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To cite this article: V. Umadevi, L. Senthilkumar & P. Kolandaivel (2013) Theoretical investigations on the hydrogen bonding
of nitrile isomers with H2O, HF, NH3 and H2S, Molecular Simulation, 39:11, 908-921, DOI: 10.1080/08927022.2013.777840
To link to this article: http://dx.doi.org/10.1080/08927022.2013.777840
Theoretical investigations on the hydrogen bonding of nitrile isomers with H2O, HF, NH3
and H2S
V. Umadevia, L. Senthilkumarb* and P. Kolandaivelb
a
Faculty of Physics, Dr. Mahalingam College of Engineering and Technology, Pollachi, Coimbatore, Tamil Nadu, India; bDepartment of
Physics, Bharathiar University, Coimbatore, Tamil Nadu, India
1. Introduction
Hydrogen bonding is of central importance in the
molecular sciences for both theoretical and practical
reasons [1 8]. The study of hydrogen bond has generated
substantial interest, given its relevance in the field of
chemistry and biology [9,10]. It largely determines the
physical properties of many common condensed phase
systems including water [11,12]. It represents the strongest
force governing the influence of solvents on molecular
structure and reactivity, and is a prerequisite for the proper
understanding of chemical activity taking place in aqueous
solution. The formation of typical moderate or strong
conventional hydrogen bonds is relatively easy to verify,
because the presence of these bonds substantially modifies
the structural, energetic and spectroscopic properties of the
system in question [13 15]. In moderate and strong
hydrogen bonds, the acceptor atom is commonly expected
to be an electronegative atom with an accessible lone pair
[13,16,17]. In recent years, considerable attention has
focused upon the CZH Y type of weak hydrogen bonds
due to their proper red-shifting and improper blue-shifting
nature. By red shifting, it is meant that the CZH bond in
the complex CZH Y is longer and has a lower vibration
frequency than in isolated CZH. This had long been
viewed as characteristic of hydrogen bonding [18 21],
and correlations were found between the frequency shifts,
bond length changes and interaction energies [20,23,24].
2. Computational details
The geometry optimisation of the complexes formed from
interaction of nitrile isomers (C3H3NO) with water,
hydrogen fluoride, ammonia and hydrogen sulphide have
been carried out using B3LYP and MP2 methods and 6311 G(d,p) basis set. Frequency calculations were
carried out to verify that the structures were minima on the
potential energy surface. The interaction energy was
corrected for the basis set superposition error using the
counterpoise method of Boys and Bernardi [35] and has
been calculated by the following equation:
DE EAB 2 EA AB EB AB;
where DE is the interaction energy of the complex, EAB is
the energy of the complex, EA(AB) and EB(AB) are the
energies of monomers A and B in the complex,
respectively. Topological analysis was carried out to
calculate the charge density (r) and Laplacian of charge
density 72 r for bonds using Baders (AIM theory) [32].
NBO analysis have been carried out on the optimised
structures at B3LYP and MP2 methods of theories with 6311 G(d,p) basis set using NBO 3.1 program [34].
All the calculations were carried out using Gaussian 03
program [36]. Finally, the Morokuma energy decomposition analysis was carried out for all the complexes using
HF method with 6-311 G(d,p) basis set using the
GAMESS electronic structure program [37].
3.
Bond
OZH O
FZH N
OZH N
OZH S
Structure
oxo4H2O
oxo4HF1
oxo4NH3
oxo4H2S
1.811
1.774
1.794
2.421
B3LYP
1.823
1.829
1.793
2.415
MP2
Bond length
178.2
179.5
171.7
169.3
B3LYP
178.5
179.6
173.2
177.2
MP2
Bond angle
MP2
2 7.98
2 8.14
2 10.96
2 3.90
B3LYP
28.69
29.76
212.01
24.33
0.032
0.037
0.043
0.018
B3LYP
DE
0.031
0.031
0.042
0.018
MP2
0.117
0.115
0.097
0.042
B3LYP
f2r
0.116
0.110
0.102
0.045
MP2
0.0010
2 0.0017
2 0.0057
0.0008
B3LYP
H(r)
0.0010
0.0003
20.0059
0.0008
MP2
and bond angle in degrees), interaction energy (DE) in kcal/mol, topological analysis of electron density (r), Laplacian of
Table 1. Optimised structural parameters (bond length in A
electron density (f2r) and electronic energy density H(r) in a.u. for the most stable C3H3NO X (X H2O, HF, NH3 and H2S) complexes calculated using B3LYP and MP2 methods
at 6-311 G(d,p) basis set.
n(X) (X O, N and S)
E (2) (kcal/mol)
Structure
Bond
B3LYP
MP2
B3LYP
MP2
B3LYP
MP2
oxo4H2O
oxo4HF1
oxo4NH3
oxo4H2S
OZH O
FZH N
OZH N
OZH S
1.971(1.997)
1.939(1.971)
1.934(1.997)
1.965(1.999)
1.980(1.997)
1.960(1.976)
1.952(1.997)
1.977(1.999)
0.034(0.010)
0.037(0.0)
0.069(0.010)
0.039(0.010)
0.023(0.007)
0.018(0.0)
0.050(0.007)
0.026(0.010)
13.73
17.22
27.53
9.09
14.42
14.12
31.80
10.36
Note: All values were calculated using B3LYP and MP2 methods at 6-311 G(d,p) basis set. Monomer values are within parentheses.
CZO
CZH
OZH
B3LYP
MP2
B3LYP
MP2
B3LYP
MP2
B3LYP
MP2
1.154
1.152
1.153
1.157
1.175
1.177
1.175
1.176
1.177
1.175
1.205
1.199
1.433
1.214
1.210
1.433
1.092
1.098
1.082
1.084
1.085
1.092
1.098
1.083
1.085
1.085
0.9646
0.9659
0.9644
0.9640
3.2
3.2.2
X HF
X NH3
X H2S
Structure/Bond
B3LYP
MP2
B3LYP
MP2
B3LYP
MP2
B3LYP
MP2
oxo1X/ CZO
oxo2X/ CZO
oxo5 X / CZO
oxo1X1/ CZN
oxo2X1/ CZN
oxo3X1/ CZN
oxo4X1/ CZN
oxo5X1/ CZN
1.208
1.204
1.435
1.154
1.152
1.153
1.157
1.151
1.214
1.214
1.440
1.175
1.173
1.175
1.176
1.174
1.213
1.207
1.440
1.151
1.150
1.151
1.154
1.150
1.221
1.216
1.443
1.174
1.171
1.173
1.174
1.172
1.208
1.203
1.430
1.153
1.153
1.154
1.158
1.153
1.217
1.214
1.436
1.177
1.175
1.176
1.178
1.176
1.207
1.202
1.432
1.153
1.152
1.153
1.156
1.152
1.214
1.212
1.434
1.177
1.174
1.176
1.177
1.175
12
10
E (kcal/mol)
4
1.8
2.0
2.2
2.4
R()
Figure 2. Correlation between interaction energy and the Hbond distance calculated using B3LYP and MP2 level of theories,
for the most stable C3H3NO X (X H2O, HF, NH3 and H2S)
complexes.
acid and NH3 a strong base in the gas phase. The hydrogen
bonds OZH O, OZH F, OZH N, OZH S have
their bond distances decreasing in the order of H S .
H F . H O . H N and their bond angles are around
1708, showing that all the hydrogen bonds are reasonably
linear and strong. The interaction energy for NH3
complexes is found to be greater (, 11.61 kcal/mol in
B3LYP and , 10.71 kcal/mol in MP2). The increase in
energy of the NH3 complex is due to the larger proton
affinity of NH3. Since HF is a weak proton acceptor, the
HF complexes have a lesser (, 4.38 kcal/mol in B3LYP
and , 3.99 kcal/mol in MP2) interaction energy than the
corresponding H2O, NH3 and H2S complexes (Supporting
information, Tables S1 S4). In particular, comparing
the H2S and HF interaction energies (, 3.84 and
, 3.99 kcal/mol) with those of H2O and NH3 (, 7.77
and , 10.71 kcal/mol) in MP2 level of theory shows that
OZH S hydrogen bond is much weaker followed by
OZH F, OZH O and OZH N. By clearly comparing the complexes where the hydroxyl group acts as proton
donor, the basicity strength of the hydrogen bond acceptor
increases in the order H2S , HF , H2O , NH3. Finally,
an inverse correlation between interaction energy and Hbond length [48] with the coefficient value greater than
0.97 is noticed for all the complexes (except C3H3NO
NH3), and is shown in plots (Supporting information,
Figures S5, S6 and S8). Figure S7 shows an inverse
correlation value of , 0.9 for C3H3NO NH3 complexes.
0.040
0.12
0.11
0.10
0.030
(au)
(au)
0.035
0.08
0.025
0.09
0.07
0.020
1.8
1.9
2.0
2.1
2.2
2.3
2.4
2.5
0.11
(au)
0.10
0.09
0.08
0.07
0.06
0.05
0.04
1.7
1.8
1.9
2.0
2.1
0.05
0.04
R()
0.06
0.015
1.7
2.2
2.3
2.4
2.5
R()
10
E(kcal/mol)
3.5
NBO analysis
The NBO analysis [52,53] has been a reliable tool for the
rationalisation of H-bonds that correlate well with changes
in bond length in accordance with the basic chemical
concepts. It is also used to derive information on the
changes of charge densities in proton donor and acceptor
as well as in the bonding and antibonding orbitals. As we
know, H-bonds are formed due to charge transfer (CT)
from the proton acceptor to proton donor, and hence the
amount of CT plays a significant role in the elongation and
contraction of the H Y bond. For each donor and
acceptor, the hyperconjugative interaction energy E (2)
(stabilisation energy) associated with i j delocalisation is
given by the following equation:
E 2 DEij qi
F 2 i; j
;
1j 2 1i
0.300 (0.254)
2 0.952 (20.524)
0.281 (0.253)
0.080 (0.031)
(0.251)
(2 0.376)
(0.245)
(0.046)
0.295
20.863
0.277
0.099
(20.508)
(20.279)
(20.760)
(20.061)
20.605
20.306
20.834
20.133
(20.502)
(20.270)
(20.736)
(20.092)
2 0.596
2 0.287
2 0.832
2 0.172
(0.282)
(0.302)
(0.282)
(0.282)
0.445
0.477
0.514
0.234
MP2
B3LYP
MP2
MP2
B3LYP
Z( H and C)
Y( O, N and S)
(0.268)
(0.291)
(0.268)
(0.268)
0.417
0.452
0.484
0.201
(20.230)
(20.302)
(20.230)
(20.230)
20.359
20.424
20.385
20.198
(2 0.170)
(2 0.291)
(2 0.170)
(2 0.170)
20.282
20.416
20.293
20.121
OZH OZH
FZH NZC
OZH NZH
OZH SZH
B3LYP
MP2
B3LYP
oxo4H2O
oxo4HF1
oxo4NH3
oxo4H2S
Bond
(XZH YZZ)
Structure
3.7
X( O and F)
Table 5. Natural atomic charges of the atoms involved in (XZH Y) bond upon complexation and monomers (within parentheses) calculated using B3LYP and MP2 methods at
6-311 G(d,p) basis set.
EX
PL
CT
MIX
20
Energy(kcal/mol)
20
B
Structure
Table 6. Morokuma analysisa of interaction energiesb (DE, kcal/mol) of the most stable C3H3NOX (X H2O, HF, NH3 and H2S)
complexes and Dipole moment (in Debye) calculated using B3LYP and MP2 methods at 6-311 G(d,p) basis set.
Dipole moment
Structure
oxo4H2O (A)
oxo4HF1 (B)
oxo4NH3 (C)
oxo4H2S (D)
a
b
c
ES
EX
PL
CT
MIX
DE
DEBSSE
2 15.60
2 12.94
2 22.84
2 7.80
11.09
9.64
20.19
7.89
22.55
23.85
25.53
22.06
2 2.87
2 3.72
2 6.18
2 2.47
1.39
2.54
4.01
1.46
2 8.54
2 8.33
2 10.35
2 2.98
27.57
27.85
29.51
22.53
B3LYP
MP2
7.74
8.24
7.80
6.72
7.78
8.18
7.66
6.79
4. Conclusion
In this paper, we have studied the minimum energy
structures for C3H3NO H2O, C3H3NO HF, C3H3NO
NH3, C3H3NO H2S complexes using B3LYP and MP2
methods using 6-311 G(d,p) basis set. The most
stable structures have their bond length and bond angle in
and 169.68 179.58, respectively,
the range 1.774 2.421 A
confirming the presence of hydrogen bond in all the
structures. Categorisation of the type of hydrogen bond
involved in the various complexes facilitated the study of
Acknowledgements
The authors thank High Performance Computing Facility (HPCF)
of DST at Hyderabad for providing computational facility to
carry out the simulation work.
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