ACTA PHYSICO-CHIMICA SINICA
Volume 24, Issue 9, September 2008
Online English edition of the Chinese language journal
Cite this article as: Acta Phys. -Chim. Sin., 2008, 24(9): 1625-1630.
ARTICLE
Structures and Electronic Properties of HOCl···HCOCl
Complexes
Yanzhi Liu1,*,
Lihong He1,
Kun Yuan1,
Lingling Lü1,
Yunpu Wang2
1
College of Life Science and Chemistry, Tianshui Normal University, Tianshui 741000, Gansu Province, P. R. China;
2
College of Chemistry & Chemical Engineering, Northwest Normal University, Lanzhou 730070, P. R. China
Abstract:
B3LYP/6-311++G** and MP2/6-311++G** calculations were used to analyze the interaction between hypochlorous
acid (HOCl) and formyl chloride (HCOCl). The results showed that there were four equilibrium geometries (S1, S2, S3, and S4)
optimized at B3LYP/6-311++G** level, and all the equilibrium geometries were confirmed to be in stable states by analytical
frequency calculations. Complexes S1 and S3 use the 5H atom of HOCl as proton donor and the terminal 1O atom of HCOCl as
acceptor to form red shift hydrogen bond systems. However, the blue-shifted hydrogen bond (2C−3H···6O) coexists with 4Cl···5O
interaction in structures S2. As for S4, it uses the 7Cl atom of HOCl as proton donor and the terminal 1O atom of HCOCl as acceptor
to form red shift halogen bond system. Interaction energies between monomers in the four complexes corrected with basis set
superposition error (BSSE) and zero-point vibrational energy (ZPVE) lie in the range from −5.05 to −14.76 kJ·mol−1 at
MP2/6-311++G** level. The natural bond orbital (NBO) and atoms in molecules (AIM) theories have also been applied to explain
the structures and the properties of the complexes.
Key Words:
Hypochlorous acid; Formyl chloride; Noncovalent interaction; NBO theory; AIM theory
From a fundamental point of view, the complexes formed
by the noncovalent interactions are significant per se as they
bridge the gap between the free molecular systems and the
corresponding condensed phases. Also, in recent years, noncovalent intermolecular interaction has been implicated as an
important type of interaction in many different types of
physical systems and is especially of great interest within the
fields of biochemistry[1−8], material science[9−14], and atmospheric chemistry[15−17]. The noncovalent interactions, especially hydrogen bond and halogen bond, play roles in a wide
variety of biochemical phenomena such as protein-ligand
complexation[18] and are responsible for many novel properties
of materials[11,12]. As an illustrative example related to the significance of noncovalent systems in atmospheric chemistry,
the proposed very accurate quantum mechanical procedures
aiming to explain ozone layer depletion involve formation of
certain intermolecular complexes[15,16]. Halogen-containing
species, not only chlorofluorocarbons, but also hypochlorous
acid (HOCl) and in particular, halogen monoxide radical (ClO,
BrO), are also involved in ozone degradation[19−21]. HOCl has
been detected in the upper stratosphere by mass spectrometry
in clusters with nitric and sulfuric acids and their anions[22,23].
Furthermore, formyl chloride, HCOCl, is a product of important atmospheric reactions[24,25]. To understand the details of
the reactions occurring in atmospheric conditions, it is necessary to study the structure, stability, and other certain properties of the intermolecular complex taking part in these reactions. Although the title complexes of the present work are of
interest in the field of atmospheric chemistry, so far studies of
noncovalent complexes of HOCl are limited to a number of
systems combining HOCl with SO3[17], X−(X=Cl, Br)[26,27],
H2O[28], HOO radical[29], and O3[30].
Despite the potential importance of both HOCl and HCOCl,
to our best knowledge, neither theoretical nor experimental
study of their possible interaction is available in the literature.
In the absence of experimental information, a theoretical
analysis of the possible existence of such complexes and their
properties appear to be in order. However, we have chosen the
Received: March 13, 2008; Revised: May 24, 2008.
*Corresponding author. Email: [email protected].
The project was supported by the Natural Science Foundation of Gansu Province, China (07-08-12).
Copyright © 2008, Chinese Chemical Society and College of Chemistry and Molecular Engineering, Peking University. Published by Elsevier BV. All rights reserved.
Chinese edition available online at www.whxb.pku.edu.cn
Yanzhi Liu et al. / Acta Physico-Chimica Sinica, 2008, 24(9): 1625-1630
HCOCl and HOCl systems (as opposed to HCOF, HCOBr,
HOBr for example) due to the ability of density functional
theory (DFT) and ab initio methods to accurately calculate
structures and energies for chlorine containing compounds[24,31]. The present work reports the electronic structure,
stabilities, and properties of the title complexes in detail.
1 Calculation details
The geometries of the isolated HOCl and HCOCl moieties
and their complexes were fully optimized using both standard
and counterpoise-corrected (CP) B3LYP/6-311++G** levels.
This method and basis set adequately describes noncovalent
interaction systems[32,33], so it is reliable for the purpose of our
study. Harmonic vibrational frequency calculations confirmed
the structures as a minimum or transition state and enabled the
evaluation of zero-point vibrational energies (ZPVE). Counterpoise-corrected procedure was used to correct the interaction energy for basis set superposition error (BSSE). In the
scheme of the CP method, the binding energy of two molecules (A and B) can be expressed as follows[34]:
ΔECP=EAB(AB)−[EAeq(A)+EBeq(B)]−[EA(AB)+EB(AB)]+
[EA(A)+EB(B)]
where EAB(AB) is the total energy of the complex, EYeq(Y)
(Y=A or B) is the total energy of monomer Y with equilibrium geometry but without extended basis sets, and EY(AB)
and EY(Y) are the total energy of monomer Y based on the
same geometry as that in the complex with and without extended basis sets. At the same time, ZPVE correction is also
considered. Natural bond orbital (NBO)[35] analysis and atoms
in molecules (AIM) theory analysis[36] are featured wholly
through a series of intermolecular interactions under the
HOCl···HCOCl system. Natural bond orbital analysis was
preformed via NBO 5.0 program[37], and the other calculations
were performed using Gaussian 03 program[38].
2
Results and discussion
2.1
Geometric configuration
All possible geometries obtained by standard and CP opti-
Fig.1
mization on the surface of HCOCl+HOCl are depicted in
Fig.1. The results show that there are four equilibrium geometries at B3LYP/6-311++G** level. And all the equilibrium
geometries were confirmed to be in stable states by frequency
analysis. S1 and S3 complexes use the 5H atom of HOCl as
proton donor and the terminal 1O atom of HCOCl as acceptor.
As for S2 and S4, S2 uses the 3H and 4Cl atoms of HCOCl as
proton donors and the terminal 6O atom of HOCl as their
same acceptor. However, S4 uses the 7Cl atom of HOCl as
proton donor and the terminal 1O atom of HCOCl as acceptor.
S1, S3 belong to conventional hydrogen bond complexes; S4
belongs to halogen bond noncovalent complex. And hydrogen
bond (C−H···O) and O···Cl interaction coexist in S2. Noncovalent interaction between two electronegative atoms such as
O and Cl predicted here in S2 structure is consistent with previous investigations that reported existence of O···Cl interaction[30,39].
Some of the key geometrical parameters optimized for these
complexes using B3LYP/6-311++G** level are also displayed
in Fig.1. By comparing the data, we can find that the 6O−5H
distances in S1 and S3 or 6O−7Cl distance in S4 increase obviously after formation of complexes. For example, 6O−5H
distances in S1 and S3 increase by 0.0007 and 0.0006 nm, respectively; 6O−7Cl distance in S4 increases by 0.0004 nm. As
for 2C−3H in S2, its length decreases by 0.0001 nm. Bondi[40]
reported that van der Waals radii of Cl and O atoms were
0.175 and 0.152 nm, respectively, and Taylor[41] reported that
van der Waals radii of H atom was 0.109 nm. Here, 7Cl···1O
in S4 is 0.2882 nm; 5H···1O in S1 and in S3 are 0.1948 and
0.1956 nm; 3H···6O and 4Cl···6O distances in S2 are 0.2273
and 0.3239 nm, respectively. It is clear that these noncovalent
interaction distances are all less than the sum of the relevant
atoms′ van der Waals radii, and this is a necessary condition
for formation of the hydrogen or halogen bond[8]. Although the
distances between noncovalent atoms in four complexes calculated under CP correction optimization method enlarged (in
italics in Fig.1), a similar trend could still be obtained. Also, it
can be observed that the distances between proton donors and
Partial bond parameters of the monomers and complexes optimized at B3LYP/6-311++G** and CP correction (in italics) levels
The lengths of the bonds are in nm.
Yanzhi Liu et al. / Acta Physico-Chimica Sinica, 2008, 24(9): 1625-1630
Table 1
Complex
S1
Vibrational mode
νm a
νca
Δνb
Approximate descriptionc,d
ν1
3776.2(79.4)
3651.8(522.8)
ν2
1226.4(37.7)
1312.1(59.1)
85.7
6O−5H rock in plane
S2
ν1
3054.3(20.3)
3077.9(1.2)
23.6
2C−3H stretch
ν2
1328.3(32.2)
1315.5(48.7)
−12.8
2C−3H rock in plane
S3
ν1
3776.2(79.4)
3678.8(592.7)
−97.4
6O−5H stretch
ν2
1226.4(37.7)
1298.7(52.6)
72.3
ν1
720.4(27.2)
690.6(32.0)
−29.8
S4
a
Partial vibrational frequencies (cm−1) of the monomers (νc) and the complexes (νm) at B3LYP/6-311++G** level
−1
b
−124.4
6O−5H stretch
6O−5H rock in plane
6O−7Cl stretch
c
d
Infrared intensities (km·mol ) are in parentheses. Δν = νc−νm. Based on the calculated atomic displacements. For atomic number, see Fig.1.
acceptors in four complexes are in the order 5H···1O (in
S1)<5H···1O (in S3)<3H···6O (in S2)<7Cl···1O (in S4). For
the moment, the shorter the above distance, the more steady
the complex. Further more, it should be noted that S1, S2, S3,
and S4 all have planar configurations.
2.2 Vibrational frequencies, energies, and rotational
constants
The partial calculated frequencies of monomers and four
complexes under B3LYP/6-311++G** level are listed in Table
1. It can be observed that the stretching frequencies of 6O−5H
in S1 and S3 and 6O−7Cl in S4 have the red shifts. For example, compared with the monomer, 6O−5H stretching frequency decreases by 124.4 cm−1 in S1. However, the stretching frequencies of 2C−3H in S2 present a blue shift with 23.6
cm−1. Furthermore, we notice that the stretching vibrational
intensities of the 6O−5H in S1 and S3 and 6O−7Cl in S4 are
all enhanced after the formation of red shift hydrogen bond or
halogen bond complex. In contrast, the stretching vibrational
intensity of 2C−3H in S2 decreases obviously, which can be
attributed to the polarizable ability of proton donor. Here,
6O−5H and 6O−7Cl are typical polar bonds and are easy to
polarize, but 2C−3H bond is only with little polarity and is
difficult to polarize. IR strength and electronic dipole at the
corresponding vibration vector are correlative with square of
displacement partial differentiation[42]. After formation of the
complexes, the electronic dipoles of 6O−5H and 6O−7Cl bond
increase but that of 2C−3H decreases. Thus, IR strengths of
6O−5H and 6O−7Cl increase, whereas that of 2C−3H decreases. In fact, the increase or decrease of stretching vibrational infrared intensity is regarded as a typical character in
red shift or blue shift system[43].
Table 2 presents the total interaction energies (ΔEtot) and
the BSSE corrected interaction energies (ΔECP) for each complex. It can be observed that the interaction energies calculated using B3LYP method are higher (less negative) than
those obtained using MP2 method. Because the interaction of
the supermolecule is comprised of electrostatic force, dispersion force, and inductive effect, the dispersion force is not included in the B3LYP method (but B3LYP method has been
proved reliable during the geometry optimization[27]); however,
we can get it from the MP2 method or the higher method[44].
Despite the basis set 6-311++G** that we chose is advantageous to the decrease of BSSE error, obviously, it is necessary
to perform a CP correction. Both BSSE and ZPVE corrected
interaction energies range between −5.05 and −14.76 kJ·mol−1
at MP2/6-311++G** level and −3.61 and −12.00 kJ·mol−1 at
B3LYP/6-311++G** level. S1 and S3 are clearly the most
strong bounds of the various complexes, with binding energies
of –18.48 and −14.63 kJ·mol−1 after correction of BSSE at
MP2/6-311++G** level. In contrast, the binding energies of
S2 and S4 are only −11.19 and −7.06 kJ·mol−1 at the same
computational level, respectively. Taking one with another,
noncovalent interaction of halogen bond is obviously weaker
than noncovalent interaction of hydrogen bond in the present
study. According to the BSSE and ZPVE corrected interaction
energies, which were calculated at MP2/6-311++G** level
and listed in Table 2, we can conclude that the stabilities of the
four complexes increase in the order of S4<S2<S3<S1.
To further investigate the relationship between the orbital
energy and the stability, the energies of the highest occupied
molecular orbital (HOMO) and the lowest unoccupied molecular orbital (LUMO), the gap between them, and the dipole
moment for all configurations are listed in Table 3. From Table 3, it can be observed that the HOCl and HCOCl monomers
have the similar ELUMO, but HOCl has higher EHOMO than
HCOCl, so they may form the donor-accepter complex. After
formation of the complexes, except for S2, both the LUMO
and HOMO energies are higher than those of monomers; this
probably attributes to the coexisting of 2C−3H···6O hydrogen
bond and 4Cl···6O interactions in S2. In comparison with all
Table 2
Complex
Interaction energies in the four complexes
B3LYP/6-311++G**
MP2/6-3111++G**
ΔEtot BSSE ΔECP ΔECP+ZPVE
ΔEtot BSSE ΔECP ΔECP+ZPVE
S1
−19.20 2.30 −16.90 −12.00
−23.34 4.86 −18.48
−14.76
S2
−13.49 2.28 −11.21
−8.16
−19.30 8.11 −11.19
−8.69
S3
−17.91 1.98 −15.93 −11.25
−21.65 7.02 −14.63
−11.31
−12.32 5.26 −7.06
−5.05
S4
−7.74 1.83
−5.91
−3.61
ΔEtot is the total interaction energy, ΔECP is the interaction energy with BSSE
correction, and ΔECP+ZPVE is the interaction energy with both BSSE and
ZPVE corrections. The energies are all in kJ·mol−1.
Yanzhi Liu et al. / Acta Physico-Chimica Sinica, 2008, 24(9): 1625-1630
Table 3
HOMO energies (EHOMO), LUMO energies (ELUMO), and
Table 4
gap (ΔELUMO-HOMO) of the monomers and four complexes calculated
complexes calculated at B3LYP/6-311++G** level
at B3LYP/6-311++G** level
Compound
A
Species
ELUMO (a.u.)
EHOMO (a.u.)
ΔELUMO-HOMO (a.u.)
HOCl
609.728 (613.380)
HOCl
−0.1016
−0.3000
−
HCOCl
78.035
6.013
5.582
S1
10.366
0.779
0.725
S2
6.162
0.834
0.736
S3
9.213
0.752
0.696
27.274
0.658
0.643
HCOCl
−0.1015
−0.3149
−
S1
−0.0950
−0.2910
0.1960
S2
−0.1114
−0.3104
0.1990
S3
−0.0958
−0.2794
0.1836
S4
−0.0914
−0.2945
0.2031
S4
where Fij is the Fock matrix element between the i and j NBO
orbitals, εσ and εσ* are the energies of σ and σ* orbitals, respectivey, and ησ is the population of the donor σ orbital.
The interaction strength between monomers could be clarified according to second-order stabilization energy (E(2)) between proton donor and acceptor obtained from the NBO
analysis. As NBO theory indicates, the larger the stabilization
energy E(2), the stronger the interaction between donor and
acceptor orbitals. In other words, the donor electrons are easier to transfer to the acceptor orbitals. In addition, the importance of the orbital hyperconjugation and electron density
transfer (EDT) from electron donor orbital to electron acceptor orbital in noncovalent interaction systems are well known,
which leads to an increase in population of electron acceptor
antibonding orbital. This weakens the filled orbital bond and
The analyses for the combining interaction between HCOCl
and HOCl with the NBO method have been performed even at
MP2/6-311++G** level. And the corresponding results are
listed in Table 5. From the results of NBO analysis for the
monomers, it can be suggested that the 5H and 7Cl atoms in
HOCl carry significant amount (0.198e and 0.477e) of positive charge, whereas the 1O atom in HCOCl carries certain
amount (−0.556e) of negative charge. Therefore, intermolecular interaction should take place in the 6O−5H···1O or
6O−7Cl···1O. This means that the noncovalent interaction involved in 6O−5H···1O and 6O−7Cl···1O can be defined as hy-
NBO analysis of the monomers and the four complexes at MP2/6-311++G** level
Complexes
(2)
1,2
C
14.140 (14.725)
drogen bond and halogen bond, respectively.
The interaction between filled orbitals in one subsystem and
unfilled orbitals of another represents a deviation of the complex from its Lewis structure and can be used as a measure of
the intermolecular delocalization, also called as hyperconjugation. The hyperconjugative interaction energy can be deduced
from the second order perturbation approach[39]:
s* Fs
F2
=ησ ij
E(2)=−ησ
ΔE
es * - es
NBO analysis
Table 5
B
14.475 (15.117)
Experimental values[30] are in parentheses.
the complexes, the values of ΔELUMO-HOMO are in the order of
S4>S2>S1>S3. The most stable complexes S1 and S3 have
low ΔELUMO-HOMO, which are 0.1960 and 0.1836 a.u., respectively. And as the most unstable complex S4 in the present
study, the ΔELUMO-HOMO is the highest (0.2031 a.u.).
For the reason of completeness, the rotational constants for
monomers and the complexes are also listed in Table 4 at
B3LYP/6-311++G** computational level. The four complexes
are asymmetric rotors and behave like prolate rotors, with
A>B≈C. The calculated rotational constants for HOCl agree
well with the experimental values[30].
2.3
Rotational constants (in GHz) for monomers and four
*
−1
Monomers
S1
S2
S3
S4
E [n (1O)→σ (6O−5H)]/(kJ·mol )
−
11.6, 18.9
−
15.5, 10.6
−
E(2)[n1,2(6O)→σ*(2C−3H)]/(kJ·mol−1)
−
−
2.9, 5.8
−
−
E(2)[n2(4Cl)→σ*(6O−7Cl)]/(kJ·mol−1)
−
−
1.8
−
−
E(2)[n1,2(1O)→σ*(6O−7Cl)]/(kJ·mol−1)
−
−
−
−
2.4, 7.3
Δσ* a (6O−5H)/e
−
0.00856
−
0.00695
−
Δσ*(2C−3H)/e
−
−
−0.0037
−
−
Δσ*(6O−7Cl)/e
−
−
0.0021
−
0.00696
sp3.3, sp8.0
sp2.86, sp8.53
sp3.18, sp7.38
sp2.86, sp8.24
sp3.3, sp7.81
sp1.7, sp2.66
sp1.7, sp2.6
sp1.59, sp2.90
sp1.7, sp2.6
sp1.7, sp2.6
spn(6O−5H or 7Cl)
spn(2C−3H or 4Cl)
b
Δ{s(6O) in σ(6O−5H or 7Cl)} (%)
−
2.69, 3.52
0.76, 4.59
2.68, 3.49
0.06, 3.01
Δ{s(2C) in σ(2C−3H or 4Cl)}c(%)
−
−0.37, 0.85
1.66, −1.67
−0.29, 0.73
−0.07, −0.27
a
change of natural population σ*; bchange of s-character of 6O hybrid orbital in σ(6O−5H or 7Cl) on the complexation;
c
change of s-character of 2C hybrid orbital in σ(2C−3H or 4Cl) on the complexation
Yanzhi Liu et al. / Acta Physico-Chimica Sinica, 2008, 24(9): 1625-1630
leads to its elongation and concomitant stretching frequency
red shift. The above theory is applicable for HOCl···HCOCl
system. In complex S1, the second-order stabilization energies
(E(2)) of n1,2(1O)→σ*(6O−5H) are 11.6 and 18.9 kJ·mol−1, and
natural population of σ*(6O−5H) increases by 0.00865e. 3D
image of the interaction between n1,2(1O) and σ*(6O−5H) is
given in Fig.2(a). In complex S3, similar to that of S1, there
are high E(2) of n1,2(1O)→σ*(6O−5H), and an efficient overlap
can be observed between the related orbitals (Fig.2(c)). As for
complex S2 and S4, n1,2(6O)→σ*(2C−3H) and n1,2(1O)→
σ*(6O−7Cl) are the two main orbital interactions, respectively.
Their E(2) values are relatively low, so the overlaps of the related orbitals are very small as shown in Fig.2(b,d). Different
from red shift bonds, we can observe that the natural population of σ*(2C−3H) in S2 decreases by 0.0037e instead of increasing by some amounts; this shows that there has been
electron density redistribution effect of HCOCl moiety in S2.
Moreover, it can be observed from Table 5, s character of 2C
in 2C−3H of HCOCl moiety increases after the formation of
complex S2. Hence, we can conclude that the total of electron
density redistribution and atom rehybridization effect exceed
orbital hyperconjugation; thus, 2C−3H bond length decreases
by 0.0001 nm, and its stretching frequency represents blue
shift after the formation of complex. Further more, we observe
that the total E(2) between natural bond orbitals in four complexes increases in the order of S4<S2<S3<S1, this agrees
well with the result of interaction energy analysis.
2.4
Fig.2
orbitals in HOCl···HCOCl systems
presence of the hydrogen or halogen bond interactions in the
four complexes. For example, in the hydrogen bond interaction (1O···5H) in complex S1, its ρ(r) is 0.0207 a.u., and its
▽2ρ(r) is 0.0929 a.u. (>0). This indicates that the charge density radiation at BCP and the hydrogen bond have more ionic
property. As for halogen bond interaction in complex S4, the
▽2ρ(r) and ρ(r) of 1O···7Cl are similar to that of 1O···5H in
S1. In addition, Lipkowski[48] pointed that the electron density
and positive values of the Laplacian in hydrogen bond system
should be in the range of 0.002−0.04 and 0.02−0.15 a.u.. Here,
in hydrogen bond complexes of S1, S2, and S3, ρ(r) and
▽2ρ(r) all lie in the range of that suggested by Lipkowski.
The value of ρ(r) is the measurement of the bond intensity. In
general, the larger the ρ(r), the stronger is the bond. Here, the
ρ(r) of hydrogen bond or halogen bond in the four complexes
increases in the order of S4<S2<S3<S1; this agrees well with
the order of stability of the four complexes. Thus, the smaller
is the value of ellipticity (ε), the stronger is the σ property, and
otherwise the stronger is π property. In the present study, the
value of ε of hydrogen bond or halogen bond in four complexes is in the range of 0.0423–0.8454 a.u. These ε values are
all small. According to AIM theory[36], the covalent content of
the halogen bond or hydrogen bond in the four complexes
AIM analysis
A topological analysis of the electron density was carried
out using Bader¢s theory of AIM[36]. This analysis has been
applied to study the properties of a variety of interactions between atoms[45−47]. Especially, the properties of the electron
density at bond critical points (BCP) for the binding interaction between HCOCl and HOCl were analyzed in present
study. Table 6 lists the electron density (ρ(r)) at BCP and its
Laplacian of electron density (▽2ρ(r)) and ellipticities (ε). λi
(λ1, λ2, λ3) listed in Table 6 are the eigenvalues of the electron
density Hessian matrix, and ▽2ρ(r)=λ1+λ2+λ3. From Table 6,
we can observe that λ1<0, λ2<0, λ3>0 in each complex, according to Bader′s theory[36], they can be labeled as (3, −1)
critical points, and christened BCP, which can indicate the
Table 6
3D images of the main interactions between natural bond
Electron density topological properties at the intermolecular bond critical points of the four complexes calculated at
MP2/6-311++G** level
a
ρ(r)
λ1
λ2
λ3
▽2ρ (r)
ε
Interaction distanceb
1O···5H
0.0207
−0.0286
−0.0272
0.1490
0.0929
0.0500
0.1948
S2
6O···3H
0.0123
−0.0132
−0.0125
0.0741
0.0485
0.0560
0.2273
S2
6O···4Cl
0.0069
−0.0048
−0.0026
0.0373
0.0299
0.8454
0.3239
S3
1O···5H
0.0194
−0.0264
−0.0253
0.1428
0.0912
0.0423
0.1956
S4
1O···7Cl
0.0118
−0.0094
−0.0086
0.0676
0.0497
0.0934
0.2882
Complex
Atom pair
S1
a
2
For atomic number, see Fig.1; ρ(r) is electron density of critical point; λi is Hessian eigenvalue; ▽ ρ(r) is density Laplacian; ε is ellipticity; ρ(r) and ▽2ρ(r) are
in atom unit (a.u.); binteraction distance (nm) was calculated at B3LYP/6-311++G** level.
Yanzhi Liu et al. / Acta Physico-Chimica Sinica, 2008, 24(9): 1625-1630
would mainly represent σ property. Furthermore, all the intermolecular interactions present small values of the electron
density and positive values of the Laplacian as an indication
of closed shell interactions.
3
Conclusions
Theoretical calculations of the 1:1 complexes formed by
HCOCl and HOCl have been carried out at B3LYP/
6-311++G** and MP2/6-311++G** computational levels.
Four stable configurations have been found at B3LYP/
6-311++G** level. The theoretical analysis showed that the
four complexes are composed by two red-shifted hydrogen
bond (O−H···O) structures (S1 and S3), one co-exist of blueshifted hydrogen bond (C−H···O) and Cl···O interaction structure (S2), and one red-shifted halogen bond (O−Cl···O) structure (S4). According to the BSSE and ZPVE corrected interaction energies, which were calculated at MP2/6-311++G**
level, it can be concluded that the stabilities of the four complexes increase in the order of S4<S2<S3<S1.
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