Sei sulla pagina 1di 15

This article was downloaded by: [The University Of Melbourne Libraries]

On: 05 October 2013, At: 12:38


Publisher: Taylor & Francis
Informa Ltd Registered in England and Wales Registered Number: 1072954 Registered office: Mortimer House,
37-41 Mortimer Street, London W1T 3JH, UK

Molecular Simulation
Publication details, including instructions for authors and subscription information:
http://www.tandfonline.com/loi/gmos20

Theoretical investigations on the hydrogen bonding of


nitrile isomers with H2O, HF, NH3 and H2S
a

V. Umadevi , L. Senthilkumar & P. Kolandaivel


a

Faculty of Physics, Dr. Mahalingam College of Engineering and Technology, Pollachi,


CoimbatoreTamil NaduIndia
b

Department of Physics, Bharathiar University, CoimbatoreTamil NaduIndia


Published online: 11 Apr 2013.

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

PLEASE SCROLL DOWN FOR ARTICLE


Taylor & Francis makes every effort to ensure the accuracy of all the information (the Content) contained
in the publications on our platform. However, Taylor & Francis, our agents, and our licensors make no
representations or warranties whatsoever as to the accuracy, completeness, or suitability for any purpose of the
Content. Any opinions and views expressed in this publication are the opinions and views of the authors, and
are not the views of or endorsed by Taylor & Francis. The accuracy of the Content should not be relied upon and
should be independently verified with primary sources of information. Taylor and Francis shall not be liable for
any losses, actions, claims, proceedings, demands, costs, expenses, damages, and other liabilities whatsoever
or howsoever caused arising directly or indirectly in connection with, in relation to or arising out of the use of
the Content.
This article may be used for research, teaching, and private study purposes. Any substantial or systematic
reproduction, redistribution, reselling, loan, sub-licensing, systematic supply, or distribution in any
form to anyone is expressly forbidden. Terms & Conditions of access and use can be found at http://
www.tandfonline.com/page/terms-and-conditions

Molecular Simulation, 2013


Vol. 39, No. 11, 908921, 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

Downloaded by [The University Of Melbourne Libraries] at 12:38 05 October 2013

(Received 6 July 2012; final version received 14 February 2013)


The hydrogen bonds formed by the interaction of nitriles with water, hydrogen fluoride, ammonia and hydrogen sulphide
have been studied using B3LYP and second-order Mller Plesset perturbation (MP2) methods and 6-311 G(d,p) basis
set. The energies and structures of 80 hydrogen-bonded complexes between nitriles and small molecules were examined
systematically using B3LYP and MP2 procedure. Categorisation of the hydrogen bonds involved in the various complexes
led to an ordering of hydrogen bond donor and acceptor abilities for some functional groups. The interaction energies have
been corrected for the basis set superposition error using Boys counterpoise correction method. The Morokuma energy
decomposition analysis reveals that the strong interactions are due to the attractive contributions from the electrostatic (ES),
polarisation (PL) and charge transfer (CT) components. The topological parameters, electron density and Laplacian of
electron density show excellent correlation with the hydrogen bond length. Natural bond orbital (NBO) analysis has also
been performed to study the CT from proton acceptor to the antibonding orbital of the H Y bond in the proton donor part of
complexes. The frequency analysis of CZH Y bond in the complexes indicates the blue-shifting nature largely in case of
sp2 hybridised carbon atom.
Keywords: nitriles; NBO; CZH S; blue shift hydrogen bond; Morokuma analysis

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].

*Corresponding author. Email: lsenthilkumar@buc.edu.in


q 2013 Taylor & Francis

In blue shifting, on the other hand, the CZH bond length


decreases and the CZH frequency increases [22,25].
Nitriles were chosen for this study because of practical
and theoretical considerations. Many nitriles are commercially available and others can be synthesised easily. They
are linear groups so that possible steric complications can
be avoided. Nitriles form moderately strong hydrogen
bonds to standard proton donors. Infrared spectroscopic
studies of the proton accepting power of nitriles are
numerous. Generally, nitriles are organic compounds that
contain a cyano group as the characteristic functional
group. They are adaptable to laboratory and industrial
applications because of their versatile chemical reactivity
and unusual physical properties. In this study, nitrile
isomers with molecular formula C3H3NO are studied. The
first structural studies of C3H3NO were reported by
Minyaev et al. [27] employing MINDO/3 and ab initio
methods. Badawi and El-Rayyes [28] have carried out
normal coordinate analysis using the vibrational wave
numbers of the stable conformers of 3-C3H3NO and 3C3H3NO2. The potential energy surfaces of acetyl cyanide
and its functional isomer acetyl isocyanide in their
electronic ground state have been investigated [29]. The
oxidative cyclisation of 3-oxopropanenitriles with alkenes
containing 2-thienyl group by manganese (III) acetate was
studied [30]. A number of nitrogen containing organic
molecules have been detected in dense interstellar clouds,

Downloaded by [The University Of Melbourne Libraries] at 12:38 05 October 2013

Molecular Simulation 909


and one such molecule of special interest is the pre-biotic
three-membered ring species oxiranecarbonitrile
(C3H3NO). This molecule has been suggested as a
precursor of important prebiotic molecules [26]. Besides,
prior researches on the structures, systematic studies of the
interactions of nitriles with H2O, HF, NH3 and H2S were
performed. The different functional groups present in the
nitriles interact with small molecules at consistent and
reliable levels of ab initio and density functional (DFT)
theory. The principle aim of this study is to understand the
hydrogen-bonding interactions between nitriles and small
molecules, which could enable us to understand the
bonding properties of nitriles at different binding sites.
In this study, five different isomers of nitriles are
considered and are labelled as oxo1, oxo2, oxo3, oxo4 and
oxo5. Linear structures have been noticed in the first four
isomers and they differ based on the position of the three
hydrogen atoms present, whereas oxo5 possess a ring-like
structure. Complexes formed between various small
molecules (X H2O, HF, NH3 and H2S) and different
binding sites (viz., the carbonyl, hydroxy and cyano
functional groups) in C3H3NO have resulted in as many as
80 structures. The molecule H2O interacts with C3H3NO
through carbonyl group forming complexes oxo1X,
oxo2X and oxo5X (labelled as) and complexes oxo3X
and oxo4X when interacted with hydroxyl group (labelled
as). All the above complexes have OZH O hydrogen
bond in common. The HF molecule interacts with
C3H3NO through carbonyl group (oxo1X, oxo2X and
oxo5X) with FZH O hydrogen bond, whereas interaction through hydroxyl group (oxo3X and oxo4X) results
in OZH F hydrogen bond. Similarly, when NH3
interacts with C3H3NO through carbonyl group, oxo1X,
oxo2X and oxo5X complexes are formed with NZH O
hydrogen bond, whereas interaction through hydroxyl
group results in oxo3X and oxo4X complexes with
OZH N hydrogen bond. The molecule H2S interacts
with C3H3NO through carbonyl group forming SZH O
hydrogen bond in complexes labelled as oxo1X, oxo2X
and oxo5X and OZH S hydrogen bond in complexes
labelled as oxo3X and oxo4X when interacted with
hydroxyl group. On the other hand, the interaction of H2O,
HF, NH3, H2S with C3H3NO through cyano group results
in complexes labelled as oxo1X1, oxo2X1, oxo3x1,
oxo4X1 and oxo5x1 forming OZH N (H2O), FZH N
(HF), NZH N (NH3) and SZH N (H2S) hydrogen
bonds, respectively. The stability of the complexes has
been analysed through analysis of interaction energies. In
addition, a study on the components within interaction
energy responsible for the stability of the complexes has
been performed using the Morokuma energy decomposition analysis [31]. The nature of the hydrogen bonds
formed in the system is analysed through the topological
analysis based on Baders [32] atoms in molecules (AIM)
theory which has proved invaluable in characterising the

hydrogen bond by a scheme through partitioning the


molecular space into domains through the vanishing
gradient of electron density. A counter study on the nature
of these hydrogen bonds has also been performed through
natural bond orbital analysis [33,34].

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.

Results and discussion

3.1 Type of hydrogen-bonding interactions


Of the 80 structures of C3H3NO H2O, C3H3NO HF,
C3H3NO NH3 and C3H3NO H2S complexes optimised
using B3LYP and MP2 level of theories with the 6-311
G(d,p) basis set, the four most stable complexes are
shown in Figure 1. The computed geometries of the
complexes provide some insights into the nature of the
stabilising interactions. The corresponding structural
parameters along with interaction energies of the most
stable complexes calculated using the same level of
theories with 6-311 G(d,p) basis set are given in
Table 1. Nitrile isomers possess three possible sites,
carbonyl, hydroxy and cyano groups, for the hydrogen
bond formation. It is evident from Table 1 that the small
molecules H2O, NH3 and H2S interact with C3H3NO
through the hydroxy group and with HF through the cyano

Downloaded by [The University Of Melbourne Libraries] at 12:38 05 October 2013

Figure 1. Optimised structures of the most stable C3H3NO X


(X H2O, HF, NH3 and H2S) complexes using B3LYP (within
parentheses) and MP2 methods at 6-311 G(d,p) basis set.

group. The structures follow the expected patterns, with a


hydrogen bond angle above 1738 and hydrogen bond
. A linear hydrogen
distance in the range 1.793 2.415 A
bond is preferred on electrostatic (ES) grounds and is
known to be common. This is true for the interaction of
C3H3NO with small molecules such as H2O, HF and NH3.
But in the case of the interaction of C3H3NO with H2S, the
bond angle is linear only when the hydrogen bond distance
(Table 1).
is around 2.415 A

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.

910 V. Umadevi et al.

Molecular Simulation 911


Table 2. The occupation number of lone pair in the proton acceptor X and of antibonds of proton donor HZY involved in hydrogen
bonds and the energy E(2) from hyper conjugative interaction [stabilisation energy (kcal/mol)] of the most stable C3H3NO X (X H2O,
HF, NH3 and H2S) complexes.
n[s*(HZY)] (Y O and F)

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

Downloaded by [The University Of Melbourne Libraries] at 12:38 05 October 2013

Note: All values were calculated using B3LYP and MP2 methods at 6-311 G(d,p) basis set. Monomer values are within parentheses.

) of the monomers calculated using B3LYP and MP2 methods at


Table 3. Selected optimised structural parameters (bond length in A
6-311 G(d,p) basis set.
CZN
Structure
oxo1
oxo2
oxo3
oxo4
oxo5

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

The remaining 76 structures are shown in the


Supporting information (Figures S1 S4, online only).
Key geometrical parameters namely bond length and bond
angle together with interaction energies of all the
complexes calculated using B3LYP and MP2 level of
theories with 6-311 G(d,p) basis set are given in the
Supporting information, Tables S1 S4, respectively. It is
evident from the structural parameters that the small
molecules interact with C3H3NO through any one of the
three possible sites, i.e. carbonyl, hydroxy and cyano
groups. In addition, CZH Y (Y O, F, N and S)
hydrogen bond formation is also possible in some
complexes. Figure S1 shows 10 C3H3NO H2O complexes
in which C3H3NO interacts with H2O through carbonyl
group forming OZH O hydrogen bond in oxo1H2O,
oxo2H2O and oxo5H2O, whereas in oxo3H2O and
oxo4H2O, the interaction is through hydroxy group
forming O HZO hydrogen bond. In the last five isomers,
namely oxo1H2O1, oxo2H2O1, oxo3H2O1, oxo4H2O1
and oxo5H2O1, C3H3NO interacts with H2O through
cyano group forming OZH N hydrogen bond. Thus in
C3H3NO H2O complex, except for oxo3H2O and
oxo4H2O, in all other isomers H2O acts as a proton
donor and C3H3NO acts as a proton acceptor. Similarly in
C3H3NO HF (Figure S2), C3H3NO NH3 (Figure S3) and
C3H3NO H2S (Figure S4) complexes, except for oxo3HF,
oxo4HF, oxo3NH3, oxo4NH3, oxo3H2S and oxo4H2S, in
all other complexes C3H3NO acts as proton donor. In
oxo3HF and oxo4HF, C3H3NO interacts with HF through

hydroxy group forming OZH F hydrogen bond. Also in


oxo3NH3 and oxo4NH3, C3H3NO interacts with NH3
through hydroxy group forming OZH N hydrogen bond.
In oxo3H2S and oxo4H2S, C3H3NO interacts with H2S
through hydroxy group forming OZH S hydrogen bond.
In oxo3HF, oxo4HF, oxo3NH3, oxo4NH3, oxo3H2S and
oxo4H2S small molecules HF, NH3 and H2S act as proton
donors and C3H3NO acts as a proton acceptor.

3.2

Relative hydrogen bond acceptor ability

3.2.1 Carbonyl groups as proton acceptors


The complexes in which the small molecules are clearly
the donors can further be categorised according to the
nature of the atom acting as the hydrogen bond acceptor
site. In complexes oxo1H2O, oxo2H2O, oxo1HF, oxo2HF,
oxo1NH3, oxo2NH3, oxo1H2S and oxo2H2S, small
molecules namely H2O, HF, NH3 and H2S interact with
C3H3NO through carbonyl oxygen which is a good
acceptor site [38,39], resulting in YZH O [Y O, F, N
and S] hydrogen bond formation (Supporting information,
Tables S1 S4). The hydrogen bond distances calculated
using MP2 are equal to or slightly greater than its
corresponding B3LYP values. Here the complex oxo2H2O
results in OZH O hydrogen bond and its bond length
(MP2). The complexes, oxo1NH3 and
value is 2.111 A
oxo2NH3 possess NZH O hydrogen bond with an
. In complexes
average bond length value of 2.442 A
oxo1H2S and oxo2H2S, SZH O hydrogen bond is

Downloaded by [The University Of Melbourne Libraries] at 12:38 05 October 2013

912 V. Umadevi et al.


. But
formed with an average bond length value of 2.673 A
oxo1HF and oxo2HF complexes with FZH O hydrogen
bond have their average bond length value of around
[39], which is less compared to its corresponding
1.792 A
H2O, NH3 and H2S complexes. The average binding
energy of the complexes oxo1HF and oxo2HF is
5.53 kcal/mol (calculated using MP2), which is greater
when compared with the average binding energies of
oxo1H2O and oxo2H2O (4.02 kcal/mol), oxo1NH3 and
oxo2NH3 (3.25 kcal/mol) and oxo1H2S and oxo2H2S
(1.84 kcal/mol). Here in the above five complexes,
carbonyl oxygen becomes a slightly weaker acceptor
when interacting with H2O, NH3 and H2S but becomes an
equally good acceptor site when it interacts with HF, thus
confirming the order of acidity of small molecules
(HF . H2O . NH3 . H2S). The complexes oxo5H2O,
oxo5HF, oxo5NH3 and oxo5H2S possess a cyclic
structure. Here, the small molecules interact with oxygen
atom, bonded to carbon atoms on either side. Here again,
the complex oxo5HF with O HZF hydrogen bond has its
bond length less compared to its corresponding H2O, NH3
and H2S complexes. The binding energies follow the same
order of basicity: oxo5HF . oxo5H 2O . oxo5NH 3
. oxo5H2S (5.97 kcal/mol . 5.05 kcal/mol . 4.15 kcal/
mol . 2.23 kcal/mol).

3.2.2

Cyano groups as proton acceptors

The second hydrogen bond acceptor site of C3H3NO is the


cyano group. The cyano group is well known to be a
moderately strong acceptor because of the directed lone
pair orbital on the nitrogen atom [40]. The linearity of the
group prevents steric complications in intermolecular
hydrogen bonding studies. Hydrogen bond strengths
between nitriles and phenol, and nitriles and methanol
have been measured [41]. Small molecules H2O, HF, NH3
and H2S interact with C3H3NO through cyano group
resulting in YZH N (Y O, F, N and S) hydrogen bond
formation. The average bond lengths of the hydrogen
bonds OZH N, FZH N, NZH N and SZH N are

(as per B3LYP),


2.080, 1.808, 2.724 and 2.403 A
respectively (Supporting information, Tables S1 S4). It
is to be noted that YZH N (Y O, F, N and S)
hydrogen bond distance formed with cyano group as
acceptor is comparatively greater than the YZH O
(Y O, F, N and S) bond distance where carbonyl group
acts as the acceptor site. This is because of the less electro
negativity of nitrogen compared with oxygen. To some
) and
extent, the CZO bond length (, 1.216 1.443 A

CZN bond length (, 1.173 1.178 A) upon complexation


(Table 4) are comparable with the monomer values (Table
3). Also, the theoretical bond lengths of few monomers
agree to a reasonable extent with the experimental bond
lengths [42]. The hydrogen bond for the OZH N angle is
found to be linear and lies along the putative position of
the lone pair on nitrogen. Interactions of cyano group with
HF also possess a linear symmetry, and the ideal bond
angles between HF donor and various acceptors is around
1808 and have been determined in previous studies
theoretically [43]. The average binding energy of H2O,
HF, NH3 and H2S complexes (formed through cyano
group as binding site) are 4.07, 8.3, 3.89 and
1.96 kcal/mol, respectively (using B3LYP). The binding
energy decreases in the order HF . H2 O . NH 3
. H2S. This trend in the binding strengths with respect
to the small molecule is similar to that reported for other
pyrimidines [44,45] and purines [46], and generally
follows the acidity of the small molecule [47].
Furthermore, water and ammonia tend to produce similar
binding strengths due to a balance between their proton
accepting and donating abilities. The average binding
energy of H2O, HF, NH3 and H2S complexes calculated
using MP2 method are 3.88, 7.10, 4.46 and 2.10 kcal/mol,
respectively. Here, the binding energy decreases in the
order HF . NH3 . H2O . H2S. Comparing the binding
energy of NH3 and H2O complexes, the larger binding
energy of the ammonia complexes is expected due to the
larger proton affinity of ammonia.

) of the complexes calculated using B3LYP and


Table 4. Selected optimised structural parameters (CZO and CZN bond lengths in A
MP2 methods at 6-311 G(d,p) basis set.
X H2O

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

3.3 Relative hydrogen bond donor ability


Of the 80 optimised structures, there are eight structures
namely oxo3H2O, oxo4H2O, oxo3HF, oxo4HF, oxo3NH3,
oxo4NH3, oxo3H2S and oxo4H2S where the hydroxyl
group of C3H3NO interacts with the small molecules
forming hydrogen bonds OZH Y (where Y O, F, N
and S). Here in all the above complexes, C3H3NO acts as a
proton donor and the small molecules act as proton
acceptors. The H-bond distances of the most stable
complexes oxo4H2O, oxo3NH3 and oxo4H2S are listed in
,
Table 1. The bond length value of oxo4H2S (2.421 A

B3LYP) is comparatively greater than oxo4H2O (1.811 A,


, B3LYP). This strong
B3LYP) and oxo4NH3 (1.794 A
bonding of oxo4NH3 is also reflected in the interaction
energy value (12.01 and 10.96 kcal/mol from B3LYP and
MP2 levels of theory, respectively). The order of stability
among oxo4H2O, oxo4NH3 and oxo4H2S shows an
inverse correlation with the H-bond length, i.e. the smaller
the H-bond length, the more stable is the structure, which
can be attributed to stronger overlap of orbitals between
two monomers. It is understood from the plot between
binding energy and hydrogen bond length (Figure 2) that
the inverse correlation coefficient value for the most stable
complexes is approximately equal to 0.90 in B3LYP and
MP2 level of theories.
In the Supporting information, Tables S1 S4, the
hydrogen bond distances calculated using both the level of
theories with hydroxyl group as the binding site are found
to be approximately the same. Here, the average bond
,
length values of oxo3H2S and oxo4H2S (, 2.427 A
B3LYP) are comparatively greater than the other
corresponding complexes with NH3 occupying the least
, B3LYP). These differences occur due to
value (, 1.801 A
the properties of small molecules, where H2S is a strong

B3LYP Corr.coeff = 0.9090

12

MP2 Corr.coeff = 0.9060

10
E (kcal/mol)

Downloaded by [The University Of Melbourne Libraries] at 12:38 05 October 2013

Molecular Simulation 913

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.

3.4 AIM analysis


The presence of hydrogen bonds in all the 80 complexes
studied is also supported by the results of AIM calculations
that describe the topology of the electron density [32]. The
criteria outlined by Koch and Popelier [51] provide
empirical guidelines to decide whether to consider a
particular interaction to be a hydrogen bond. The most
widely used criteria stipulate that the value of the electron
density and Laplacian of electron density are in the range
of 0.002 0.34 and 0.016 0.139 a.u., respectively [32].
The AIM data for the most stable complexes are given in
Table 1. As expected, strong bonds are found to be
associated with higher electron density. It is observed that
the complex oxo4NH3 has higher bond critical point
(BCP) electron density and higher stability. This is
followed by oxo4H2O, oxo4HF1 and oxo4H2S complexes.
Thus, the electron density values calculated at the BCPs
augment the stability order H2S , HF , H2O , NH3
predicted by overall interaction energy. The calculated
values of Laplacian of the electron density also follow the
same trend. The inverse correlation between electron
density with H-bond distance for the most stable
complexes is shown in Figure 3 and the correlation
value is found to be 0.9154 in B3LYP and 0.8764 in MP2.

914 V. Umadevi et al.


0.045

B3LYP Corr.coeff = 0.9779


MP2 Corr.coeff = 0.9940

B3LYP Corr.coeff = 0.9154


MP2 Corr.coeff = 0.8764

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

Figure 3. Correlation between electron density and the H-bond


distance calculated using B3LYP and MP2 level of theories, for
the most stable C3H3NO X (X H2O, HF, NH3 and H2S)
complexes.

From Figure 4, correlation fit values . 0.96 (B3LYP and


MP2) are obtained between Laplacian and hydrogen bond
distance. Also, the interaction energy versus Laplacian
curve (Figure 5) for the most stable complexes shows a
linear correlation value . 0.977 in both levels of theories.
Arnold and Oldfied pointed out that electronic energy
density (H) is an appropriate index to understand noncovalent interactions, and its sign at the BCP determines
whether the hydrogen bond interaction is ES dominant
(H . 0) or covalent dominant (H , 0) [67]. The negative
value of H is found for both oxo4HF1 and oxo4NH3
complexes. The oxo4NH3 complex possesses the more
negative value computed at both levels of theories
confirming its highest order of stability, of all the
complexes studied.
0.12

B3LYP Corr.coeff = 0.9639

0.11

MP2 Corr.coeff = 0.9753

(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()

Downloaded by [The University Of Melbourne Libraries] at 12:38 05 October 2013

0.06
0.015
1.7

2.2

2.3

2.4

2.5

R()

Figure 4. Correlation between Laplacian of the electron density


and the H-bond distance calculated using B3LYP and MP2 level
of theories, for the most stable C3H3NO X (X H2O, HF, NH3
and H2S) complexes.

10

E(kcal/mol)

Figure 5. Correlation between interaction energy and Laplacian


of the electron density calculated using B3LYP and MP2 level of
theories, for the most stable C3H3NO X (X H2O, HF, NH3
and H2S) complexes.

The results in Tables S5 S8 (Supporting information


online only) give the calculated values of electron density
(r) and Laplacian of electron density 72 r carried out
using B3LYP and MP2 methods in conjunction with the 6311 G(d,p) basis set which illustrates the presence of
hydrogen bonding in all the complexes. The relative values
of the electron density and its Laplacian as obtained by DFT
and MP2 methods show the same trend in most cases,
except a few discrepancies with small differences. In this
study, a comparison of various Baders electron density
properties for all the 80 complexes with different functional
groups as hydrogen bond donors and acceptors indicate that
these values are larger for hydroxyl groups (as proton
donors that is OZH Y where Y O, F, N and S),
followed by carbonyl group (YZH O) and then by cyano
group (YZH N) both acting as proton acceptors. This is
more clearly indicated in B3LYP calculations. Hence the
analysis of density and Laplacian of electron density
clearly indicate that all the complexes are bound with
strong hydrogen bond, with high electron density values
indicating higher structural stability [48]. Further, a
correlation between the hydrogen bond distance, electron
density and Laplacian of electron density has been
established. The curves corresponding to the correlation
fit are shown in the Supporting information (Figures S9
S16). The correlation between bond length and electron
density is inverse, that is, an increase in bond length
corresponds to a decrease in the electron density, which is
expected, since increase in distance results in reduced
orbital overlap, and hence low electron density along the
bond. The correlation between hydrogen bond length and
Laplacian is also inverse and analogous to electron density

Downloaded by [The University Of Melbourne Libraries] at 12:38 05 October 2013

Molecular Simulation 915


and hydrogen bond length. The correlation coefficient
value for the electron density and its Laplacian with
hydrogen bond distance are indicated in the plots and are
found to be greater than 0.97 for all the complexes
(Supporting information, Figures S9 S11 and S13 S15)
with the only exception that C3H3NO H2S complexes
(Supporting information, Figures S12 and S16) have
correlation fit values around 0.8743 and 0.8452 for the
electron density and its Laplacian with hydrogen bond
distance, respectively, calculated using B3LYP theory. In
addition, the correlation curves between interaction energy
and its Laplacian for all the complexes are shown in the
Supporting information (Figures S17 S20). It is a known
fact that there exists a linear relationship between
interaction energy and electron density. Therefore, as the
interaction energy increases Laplacian of the electron
density also increases and the correlation fit values are
greater than 0.94 (B3LYP) and 0.97 (MP2) for all the
complexes. From Tables S5 and S8 (Supporting information), it is understood that all H values of H2O and H2S
complexes are positive indicating that the hydrogen bond
interactions are closed shell, whereas the H value is
negative for few of the HF and NH3 complexes (Supporting
information, Tables S6 and S7) illustrating that their
hydrogen bond interactions are covalent. In general, the
more the negative value of H, the more shared the bonded
interaction and the greater the stabilisation of the structure.
We have also analysed the electron density and its
Laplacian values for CZH Y type bonds for which the
topological parameters are found to be very small in
comparison with other types of bonds. Thus, AIM analysis
is not able to provide much information on these types of
bonds and hence NBO analysis is performed.

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

where qi is the ith donor orbital occupancy, 1i, 1j are the


diagonal elements (orbital energies) and F(i,j) are the off

diagonal elements, associated with the NBO Fock matrix.


NBO describes the chemical bonding in terms of
hybridisation or charge donation [54,55]. Here the
occupancy, and its changes upon hydrogen bond formation
at the lone pairs of the electronegative atom (O, N, F and S)
and in the antibonding orbitals of HZO, HZN, HZF, HZS
along with the second order perturbation energy are
examined. The occupancy of n(x), s*(HZY) and E (2)
energies for the most stable complexes (monomer values
in parentheses) is shown in Table 2. The occupancy of the
lone pairs of the electronegative atom decreases upon
complexation and the difference is greater for nitrogen
(0.063 kcal/mol (B3LYP) and 0.045 kcal/mol (MP2)) in
OZH N bond in the oxo4NH3 complex than the rest of
the complexes. Similarly, the s*(HZY) occupation
number of the most stable complex oxo4NH3 differ from
their corresponding monomer by an amount 0.059 kcal/
mol (B3LYP) and 0.043 kcal/mol (MP2) due to charge
delocalisation interaction between orbitals and is evident
that the occupancy difference is greater in oxo4NH3
complex. It is important to note that the lone pair of
electronegative atoms (O, N and S) act as electron donor
and HZY as electron acceptor in the strong intermolecular
charge delocalisation interaction. The larger value of E(2)
for the most stable complex oxo4NH3 is found to be
27.53 kcal/mol and 31.80 kcal/mol in B3LYP and MP2,
respectively, which is very much greater when compared
with the rest of the corresponding complexes. This larger
E (2) value is as a result of the more intensive interaction
between electron donors and electron acceptors, i.e. the
more the donating tendency from electron donors to
electron acceptors the greater the extent of conjugation of
the whole system.
Tables S9 S12 (Supporting information) present the
values of NBO occupation numbers for the (HZY) proton
donor antibonding orbital n[s*(HZY)] and the proton
acceptor lone pairs n(x) for all the structures considered in
the present study. The second order perturbation energies
E (2) (donor acceptor) involving the s*(HZY) orbital are
also given. The values of isolated monomers are given
within parentheses. When NBO results for the isolated
molecules are compared, it is observed that s*(HZY)
occupation numbers are in the range 0.0 0.07. The
occupancy value of the antibonding orbitals in the
complexes are found to be greater compared with their
monomers. It is interesting to note that, upon complexation, the occupation number of the lone pairs of the
electronegative atoms (proton acceptors) decreases by an
amount 0.026 0.063 kcal/mol (B3LYP) and 0.016
0.045 kcal/mol (MP2) when compared with the monomers.
Also, it is obvious that the occupation number of the lone
pair of electronegative atoms depends on electro negativity
and increases with increase in electro negativity. Further,
the weak interaction of CZH bond with lone pair electrons
of oxygen, fluorine, nitrogen and sulphur atoms in various

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

The relative balance of interaction energy components


plays a significant role in stabilisation of hydrogen-bonded
systems. To obtain a clearer view of the interactions of
small molecules with C3H3NO, the Kitaura Morokuma
energy decomposition was carried out to analyse the
contribution of ES, exchange repulsion (EX), CT,

Bond
(XZH YZZ)

Morokuma decomposition of interaction energies

Structure

3.7

X( O and F)

3.6 Natural atomic charges


The natural charges of atoms involved in hydrogenbonding interactions for the most stable complexes are
listed in Table 5. The hydrogen atoms participating in the
bond are positively charged, whereas all other atoms are
negatively charged. In the complexes, oxo4H2O, oxo4HF1
and oxo4NH3 the negativity of the oxygen, fluorine and
nitrogen atoms increases in complexes in comparison with
those of the monomers. The proton acceptor and donor
atoms gain charge in all cases, being the charge gained by
the donor atom [0.112 0.125 (B3LYP), 0.122 0.155
(MP2)] considerably greater than the charge gained by the
acceptor atom [0.017 0.096 (B3LYP), 0.027 0.097
(MP2)]. As a result of the gain of the electronic charge,
the donor and acceptor atoms are stabilised resulting in the
formation of a strong hydrogen bond. The nitrogen atom in
oxo4NH3 is more negatively charged than oxygen and
sulphur atoms in oxo4H2O and oxo4H2S, respectively. In
oxo4NH3 (OZH N) nitrogen acts as an electron donor,
but it still has a large negative charge because it interacts
with less electronegative hydrogen atom in its remote part.
In complex oxo4H2S, the oxygen and hydrogen atoms lose
their charge upon complexation, whereas the sulphur atom
gains atomic charge which results in the weak hydrogen
bond. When considering oxo4HF1, the remote part of
nitrogen, i.e. carbon atom has higher negative charge
which may be due to the presence of double bond (C N)
nature. From Table 5, it is understood that the strength of
the hydrogen bonding decreases in the order H2S . HF .
H2O . NH3.

Natural atomic charges

Downloaded by [The University Of Melbourne Libraries] at 12:38 05 October 2013

complexes results in very low hyper conjugative


interaction energy, E (2). In general, there exists an inverse
correlation between E (2) and bond length for all the
complexes with correlation values greater than 0.98 and
0.94 at B3LYP and MP2 level of theories, respectively, and
are shown in Figures S21 S24 (Supporting information).
Further correlation curves relating binding energy and
energy E (2) from hyper conjugative interaction are shown
in Figures S25 S28 (Supporting information). It is
understood that there exists a linear relationship between
binding energy and E (2) with the correlation values greater
than 0.97 and 0.94 at B3LYP and MP2 level of theories,
respectively.

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.

916 V. Umadevi et al.

Downloaded by [The University Of Melbourne Libraries] at 12:38 05 October 2013

Molecular Simulation 917


ES

EX

PL

CT

MIX

20

Energy(kcal/mol)

polarisation (PL), higher order coupling terms (MIX), total


interaction energy (DE) and total interaction energy with
BSSE (DEBSSE). In case of non-covalent interactions, the
total interaction energy has been shown to be largely
determined by the attractive ES energy term and the
repulsive exchange repulsion term (EX) [48-50], both of
which generally have larger values compared to the
contribution from other components. In case of hydrogen
bonding, in general both ES as well as EX increase as the
donor and acceptor comes close to each other. The
optimum geometry is defined by the net balance of the two
terms one positive and the other negative. The PL and
CT terms describe the interaction between filled and
unfilled orbitals of the complex, wherein PL arises from
mixing of occupied and empty orbitals of the same
fragments, while the CT term represents the mixing of
orbitals of one fragment with the other in a complex.
The Morokuma analysis of the most stable complexes
using the HF/6-311 G(d,p) method is listed in Table
6 and the corresponding plot is shown in Figure 6. As
mentioned earlier, the optimum geometry and the
corresponding interaction energy of hydrogen bonded
systems are determined by the variation in ES and EX with
donor acceptor distances. It is to be noted that the ES
energy for oxo4NH3 (22.84 kcal/mol) is greater and is
followed by oxo4H2O (15.60 kcal/mol) complex. This is
because, OZH N and OZH O hydrogen bond
distances are smaller. It is clear from the results of
oxo4NH3 complex that the ES and EX contributions are of
the same order of magnitude with opposite sign, thus
cancelling each other, and thus PL, CT and MIX terms
contribute to the interaction energy. This is further
supported by the fact that consideration of the PL, CT and
MIX components alone predicts that oxo4NH3 is the most
stable complex, in agreement with the prediction from the
total interaction energy. This structure, in fact, has
maximum contribution from all the energy components,
viz., PL, CT and MIX and is responsible for stabilising the
complex. The high contribution of PL term to the
interaction energy also substantiates the fact that high
dipole moment of the complex is responsible for greater
contribution of PL to the total interaction energy. The

20
B

Structure

Figure 6. Various energy components as obtained using


Morokuma analysis calculated using HF level of theory, for
the most stable C3H3NO X (X H2O, HF, NH3 and H2S)
complexes (where oxo4H2O A, oxo4HF1 B, oxo4NH3 C
and oxo4H2S D).

covalent bonds are characterised by large PL energies, and


hence the covalent nature and stability of oxo4NH3 as
predicted by AIM analysis using electronic energy density
(H(r)) are confirmed. Therefore, when small molecules act
as proton acceptors, the hydrogen bond length and hence
their corresponding interaction energies along with ES,
follows the order of basicity H2S , HF , H2O , NH3.
The lesser electro negativity of sulphur results in sulphur
having a much smaller negative charge. This, coupled with
the larger radius of sulphur, greatly reduces its ability to
participate in stabilising interactions (Table 6).
The calculated results from the Morokuma analysis
using the HF/6-311 G(d,p) method for all the
complexes are listed in Tables S13 S16 (Supporting
information). To elucidate the role of each term in the total
interaction energy, the magnitude of the individual
interaction energy components is plotted in Supporting
information (Figures S29 S32). Thus, inspection of
energy components for all the studied complexes suggests

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

For the explanation of different terms see text.


Calculated using HF/6-311 G(d,p) method.
Basis set superposition error corrected interaction energy.

B3LYP

MP2

7.74
8.24
7.80
6.72

7.78
8.18
7.66
6.79

Downloaded by [The University Of Melbourne Libraries] at 12:38 05 October 2013

918 V. Umadevi et al.


that ES components are the largest attractive components
in all the complexes. The exchange repulsion, the
repulsive component of interaction energy is relatively
smaller in magnitude compared to ES. CT and PL
components also play a significant role in the interaction
between small molecules and C3H3NO isomers. As
mentioned earlier, the large dipole moment of the
complexes is responsible for greater contribution of PL
to the total interaction energy, whereas in C3H3NO HF
complexes alone, the relatively higher dipole moments of
the complexes results in less contribution of polarised
term. This is due to high electro negativity of fluorine atom
which results in the polar nature of OZH F bond. The
results of the Morokuma analysis on interaction energies
(sum of all the components) for all the structures are in
agreement with the MP2 and B3LYP results but with some
error percentage. Further, by using Morokuma analysis on
interaction energies the basicity order as predicted in all
the above analysis is confirmed. It is to be noted that even
after correction for basis-set-superposition error, the
relative interaction energies almost remains the same.
The correlation between electron density and various
energy components calculated using Morokuma analysis
is shown in the Supporting information (Figures S33
S36). In general, it is obvious from the figures that for all
the complexes, the various energy components increase
with increase in electron density values.

3.8 Nature of CZH Y bonds


Weak interactions of the type CZH Y are of current
interest now. A number of CZH O [56 60], CZH N
[61], CZH p [62 66] complexes have been investigated, in which one of the interesting aspects is the
frequency shift for the CZH stretching vibration. In this
study, the interaction of C3H3NO with small molecules
results in the formation of ZZCZH Y [Z (C and O)
and Y (O, F, N and S)] hydrogen bond in some
complexes where Y is the hydrogen bond acceptor. In
Table S1 (Supporting information), the CZH O hydrogen bond for complexes oxo1X, oxo2X, oxo3X, oxo4X
and oxo5X (X H2O) have their hydrogen bond lengths
(B3LYP) and 2.538 2.760 A

in the range 2.536 2.868 A


(MP2). It is found that the CZH O hydrogen bond length
values are minimum for oxo1H2O, oxo2H2O and
oxo5H2O complexes. On the contrary, it is found that
the weak interaction with maximum hydrogen bond length
value is found in the oxo3H2O and oxo4H2O complexes
that have maximum interaction energy. Comparing the
) and
complexes with maximum (oxo3H2O 2.760 A

minimum (oxo2H2O 2.538 A) CZH O hydrogen


bond lengths, it is evident that the maximum contribution
to the interaction energy is through conventional hydrogen
bonding (OZH O) and the stability order is not disturbed

by the presence of weak interactions. The oxo1HF and


oxo4HF complexes possess CZH F hydrogen bond and
(Table S2),
their bond length values are 2.630 and 2.688 A
respectively. The CZH N interaction is found in all
C 3H 3NO NH 3 complexes (except oxo3NH 3 and
oxo4NH3) with the bond length ranging from 2.375 to
. This weak interaction is strongest in complexes
2.881 A
oxo1NH31 and oxo2NH31 which have interaction energy
values of 4.44 and 4.66 kcal/mol, respectively. The
CZH S interaction is seen in complexes oxo1H2S,
oxo2H2S and oxo5H2S. The bond length values are in the
(Table S4). Overall, the average
range 2.959 3.200 A
CZH Y hydrogen bond length values of H2O, HF, NH3
and H2S complexes calculated using MP2 method are
, respectively. In this
2.619, 2.659, 2.550 and 3.094 A
study, it is evident that CZH N hydrogen bond length is
found to be strongest and CZH S to be the least strong.
The above results are well supported due to the lower
basicity of sulphur which acts as the proton acceptor
within hydrogen bonds. The charge density, Laplacian and
electronic energy density (H(r)) values (Tables S5 S8) are
minimum for CZH Y (Y O, F and N) interactions
than the other types of hydrogen bond interactions. The r
and f2r values calculated indicate that all the complexes
possess hydrogen bonding, which agrees well with the
theoretical results [32].
To investigate the red- and blue-shifting nature of the
CZH Y (Y O, F, N and S) bonds, the various
geometrical parameters along with the frequency,
calculated using B3LYP and MP2 methods using 6311 G(d,p) basis set are listed in Table S17
(Supporting information). The CZH Y bonds have
been thoroughly analysed by calculating the bond lengths
of the CZH fragment, the occupation numbers of the
antibonding orbital (CZH) as well as of the remote part
ZZC fragment, charge density and stretching frequency of
the CZH bond in the monomer as well as complex. It is
found that in all the complexes possessing CZH Y
(Y O, F, N and S) interaction, carbon atoms are either
sp2 or sp3 hybridised. It is well known that the carbon
atoms with tetrahedral structure possess sp3 and those with
trigonal structure possess sp2 hybridisation. In this study,
the carbon atom in the complexes oxo1X, oxo5X,
oxo1NH31 and oxo5NH31 (X H2O, HF, NH3 and
H2S), possess tetrahedral structure and hence sp3
hybridisation. The carbon atom in the remaining
complexes possesses sp2 hybridisation. The CZH bond
length values calculated for all the complexes are found to
. The contraction of CZH
be in the range 1.083 1.106 A
when compared with
bond is in the range 0.001 0.004 A
the monomer. The reason for this kind of charge
contraction is the structural reorganisation induced by
CT from the donor to the antibonding orbital of remote
part of the acceptor, which results in strengthening of the
CZH bond and a possible change in its frequency,

Downloaded by [The University Of Melbourne Libraries] at 12:38 05 October 2013

Molecular Simulation 919


characteristics of the so-called improper hydrogen
bonding. The CT has been analysed to confirm this
process, and the results indicate the transfer of charge from
the proton acceptor to the antibonding orbital of the remote
part of the proton donor, confirming the bonds to be
improper and substantiating the reason for shortening of
the CZH bond. Also, it is observed that the charge density
of the CZH bond increases upon complexation which is
due to the localisation of charges and hence contraction of
CZH bond. The stretching frequency was calculated
through vibrational analysis of the CZH bond in the
complex as well as monomer. The values of the
frequencies have shown considerable increase in going
from monomer to complex (3.5 61.5 cm21), which
confirms that the bonds have improper blue-shifting
nature. The average blue shift involving sulphur atom in
H2S complexes is comparatively less (, 8 cm21) than the
rest of the complexes and, therefore, of all the acceptors
(Y O, F, N and S) involved in weak hydrogen bonding,
sulphur is the weak acceptor. Further, the E (2) values for
the CZH Y (Y O, F, N and S) predict interactions to
be weak and values are in the range 0.06 1.39 kcal/mol.
In complexes oxo1NH3, oxo3NH31 and oxo4NH31,
the occupancy of the antibonding orbital of CZH is more
when compared with its monomer and thereby it leads to
the elongation of CZH bond, followed by downshift of
stretching vibrational frequency. The magnitude in red
shift is decreased by 9.6 141.7 cm21 in the complexes
than the corresponding monomers and is similar to the
conventional hydrogen bond, with their E (2) value in the
range of 2.71 4.63 kcal/mol. Moreover, the charge density
of CZH bond for these complexes is also higher. Even
though they are proper hydrogen bonded complexes, the
hyper conjugative interaction energy E (2) is less, since,
part of the energy density from the lone pair electrons of
the acceptor atom is transferred to the CZH bond of the
proton donor as well as its remote part ZZC. The
dependence of the change of the CZH bond length due to
complexation based on the level of theory was analysed for
oxo5H2O, oxo5NH31 and oxo5H2S. From the above
study, it is also inferred that sp2 hybridised C atom favours
blue-shifting hydrogen bonds.

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

hydrogen bond donor and acceptor abilities for some


common functional groups. Among all the complexes
considered, the interaction energy of the most stable
structure lies in C3H3NO NH3 complex followed by
C3H3NO H2O, C3H3NO H2S and C3H3NO HF complexes. The stability order is same as that of the order of
basicity. This is well established from the nature of atom
acting as acceptor site and donor site in C3H3NO and the
type of small molecules interacting with it. Interestingly,
sulphur was found to be close to oxygen in hydrogen bond
acceptor strength, and for that reason the complexes in
which sulphur accepts a hydrogen bond are quite stable.
Beyond question is the fact that hydrides of the first row
(H2O and NH3) are much better proton acceptors as
compared with hydrides of the next row (H2S). Also,
ammonia forms stronger complexes as compared with
water.
Further, the Morokuma energy decomposition analysis
for all the complexes reveals that the attractive absolute ES
energy along with CT and PL energy outweighs exchange
energy, leading to strong interactions.
The relative stability order obtained from the
interaction energies is found to be consistent with the
corresponding electron density-based topological parameters. The correlation of H-bond length with charge
density and its Laplacian shows a linear fit. The NBO
analysis of the H-bond indicates that there is an increase in
the population of the (HZY) orbital in all the complexes
when compared with the monomers. In most of the
complexes with sp2 hybridised C atom in CZH Y
(Y O, F, N and S) hydrogen bond, there exists
contraction of CZH bond length resulting in blue-shifted
vibrational frequency.

Acknowledgements
The authors thank High Performance Computing Facility (HPCF)
of DST at Hyderabad for providing computational facility to
carry out the simulation work.

References
[1] Pimentel GC, McClellan AL. The hydrogen bond. San Francisco:
W.H. Freeman; 1960.
[2] Joesten MD, Schaad LJ. Hydrogen bonding. New York: Marcel
Dekker; 1974.
[3] Vinogradov SN, Linnell RH. Hydrogen bonding. New York: Van
Nostrand-Reinhold; 1971.
[4] Legon AC, Millen D. The nature of the hydrogen bond to water in
the gas phase. J Chem Soc Rev. 1992;21:7178.
[5] Scheiner S. Bent hydrogen bonds and proton transfer. Acc Chem
Res. 1994;27:402408.
[6] Etter MC. Encoding and decoding hydrogen bond patterns of
organic compounds. Acc Chem Res. 1990;23:120 126.
[7] Gordon MS, Jensen JH. Understanding the hydrogen bond using
quantum chemistry. Acc Chem Res. 1996;29:536 543.
[8] Hibbert F, Emsley J. Hydrogen bonding and chemical reactivity.
Adv Phys Org Chem. 1990;26:255379.

Downloaded by [The University Of Melbourne Libraries] at 12:38 05 October 2013

920 V. Umadevi et al.


[9] Jeffrey GA, Saenger W. Hydrogen bonding in biological structures.
Berlin, Springer J Mol Struct. 1991;299:197.
[10] ACS Washington DC. Smith DA. Modeling the hydrogen bond;
1994.
[11] Li JC, Ross DK. Evidence for two kinds of hydrogen bond in ice.
Nature. 1993;365:327 329.
[12] Franks F. Water. London: Royal Society of Chemistry; 1983.
[13] Jeffrey GA. An introduction to hydrogen bonding. New York:
Oxford University Press; 1997.
[14] Steiner T. The hydrogen bonds in the solid state. Angew Chem Int
Ed. 2002;41:4876.
[15] Scheiner S. Hydrogen bonding, a theoretical perspective. New
York: Oxford University Press; 1997.
[16] Pauling L. The nature of the chemical bond. Ithaca, New York:
Cornell University Press; 1939.
[17] Gordon MS, Jensen JH. Understanding the hydrogen bond using
quantum chemistry. Acc Chem Res. 1996;29:36543.
[18] Lindquist BA, Furse KE, Corcelli SA. Nitrile groups as vibrational
probes of biomolecular structure and dynamics: an overview. Phys
Chem Chem Phys. 2009;11:8119 8132.
[19] Allerhand A, Schleyer PvR. A survey of CZH groups as protons
donors in hydrogen bonding. J Am Chem Soc. 1963;85:1715 1723.
[20] Scheiner S. Hydrogen bonding: a theoretical perspective. Oxford:
Oxford University Press; 1997.
[21] Desiraju GR, Steiner T. The weak hydrogen bond in structural
chemistry and biology. Oxford: Oxford University Press; 1999.
[22] Kryachko ES. Neutral blueshifting and blue shifted hydrogen
bonded systems. Dordrecht: Springer; 2006 p. 293 336 Ch. 8.
[23] Maes G, Smets J, Adamowicz L, Mc Carthy W, VanBael MK,
Houben L, Schoone K. Correlations between ab initio and
experimental data for isolated H-bonded complexes of water with
nitrogen bases. J Mol Struct. 1997;410:15 322.
[24] Smets J, Mc Carthy W, Maes G, Adamowicz L. Correlations
between ab initio and experimental data for isolated 1:1 hydrogen
bonded complexes of pyridine and imidazole derivatives with water.
J Mol Struct. 1999;476:27 43.
[25] Hozba P, Havlas Z. Blue-shifting hydrogen bonds. Chem Rev.
2000;100:253 4264.
[26] Behnke M, Medvedev I, Winnewisser M, De Lucia FC, Herbst E.
The millimeter and sub-millimetre wave spectrum of oxirane
carbonitrile. Astrophys J Suppl Ser. 2004;152:97 101.
[27] Minyaev RM, Yudilevich IA, Minkin VI. Calculation of the
topomerization and isomerization of nitrosocyclopropene. Zh Org
Khim. 1986;22:19 29.
[28] Badawi HM, El-Rayyes AA. Vibrational spectra and potential
energy distributions of normal modes of 3-nitroso- and 3nitrocyclopropenes. J Mol Struct. 2002;588:17 27.
[29] Sumathi R, Nguyen MT. Theoretical study on unimolecular
reactions of acetyl cyanide and acetyl isocyanide. J Phys Chem A.
1998;102:412 421.
[30] Yilmaz M, Uzunalioglu N, Yakut M, Pekel AT. Oxidative
cyclisation of 3-oxopropanenitriles mediated manganese(III)
acetate with 2-thienyl substituted alkenes. Turk J Chem.
2008;32:411422.
[31] Morokuma K. Why do molecules interact? The origin of electron
donoracceptor complexes, hydrogen bonding and proton affinity.
Acc Chem Res. 1977;10:294 300.
[32] Bader RFW. Atoms in molecules a quantum theory. Vol. 22,
International Series of Monographs on Chemistry. Oxford: Oxford
University Press; 1990.
[33] Reed E, Weinhold F. Natural bond orbital analysis of near Hartree
fock water diver. J Chem Phys. 1983;78:4066 4073.
[34] Gledening ED, Reed AE, Carpenter JA, Weinhold F, NBO Version
3.1.
[35] Boys SF, Bernardi F. Calculation of small molecular interactions by
differences of separate total energies some procedures with reduced
errors. Mol Phys. 1970;19:53566.
[36] Frisch MJ, Trucks GW, Schlegel HB, Scuseria GE, Robb MA,
Cheeseman JR, Zakrzewski VG, Montgomery JA Jr., Stratmann RE,
Burant JC, Dapprich S, Millam JM, Daniels AD, Kudin KN, Strain
MC, Farkas O, Tomasi J, Barone V, Cossi M, Cammi R, Mennucci
B, Pomelli C, Adamo C, Clifford S, Ochterski J, Petersson GA,
Ayala PY, Cui Q, Morokuma K, Malick DK, Rabuck AD,

[37]

[38]

[39]

[40]

[41]
[42]
[43]

[44]

[45]

[46]

[47]

[48]

[49]
[50]

[51]

[52]

[53]

[54]

[55]

Raghavachari K, Foresman JB, Cioslowski J, Ortiz JV, Baboul AG,


Stefanov BB, Liu G, Liashenko A, Piskorz P, Komaromi R,
Gomperts RL, Martin DJ, Fox T, Keith MA, Al-Laham CY, Peng A,
Nanayakkara C, Gonzales M, Challacombe PMW, Gill B, Johnson
W, Chen MW, Wong JL, Andres C, Gonzalez M, Head-Gordon ES,
Replogle JA, Pople JA. Gaussian 03. Revision A.11. 2. Pittsburgh,
PA: Gaussian, Inc.; 2005.
Schmidt MW, Bal Dridge KK, Boatz JA, Elbert T, Gordon MS,
Jensen JH, Koseki S, Matsunaga N, Nguyen KA, Su SJ, Windus TL,
Dupuis M, Montgomery JA Jr. General atomic and molecular
electronic structure system. J Comp Chem. 1993;14:13471363.
Nguyen MT, Leroux N, Zeegers-Huyskens T. Theoretical
characterization of the hydrogen-bond interaction of diacetamide
with water and methanol. J Chem Soc Faraday Trans.
1997;93:3341.
Tanaka N, Urashima Y, Nishikiori H, Fujii T. Ab initio and density
functional studies on cyclopropanone complexes with HF and HCl.
Inter Electronic J Mol Design. 2003;2:723 731.
Allerhand A, Schleyer PvR. Nitriles and isonitriles as proton
acceptors in hydrogen bonding: correlation of DnOH with acceptor
structure. J Am Chem Soc. 1963;85:866870.
Mitra SS. Infrared studies of nitriles as proton acceptors in hydrogen
bond formation. J Chem Phys. 1962;36:32863291.
Sugie M, Kuchitsu KJ. Molecular structure of acetyl cyanide as
studied by gas electron diffraction. J Mol Struct. 1974;20:437 448.
Rablen PR, Lockman JW, Jorgensen WL. Ab initio study of
hydrogen bonded complexes of small organic molecules with water.
J Phys Chem A. 1998;102:3782 3797.
Di Laudo M, Whittleton SR, Wetmore SD. The effects of hydrogen
bonding on the acidity of uracil. J Phys Chem A.
2003;107:1040610413.
Whittleton SR, Hunter KC, Wetmore SD. The effects of hydrogen
bonding on the acidity of uracil derivatives. J Phys Chem A.
2004;198:7709 7718.
McConnell TL, Wheaton CA, Hunter KC, Wetmore SD. Effects of
hydrogen bonding on the acidity of adenine, guanine and their 8-oxo
derivatives. J Phys Chem A. 2005;109:6351 6362.
B3LYP/6-311 G(2d,p) acidities decrease according to HF
(1606.8 kJ/mol).H2O (1678.2 kJ/mol).NH3 (1725.5 kJ/mol).
B3LYP/6-311 G(2d,p) proton affinities decrease according to
NH3 (806.5 kJ/mol).H2O (630.4 kJ/mol).HF (407.3 kJ/mol). Ref.
No. 35 in K.C. Hunter, L.R. Rutledge, S.D. Wetmore, Hydrogen
bonding properties of cytosine: a computational study of cytosine
complexed with hydrogen flouride, water and ammonia, J Phys
Chem A. 2005;109:9554 9562.
Senthilkumar L, Ghanty TK, Ghosh SK, Kolandaivel P. Electron
density and energy decomposition analysis in hydrogen-bonded
complexes of Azabezenes with water, acetamide. J Phys Chem A.
2005;109:7575 7582.
Grimme S. Semiempirical GGA-type density functional constructed
with a long-range dispersion correction. 2006;27:1787 1799.
Grimme S, Antony J, Schwabe T, Lichtenfeld CM. Density
functional theory with dispersion corrections for supramolecular
structures, aggregates, and complexes of (bio)organic molecules.
Org Biomol Chem. 2007;5:741758.
Koch U, Popelier PLA. Characterization of CZHZO hydrogen
bonds on the basis of the charge density. J Phys Chem.
1995;99:9747 9754.
Reed AE, Curtiss LA, Weinhold F. Intermolecular interactions from
a natural bond orbital, donoracceptor viewpoint. Chem Rev.
1988;88:899926.
Weinhold F. Nature of H-bonding in clusters, liquids, and enzymes:
an ab initio, natural bond orbital perspective. J Mol Struct.
1997;398:181 197.
Szatylowicz H, Krygowski TM, Hobza P. How the shape of the NH2
group depends on the substituent effect and H-bond formation in
derivatives of aniline. J Phys Chem A. 2007;111:170 175.
Szatylowicz H, Krygowski TM, Panek JJ, Jezeierska A. H-bonded
complexes of aniline with HF/F2 and anilide with HF in terms of
symmetry-adapted perturbation, atoms in molecules and natural
bond orbitals theories. J Phys Chem A. 2008;112:98959905.

Downloaded by [The University Of Melbourne Libraries] at 12:38 05 October 2013

Molecular Simulation 921


[56] Alkorta I, Maluendes S. Theoretical study of CH . . . O hydrogen
bonds in H2OCH3F, H2O CH2F2, H2O CHF3. J Phys Chem.
1995;99:6457 6460.
[57] Steiner T. Unrolling the hydrogen bond properties of CZH . . . O
interactions. Chem Commun. 1997;(8):727734.
[58] Gu Y, Kar T, Scheiner S. Fundamental properties of the CH . . . O
interaction: is it a true hydrogen bond?. J Am Chem Soc.
1999;121:94119422.
[59] Hartmann M, Wetmore SD, Radom L. CZH . . . X hydrogen bonds
of acetylene, ethylene, and ethane with first- and second-row
hydrides. J Phys Chem A. 2001;105:44704479.
[60] Kryachko ES, Huyskens TZ. Theoretical study of the CH . . . O
interaction in fluoromethanes.H2O and chloromethanes.H2O complexes. J Phys Chem A. 2001;105:71187125.
[61] Gu Y, Kar T, Scheiner S. Comparison of the CH . . . N and CH . . . O
interactions involving substituted alkanes. J Mol Struct.
2000;552:17 31.
[62] Umezawa Y, Tsuboyama S, Honda K, Uzawa J, Nishio M.
CH/(interaction in the crystal structure of organic compounds.
A database study. Bull Chem Soc Jpn. 1998;71:12071213.

[63] Jemmis ED, Giju KT, Sundararajan K, Sankaran K, Vidya V,


Viswanathan KS, Leszczynski J. An abinitio and matrix isolation
infrared study of the 1:1 C2H2 CHCl3 adduct. J Mol Struct.
1999;510:5968.
[64] Hobza P, Spirko V, Havlas Z, Buchhold K, Reimann B, Barth H-D,
Brutschy B. Anti-hydrogen bond between chloroform and
fluorobenzene. Chem Phys Lett. 1999;299:180186.
[65] Jemmis ED, Subramanian G, Nowek A, Gora RW, Sullivan RH,
Leszcynski J. CZH . . . (interactions involving acetylene: an ab initio
MO study. J Mol Struct. 2000;556:315 320.
[66] Lopes KC, Pereira FS, de Araujo RCMS, Ramos MN. An ab initio
study of the structural and vibrational properties of the C3H6 HCN,
C2H4 HCN and C2H2 HCN. J Mol Struct. 2001;5652566:
417420.
[67] Arnold WD, Oldfied E. The chemical nature of hydrogen bonding in
proteins via NMR: J-couplings, chemical shifts and AIM theory.
J Am Chem Soc. 2000;122:1283512841.

Potrebbero piacerti anche