Interaction of dimethyl sulfoxide with two water
molecules induces three quite stable complexes with
interaction energies between -30.3 and -52.7 kJ.mol-
1 at MP2/6-311++G(2d,2p) level. The stability of
obtained complexes is mainly determined by the
O−H∙∙∙O hydrogen bonds along with the
complementary role of O−H∙∙∙S and C−H∙∙∙O
hydrogen bonds. Obtained results show that there is
a great cooperativity between both types of
hydrogen bonds with cooperative energies from -
12.9 to -22.9 kJ.mol-1. In ring structure of
DMSO∙∙∙2H2O, the formation of O−H∙∙∙O hydrogen
bond in the H2O∙∙∙H2O dimer enhances the stability
of O−H∙∙∙O and C−H∙∙∙O hydrogen bonds in the
ternary complexes. The strength increase of the
O−H∙∙∙O hydrogen bonds is larger than that of the
C−H∙∙∙O hydrogen bonds when the cooperativity
between types of hydrogen bonds happens. The
water molecule plays a different role in two types of
hydrogen bonds: proton-donor in O−H∙∙∙O(S) redshifting hydrogen bond and proton-acceptor in blueshifting C−H∙∙∙O hydrogen bond. In going from
binary complexes to relevant ternary complexes, the
magnitude of stretching frequency red shift of the
O−H bonds in the O−H∙∙∙O hydrogen bonds is
enhanced, while the magnitude of stretching
frequency blue shift of C−H bonds in C−H∙∙∙O
hydrogen bonds is weakened.
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Vietnam Journal of Chemistry, International Edition, 55(5): 578-584, 2017
DOI: 10.15625/2525-2321.2017-00511
578
A thoroughly theoretical investigation into complexes formed by
interaction of dimethyl sulfoxide with two water molecules
Pham Ngoc Khanh, Nguyen Thi Viet Nga, Nguyen Tien Trung
*
Laboratory of Computational Chemistry and Modelling, Department of Chemistry, Quy Nhon University
Received 14 April 2017; Accepted for publication 20 October 2017
Abstract
A computational study of the stability and the cooperative effect of hydrogen bonds in the complexes of dimethyl
sulfoxide and two water molecules was undertaken at the MP2/6-311++G(2d,2p) level of theory. The cooperative
energies of obtained complexes are significantly negative, indicating that there is a large cooperativity between types of
hydrogen bonds. The existence of the O−H∙∙∙O hydrogen bond present at dimer of water increases the stability of
O−H∙∙∙O and C−H∙∙∙O hydrogen bonds in the ternary complexes compared to relevant binary complexes. By vibrational
and NBO analyses, it is found that the magnitude of stretching frequency red shift of O−H bonds in the O−H∙∙∙O
hydrogen bonds is enhanced, whereas the extent of stretching frequency blue shift of C−H bonds in the C−H∙∙∙O
hydrogen bonds is weakened when the cooperativity of hydrogen bonds happens in the ternary complexes. Obtained
results of AIM analysis and stabilization energies indicate the larger contribution of the O−H∙∙∙O relative to the C−H∙∙∙O
hydrogen bond to cooperativity.
Keywords. Dimethyl sulfoxide, hydrogen bond, cooperativity.
1. INTRODUCTION
Noncovalent bonding interactions play an important
role in crystal packing, molecular recognition,
biological processes, and reaction selectivity [1, 2].
Understanding these interactions is thus essential for
unraveling the mysteries of cellular function in
health and disease as well as developing new drugs
and materials that serve human life [3]. Among
them, the subject of hydrogen bond A−H∙∙∙B can be
considered as a major interest due to a very
important role in many fields of chemistry, physics,
and biology. For instance, the presence of
C−H∙∙∙O/N hydrogen bonds has been found in
protein, DNA double helix, RNA, [4] However,
the origin of the blue-shifting hydrogen bond has not
been conformably understood [5, 6].
It is becoming increasingly apparent that
cooperativity involving many molecules is an
important component of intermolecular interactions,
particularly those involving hydrogen bonds. When
noncovalent binding interactions occur with positive
cooperativity, the observed binding energy is greater
than that in the isolated interaction, and vice versa
that is negative cooperativity. The cooperativity of
hydrogen bond plays an important role in controlling
and regulating the processes occurring in living
organisms. The occurrence of the cooperativity
among the subunits in hydrogen bonding system is
accompanied with changes in the dynamics of the
structures, for example, in DNA duplexes [7]. The
cooperativity is also important in the formation of
non-covalently bound aggregates of synthetic
materials [8]. Therefore, the cooperativity of
hydrogen bonds has paid much attention to
theoretical and experimental researches.
The aqueous solutions of dimethyl sulfoxide
(DMSO) have been extensively studied for their
unique biological and physicochemical properties
[9]. The use of the mixture of DMSO and CO2 in
PCA (Precipitation with a Compressed Antisolvent)
process to precipitate proteins and polar polymers
confronts some difficulties in both operation regions
that are below and upper the critical pressure of the
DMSO-CO2 mixture. Some experimental studies
suggested the use of water (H2O) as a cosolvent of
DMSO to modify the phase behavior of DMSO-CO2
and solve limitations of the PCA process [10, 11].
Kirchner and Reiher [12] classified interactions
between DMSO and water into O−H∙∙∙O red-shifting
and C−H∙∙∙O blue-shifting hydrogen bonded
contacts. The cooperativity between conventional
and unconventional hydrogen bonds in DMSO
aqueous solutions was reported by Li et al. [13, 14]
with some of different structures. Consequently, the
complexes between DMSO and two water molecules
VJC, 55(5), 2017 Nguyen Tien Trung et al.
579
are investigated thoroughly in the present work in
order to consider the cooperative effect of
interactions on the stability of complexes.
Additionally, stretching vibrational frequency and
natural bond orbital (NBO) analyses for the
complexes and relevant monomers are also
performed to understand further origin and
cooperativity of interactions formed in complexes.
2. COMPUTATIONAL DETAILS
Geometry optimizations, harmonic vibrational
frequencies of both monomers and complexes are
carried out at the MP2/6-311++G(2d,2p) level of
theory. Single point energy and basis set
superposition errors (BSSE) are also calculated at
the same level of theory. The interaction and
cooperative energies are corrected both ZPE (zero
point energy) and BSSE. All of the quantum
chemical calculations mentioned above are executed
using the Gaussian 09 program package [15]. The
“atoms-in-molecules” (AIM) [16] analysis at the
MP2/6-311++G(2d,2p) level is applied to determine
the bond critical points (BCP) and to estimate
electron densities and their Laplacians. Individual
energy of each hydrogen bond (EHB) is based on the
formula of Espinosa-Molins-Lecomte: EHB =
0.5V(r), in which V(r) is electron potential energy
density at BCP [17]. Electron density in antibonding
orbitals and electron density transfer between
monomers originated from complexation are
calculated by means of the natural bond orbital
(NBO) method using NBO 5.G software [18].
3. RESULTS AND DISCUSSION
3.1. Structures and AIM analysis
The geometric shapes and intermolecular distances
of the complexes optimized at the MP2/6-
311++G(2d,2p) level are displayed in Fig. 1, while
the features of BCPs and individual energy of each
hydrogen bond in the binary and ternary complexes
are tabulated in table 1. Each complex is stabilized
by different intermolecular contacts including
C5−H6∙∙∙O11 and O11−H12∙∙∙O10 in P1-B;
C1−H3∙∙∙O11, C5−H7∙∙∙O11 and O11−H12∙∙∙O10 in
P2-B; C1−H4∙∙∙O11, C5−H8∙∙∙O11 and S9∙∙∙O11 in
P3-B; C1−H2∙∙∙O11, O14−H15∙∙∙O10 and
O11−H12∙∙∙O14 in P1-T; C1−H3∙∙∙O11,
C5−H7∙∙∙O11, O14−H15∙∙∙O10 and O11−H12∙∙∙O14
in P2-T; C1−H4∙∙∙O11, C5−H8∙∙∙O11,
O14−H15∙∙∙S9 and O11−H12∙∙∙O14 in P3-T. There
is a difference in structure between binary and
ternary systems for the complexes of DMSO and
H2O that is presence of O−H∙∙∙O interaction in
H2O∙∙∙H2O in the ternary complexes, except for P3-
T with existence of O14−H15∙∙∙S9 interaction as
compared to S9∙∙∙O11 interaction in P3-B. The
complexes of ternary system found in present work
were not reported by Li et al. [13, 14].
P1-B P2-B P3-B
P1-T P2-T P3-T
Figure 1: Stable geometries of complexes formed by interactions of DMSO with 1H2O and 2H2O at
MP2/6-311++G(2d,2p)
VJC, 55(5), 2017 A thorough theoretical investigation into
580
Table 1: Selected parameters at the BCPs of intermolecular contacts at MP2/6-311++G(2d,2p)
Complex Contacts
ρ(r)
(au)
2ρ(r)
(au)
H(r)
a)
(au)
EHB
b)
(kJ.mol
-1
)
P1-B
C5−H6∙∙∙O11 0.009 0.036 0.0013 -8.3
O11−H12∙∙∙O10 0.029 0.098 0.0000 -32.2
P2-B
C1−H3∙∙∙O11 0.009 0.034 0.0011 -8.2
C5−H7∙∙∙O11 0.009 0.034 0.0011 -8.2
O11−H12∙∙∙O10 0.033 0.105 -0.0012 -37.5
P3-B
C1−H4∙∙∙O11 0.007 0.023 0.0008 -5.6
C5−H8∙∙∙O11 0.007 0.023 0.0008 -5.6
S9∙∙∙O11 0.008 0.030 0.0009 -
P1-T
C1−H2∙∙∙O11 0.014 0.048 0.0013 -12.4
O14−H15∙∙∙O10 0.035 0.112 -0.0015 -40.9
O11−H12∙∙∙O14 0.032 0.103 -0.0005 -35.2
P2-T
C1−H3∙∙∙O11 0.011 0.041 0.0013 -10.1
C5−H7∙∙∙O11 0.011 0.038 0.0010 -9.8
O14−H15∙∙∙O10 0.038 0.117 -0.0022 -44.3
O11−H12∙∙∙O14 0.035 0.109 -0.0009 -38.0
P3-T
C1−H4∙∙∙O11 0.009 0.032 0.0010 -8.0
C5−H8∙∙∙O11 0.009 0.029 0.0007 -7.4
O14−H15∙∙∙S9 0.018 0.044 0.0000 -14.6
O11−H12∙∙∙O14 0.026 0.092 0.0000 -28.3
a)
the total electron energy density;
b)
individual energy of each hydrogen bond.
All H∙∙∙O(S) and S∙∙∙O intermolecular distances
are in the range of 1.74−2.67 and 3.21 Å
respectively (table 1), which are shorter to sums of
van der Waals radii of the relevant atoms (being
2.72 Å and 3.0 Å for H∙∙∙O and H∙∙∙S corresponding
contact). This roughly suggests the presence of these
intermolecular interactions in the complexes
investigated. All the values of electron density (ρ(r))
and Laplacian (
2ρ(r)) at these BCPs are in the
range of 0.007-0.035 au and 0.023-0.117 au, except
for H15∙∙∙O10 contact in P2-T has very large
electron density of 0.038 au. All of them fall within
the limitation criteria for the formation of hydrogen
bond (0.002-0.035 au and 0.020-0.150 au for ρ(r)
and
2ρ(r), respectively). Therefore, the
intermolecular contacts in the complexes are
considered as hydrogen bonds, except for S9∙∙∙O11
chalcogen-chalcogen interaction in P3-B. The
C−H∙∙∙O and O−H∙∙∙S interactions are weak
hydrogen bonds as indicated by both the values
2ρ(r) > 0 and H(r) ≥ 0, whereas very large values of
ρ(r) and negative values of H(r) at BCPs of the
O−H∙∙∙O contacts are estimated, implying that these
strong hydrogen bonds are partly covalent in nature.
The formation of the S9∙∙∙O11 chalcogen-chalcogen
interaction in P3-B is more clarified by NBO
analysis being discussed below.
As indicated in table 1, there is an increase in
electron density at the BCPs and negative value of
EHB in the order of C−H∙∙∙O to O−H∙∙∙S and to
O−H∙∙∙O, implying that the strength of hydrogen
bonds tends to increase according to this trend. As a
result, the role of the contribution of interactions
formed into the total interaction energy of
complexes decreases in going from O−H∙∙∙O to
O−H∙∙∙S to C−H∙∙∙O and S∙∙∙O interaction. For both
binary and ternary systems, a decrease of both
electron density at the BCPs and the strength of
O−H∙∙∙O hydrogen bonds in the order of P2 to P1 to
P3 shape is observed. The obtained results suggest
that the stability of complexes decreases in the order
of P2 to P1 and finally to P3 shape.
Compared with corresponding complexes in
binary system, the electron densities at the BCPs in
ternary complexes are larger, by 0.002-0.005 au for
C−H∙∙∙O and 0.005-0.006 au for O−H∙∙∙O hydrogen
bonds. Furthermore, the individual energies of the
hydrogen bonds in ternary complexes are more
negative than those in corresponding binary
complexes by 1.6-4.1 kJ.mol
-1
for C−H∙∙∙O hydrogen
bonds and 6.8-8.7 kJ.mol
-1
for O−H∙∙∙O hydrogen
bonds. These results imply that the strength of
hydrogen bonds is enhanced when cooperativity
happens, and the larger magnitude of cooperativity
is observed for the O−H∙∙∙O hydrogen bond
compared to C−H∙∙∙O hydrogen bond. This result is
different from publication reported by Li et al. [13],
where the authors suggested the larger increase in
VJC, 55(5), 2017 Nguyen Tien Trung et al.
581
stability of the C−H∙∙∙O relative to O−H∙∙∙O
hydrogen bond taken from the cooperativity. This
should be due to the difference in the geometric
structure of complexes investigated.
3.2. Interaction and cooperative energies
Interaction and cooperative energies of complexes at
the MP2/6-311++G(2d,2p) level are summarized in
Table 2. All interaction energies of the complexes
for both binary and ternary systems are significantly
negative, indicating that the obtained complexes are
quite stable. Interaction energies for ternary
complexes range from -30.3 to -52.7 kJ.mol
-1
with
ZPE + BSSE corrections, which is more negative
than relevant binary complexes by ca. -24.4, -25.2
and -20.5 kJ.mol
-1
for P1, P2 and P3 shape
respectively. As be seen in Table 2, the decreasing
magnitude in complex strength is ordered in going
from P2 to P1 and finally to P3 shape for both
binary and ternary systems, which is in good
agreement with the results taken from the AIM
analysis mentioned above. Thus, the P2-T complex
is more stable than the P1-T and P3-T complexes by
ca. 5.3 and 22.4 kJ.mol
-1
respectively. Remarkably,
interaction energy of -27.5 kJ.mol
-1
for P2-B is
rather close to that for DMSO∙∙∙1H2O complex
(-28.3 kJ.mol
-1
) reported by Li et al. [14].
Table 2: Interaction energy ( E, EABC) and cooperativity energy (Ecoop) of binary and ternary complexes at
MP2/6-311++G(2d,2p), all in kJ.mol
-1
Complex E Complex EABC EAB EAC EBC Ecoop
P1-B -29.6 (-23.0) P1-T -60.5 (-47.4) -9.1 (-5.9) -23.3 (-17.1) -8.5 (-4.0) -19.7 (-20.5)
P2-B -35.3 (-27.5) P2-T -67.1 (-52.7) -26.8 (-20.1) -26.8 (-7.3) -11.2 (-2.3) -22.2 (-22.9)
P3-B -13.6 (-9.8) P3-T -40.9 (-30.3) -10.8 (-7.4) -7.5 (-3.8) -10.2 (-6.3) -12.2 (-12.9)
Values in brackets for both ZPE and BSSE corrections, A = DMSO, B = H2O, C = H2O.
The interaction energy (-52.7 kJ.mol-1) for the
most stable complex of ternary system (P2-T) is
more negative than that of DMSO∙∙∙1H2O (-28.28
kJ.mol
-1
) and DMSO∙∙∙2H2O (-47.92 kJ.mol
-1
)
reported by Li et al. at the MP2/6-31++G(d,p) level
[14]. However, the complex DMSO∙∙∙3H2O with
interaction energy of -58.23 kJ.mol
-1
in the literature
[14] is ca. 5.53 kJ.mol
-1
more stable than
DMSO∙∙∙2H2O (P2-T) in the present work. These
results show that the adding of water molecules into
DMSO system leads to increase the stability of
complexes.
The cooperative energy (Ecoop) is applied here to
evaluate the cooperativity of the hydrogen bonds in
the ternary system. Cooperative energies are
calculated using the expression:
Ecoop = ΔEABC - ΔEAB - ΔEBC - ΔEAC
Where ΔEAB, ΔEBC, ΔEAC are the interaction energies
of dimers A and B, B and C, A and C, respectively,
in the optimized geometry of the ternary system.
From Table 2, it can be seen that all the values of
Ecoop are significantly negative, indicating the
hydrogen bonds in the ternary complexes work in
concert with each other and enhance each other’s
strength. In these ternary systems, the absolute
values of Ecoop decrease in the order of P2-T > P1-T
> P3-T, which is consistent with the increase of the
interaction energy in this direction. It indicates that
there is a good correlation between cooperativity and
interaction energies of complexes examined. The
calculated energies due to cooperativity in the
ternary complexes are from -12,9 to -22.9 kJ.mol
-1
with ZPE + BSSE corrections, which are
significantly different with the values of -1.16 and -
1.67 kJ.mol
-1
for two other structures of
DMSO∙∙∙2H2O reported by Li et al. [14]. As a result,
it should be noteworthy that the second O−H∙∙∙O
hydrogen bond between two water molecules in the
ternary complexes found in our research induces
such a significant change of cooperativity.
3.3. Vibrational and NBO analyses
To classify and gain a clearer view on the origin and
cooperativity of the hydrogen bonds, the changes in
the C(O)−H bond lengths and its stretching
frequency, directions of electron density transfer
(EDT) and the factors causing the red and blue shift
of the C(O)−H bonds in hydrogen bonds at the
MP2/6-311++G(2d,2p) level are given in table 3.
Following complexation, the C−H bond lengths
are shortened by 0.0014−0.0036 Å and accompanied
by a stretching frequency increase of 8.4-40.7 cm
-1
,
whereas an elongation of O−H bond lengths by
0.0084-0.0223 Å and a decrease in its corresponding
stretching frequency from 167.1 to 438.4 cm
-1
are
observed as compared to those in the relevant
monomers. These results indicate that the C−H∙∙∙O
hydrogen bonds in the complexes belong to the blue-
shifting hydrogen bond, while the O−H∙∙∙O(S)
VJC, 55(5), 2017 A thorough theoretical investigation into
582
hydrogen bonds are red-shifting hydrogen bond. As
shown in Table 3, an elongation of O−H bond
lengths and a concomitant red shift of its stretching
frequency increase in the order of P3 < P1 < P2 for
both binary and ternary systems, which is consistent
with the increase in the stability of complexes
mentioned above.
In going from binary complexes to
corresponding ternary complexes, it is remarkable
that there is an opposite change in the red and blue
shift of O−H and C−H bonds in O(C)−H∙∙∙O
hydrogen bonds. Thus, a much larger red shift by ca.
90.8−120.7 cm-1 of the stretching frequencies of
O−H bonds in the O−H∙∙∙O hydrogen bonds is
obtained, whereas a magnitude of stretching
frequency blue shift of the C−H bonds in the
C−H∙∙∙O hydrogen bonds decreases by ca. 0.7−21.3
cm
-1
in the ternary complexes compared to the
corresponding binary complexes. As a result, the
cooperativity between types of hydrogen bonds
induces an enhancement of magnitude of stretching
frequency red shift of the O−H bonds in the O−H∙∙∙O
hydrogen bonds, but that causes a decrease in the
magnitude of blue shift of the C−H bonds in the
C−H∙∙∙O hydrogen bonds.
Table 3: Changes of bond length ( r) and corresponding stretching frequency ( ) of C(O)−H bonds
involved in hydrogen bond along with selected results for NBO analysis at MP2/6-311++G(2d,2p)
Complex EDT Hydrogen bond
r
(Å)
(cm
-1
)
Einter
(kJ.mol
-1
)
q(C/O)
(e)
q(H)
(e)
Δσ*
(C(O)−H)
(e)
Δ%s
(C(O))
(%)
P1-B
0.021
a)
-0.021
b)
C5−H6∙∙∙O11 -0.0028 29.7 2.9 -0.749 0.245 0.0004 0.77
O11−H12∙∙∙O10 0.0132 -261.5 50.0 -0.963 0.485 0.0208 3.16
P2-B
0.026
a)
-0.026
b)
C1−H3∙∙∙O11 -0.0033 33.9 3.8 -0.760 0.238 -0.0006 0.94
C5−H7∙∙∙O11 -0.0033 34.3 3.8 -0.760 0.238 -0.0006 0.94
O11−H12∙∙∙O10 0.0172 -347.6 60.5 -0.971 0.485 0.0284 3.52
P3-B
0.006
a)
-0.006
b)
C1−H4∙∙∙O11 -0.0036 38.7 1.3 -0.759 0.223 -0.0006 0.47
C5−H8∙∙∙O11 -0.0036 40.7 1.3 -0.759 0.223 -0.0006 0.47
S9∙∙∙O11 - - 2.3/0.3 - - - -
P1-T
0.025
a)
-0.019
b)
-0.006
c)
C1−H2∙∙∙O11 -0.0014 8.4 14.2 -0.764 0.261 0.0048 1.52
O14−H15∙∙∙O10 0.0196 -382.2 78.7 -0.970 0.493 0.0292 4.19
O11−H12∙∙∙O14 0.0152 -300.3 57.7 -0.968 0.499 0.0239 3.72
P2-T
0.025
a)
-0.007
b)
-0.018
c)
C1−H3∙∙∙O11 -0.0032 33.2 9.5 -0.762 0.245 0.0010 1.44
C5−H7∙∙∙O11 -0.0031 30.5 8.3 -0.762 0.245 0.0015 1.39
O14−H15∙∙∙O10 0.0223 -438.4 106.9 -0.972 0.499 0.0337 4.32
O11−H12∙∙∙O14 0.0168 -331.9 63.1 -0.974 0.495 0.0263 3.93
P3-T
0.026
a)
-0.012
b)
-0.014
c)
C1−H4∙∙∙O11 -0.0030 32.9 5.3 -0.763 0.237 0.0003 0.88
C5−H8∙∙∙O11 -0.0029 32.8 4.4 -0.762 0.236 0.0004 0.79
O14−H15∙∙∙S9 0.0084 -167.1 21.8 -0.950 0.466 0.0153 2.17
O11−H12∙∙∙O14 0.0107 -206.6 36.3 -0.964 0.490 0.0223 3.01
a),b),c)
for charge of A, B, C respectively.
There are various trends of electron density
transfer between DMSO and H2O as a result of
complex formation. The positive values of EDT(a)
ranging from 0.006 to 0.026 e indicate that the
electron density is transferred from DMSO to H2O.
The formation of S9∙∙∙O11 chalcogen-chalcogen
interaction in P3-B complex is resulted from
electron density transfer of both from S9 lone pairs
to σ*(O11−H12(13)) orbital (2.3 kJ.mol-1) and from
O11 lone pairs to σ*(S9−O10) orbital (0.3 kJ.mol-1).
As shown in table 3, there are increases in s-
character of the O(H) atoms from 2.17 to 4.32% and
electronic population of the σ*(O−H) orbitals
between 0.0153 and 0.0337 e for all complexes,
meaning that an elongation of the O−H bond lengths
and a red shift of its stretching frequency arise from
an increase in electron population in the σ*(O−H)
orbitals overcoming an increase in s-character of the
O(H) hybrid orbital. Remarkably, the increase in
electron population of σ*(O−H) orbitals is larger for
ternary complexes than for binary complexes. For
the C−H∙∙∙O hydrogen bonds of binary complexes, a
C−H bond contraction of and a blue shift of its
stretching frequency in the C−H∙∙∙O hydrogen bonds
are contributed by a decrease of population in the
σ*(C−H) orbital and an increase of s-character
VJC, 55(5), 2017 Nguyen Tien Trung et al.
583
percentage of C(H) orbital, except for C5−H6∙∙∙O11
hydrogen bond of P1-B complex. However, a C−H
bond contraction accompanied by its stretching
frequency blue shift in the C−H∙∙∙O hydrogen bonds
for all ternary complexes is mainly determined by an
increase of s-character percentage of C(H) atoms
since the population of the σ*(C−H) orbital is
enhanced upon complexation (cf. table 3). These
results also support for observation of change in the
magnitude of stretching frequency red and blue shift
of the O(C)−H bonds in hydrogen bonds that there is
cooperativity mentioned above.
From the structure of binary to corresponding
ternary complexes, the Einter(n(O) σ*(O−H)) values
are increased by ca. 28.2−46.4 kJ.mol-1, while the
Einter(n(O) σ*(C−H)) values are also increased by
ca. 3.1−11.3 kJ.mol-1. This suggests the contribution
from the orbital interaction to the cooperativity is
much larger for O−H∙∙∙O as compared to C−H∙∙∙O
hydrogen bond, which is in good accordance with
AIM analysis mentioned above. Furthermore, there
is an increase in both negative charge on the O/C
atoms and positive charge on H atoms in ternary
complexes compared to binary complexes, making it
easier than to form C(O)−H∙∙∙O hydrogen bonds in
ternary complexes. These results affirm again that
the strength of C(O)−H∙∙∙O hydrogen bonds is
enhanced in ternary with respect to binary
complexes.
4. CONCLUDING REMARKS
Interaction of dimethyl sulfoxide with two water
molecules induces three quite stable complexes with
interaction energies between -30.3 and -52.7 kJ.mol
-
1
at MP2/6-311++G(2d,2p) level. The stability of
obtained complexes is mainly determined by the
O−H∙∙∙O hydrogen bonds along with the
complementary role of O−H∙∙∙S and C−H∙∙∙O
hydrogen bonds. Obtained results show that there is
a great cooperativity between both types of
hydrogen bonds with cooperative energies from -
12.9 to -22.9 kJ.mol
-1
. In ring structure of
DMSO∙∙∙2H2O, the formation of O−H∙∙∙O hydrogen
bond in the H2O∙∙∙H2O dimer enhances the stability
of O−H∙∙∙O and C−H∙∙∙O hydrogen bonds in the
ternary complexes. The strength increase of the
O−H∙∙∙O hydrogen bonds is larger than that of the
C−H∙∙∙O hydrogen bonds when the cooperativity
between types of hydrogen bonds happens. The
water molecule plays a different role in two types of
hydrogen bonds: proton-donor in O−H∙∙∙O(S) red-
shifting hydrogen bond and proton-acceptor in blue-
shifting C−H∙∙∙O hydrogen bond. In going from
binary complexes to relevant ternary complexes, the
magnitude of stretching frequency red shift of the
O−H bonds in the O−H∙∙∙O hydrogen bonds is
enhanced, while the magnitude of stretching
frequency blue shift of C−H bonds in C−H∙∙∙O
hydrogen bonds is weakened.
Acknowledgement. This research is funded by the
Vietnam National Foundation for Science and
Technology Development (NAFOSTED) under grant
number 104.06-2017.11.
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Corresponding author: Nguyen Tien Trung
Quy Nhon University
No. 170, An Duong Vuong, Quy Nhon, Binh Dinh Vietnam
E-mail: nguyentientrung@qnu.edu.vn.
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