacian of electron density demonstrate
excellent linear inverse correlation with hydrogen bond length
for all the complexes considered. The total energy profile of
the AAILs show interaction energies of these IL systems is of
the order of covalent bond energy. NBO analysis predicts that
the C–H···O hydrogen bonds to be proper and red shifted in all
the complexes.
Acknowledgments Authors Dr. Senthilkumar Lakshmipathi and Mrs.
Shyama Muraledharan gratefully acknowledge the DST-SERB, New
Delhi, India, for granting the project and fellowship (EEQ/2016/000331).
Compliance with ethical standards
Ethical statement All the ethical guidelines have been adhered.
Conflict of interest The authors declare that they have no conflict of
interest
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