ORIGINAL RESEARCH

Influence of insertion of a noble gas atom on halogen bondingin H2O���XCCNgF and H3N���XCCNgF (X 5 Cl and Br; Ng 5 Ar,Kr, and Xe) complexes

Qing-Zhong Li • Wen-Ming Liu • Ran Li •

Wen-Zuo Li • Jian-Bo Cheng • Bao-An Gong

Received: 16 April 2012 / Accepted: 26 April 2012

� Springer Science+Business Media, LLC 2012

Abstract The H2O���XCCNgF and H3N���XCCNgF

(X = Cl and Br; Ng = Ar, Kr, and Xe) complexes have

been studied with quantum chemical calculations at the

MP2/aug-cc-pVTZ level. The results show that the inserted

noble gas atom has an enhancing effect on the strength of

halogen bond, and this enhancement is weakened with the

increase of noble gas atomic number. The methyl and Li

substituents in the electron donor strengthen the halogen

bond. The interaction energy increases from -3.75 kcal/mol

in H3N–BrCCF complex to -9.66 kcal/mol in H2LiN–

BrCCArF complex. These complexes have been analyzed

with atoms in molecules, natural bond orbital, molecu-

lar electrostatic potentials, and energy decomposition

calculations.

Keywords Halogen bond � Noble gas � Substitution �Electrostatic interaction � Dependence of noble gas atomic

number

Introduction

The investigation of the properties of noble gas compounds

has been the subject of many studies in recent years. Some

noble gas compounds have been synthesized and observed

experimentally. The first reported Xe derivative is Xe[PtF6]

[1]. Then other Xe-containing compounds including

HXeH, HXeCl, HXeBr, HXeI, HXeCN, HXeNC, HXeSH,

and HXeOH have been prepared [2–7]. Some Kr-contain-

ing compounds such as HKrF and HKrCl have also been

synthesized [8–11]. The first Ar-containing compound,

HArF, was first discovered and characterized in a low

temperature solid Ar matrix [12]. These noble gas insertion

compounds can be expressed with the general formula

HNgX, where Ng = Ar, Kr, Xe; and X = electronegative

atom or group. The H–Ng bond exhibits covalent bonding,

while the Ng–X bond is ionic [13]. The HNgX and other

types of noble gas compounds have also been investigated

with theoretical methods. It has been demonstrated that the

inserted noble gas atoms have a great effect on the charge

distribution in molecules. In FNgCCF (Ng = Ar and Kr),

the charge distribution indicates highly positive charges on

the noble gas atoms, highly negative charges on the halo-

gen atoms, and relatively neutral charges on the carbon

atoms [14]. The electric properties, such as dipole moment,

polarizabilities, and first hyperpolarizabilities were also

changed accordingly [15–17].

These noble gas compounds have been found to form

some hydrogen-bonded complexes such as N2���HArF [18],

CO���HArF [19], OCO���HArF [20], N2���HKrF [21], and

N2���HKrCl [22]. An unusual vibrational characteristic, a

large blue shift of the H–Ng-stretching frequency, was

observed for these complexes. They also formed dihydro-

gen-bonded complexes with metal hydrides [23–26], in

which the H–Ng stretch vibration moves to low frequency.

Electronic supplementary material The online version of thisarticle (doi:10.1007/s11224-012-0036-9) contains supplementarymaterial, which is available to authorized users.

Q.-Z. Li (&) � W.-M. Liu � R. Li � W.-Z. Li � J.-B. Cheng

The Laboratory of Theoretical and Computational Chemistry,

School of Chemistry and Chemical Engineering, Yantai

University, Yantai 264005, People’s Republic of China

e-mail: liqingzhong1990@sina.com

B.-A. Gong (&)

Yantai Nanshan University, Yantai 264005,

People’s Republic of China

e-mail: gba1960@163.com

123

Struct Chem

DOI 10.1007/s11224-012-0036-9

The presence of noble gas atom also imposes an influence

on the strength of C–H hydrogen bond in FNgCCH

(Ng = Ar and Kr) complexes [27–29]. The hydrogen bonds

formed by FKrCCH are stronger than those formed by the

parent FCCH, which can be attributed to the increased

acidity of the C–H proton due to insertion of the Ng atom.

A halogen bond is a noncovalent interaction between a

region of positive electrostatic potential on the outer side of

the halogen X in a molecule and a negative site B, such as a

lone pair of a Lewis base or the p-electrons of an unsaturated

system [30]. In recent years, more and more attention has

been paid to halogen bonding because of its extensive

applications in molecular recognition, crystal engineering,

and biological systems [31–36]. We studied the halogen-

boned complexes of HArF and dihalogen molecules and

found that they are more stable than the corresponding

hydrogen-boned ones [37]. A large blue shift of the

H–Ar-stretching frequency was observed for both types of

complexes. However, the ability of these rare gas-inserted

molecules to form halogen bonding has not been investigated

with colloquial acceptor molecules for halogen bonding,

such as water, ammonia, alcohols, amines, and others.

In this article, we study the complexes of H2O���XCCNgF

and H3N���XCCNgF (X = Cl and Br; Ng = Ar, Kr, and Xe)

with quantum chemical calculations. The corresponding

H2O���XCCF and H3N���XCCF complexes are also studied.

The first aim is to explore the ability of C–X group in noble

gas-inserted molecule XCCNgF to form halogen bonding.

The second aim is to study the dependence of the ability on

the noble gas atomic number. Third, we compare the stability

of halogen-bonded complexes through substituting the pro-

ton in water and ammonia with a methyl group or Li atom.

The properties and nature of halogen bonds have been

understood by means of natural bond orbital (NBO), atoms in

molecules (AIM), and symmetry-adapted perturbation

theory (SAPT) methods.

Theoretical methods

All calculations were performed by means of the Gaussian

09 suite of programs [38]. We applied the most widely used

method in WFT procedures, second-order Møller-Plesset

perturbation theory (MP2) [39], which contains the essen-

tial portion of the correlation energy. This method has been

proven to be effective and accurate in determining the

equilibrium structure and interaction energy for many

halogen-bonded complexes [40–42]. All calculations were

carried out with the aug-cc-pVTZ basis set. Core electrons

were not included in the correlation treatment with MP2

calculations.

The geometries of the isolated species and halogen-

bonded complexes were optimized at the MP2/aug-cc-

pVTZ level. Then at the same level, we performed fre-

quency calculations to affirm that the obtained structures

are characterized as minima with no imaginary frequency.

The interaction energies were obtained by using the

supermolecule method as the difference between the

energy of a complex and the energy sum of the isolated

subsystems forming the complex. The basis set superpo-

sition error (BSSE) was removed by the standard coun-

terpoise correction method of Boys and Bernardi [43].

On the basis of the MP2-optimized structures, we per-

formed AIM and NBO analyses as well as molecular

electrostatic potentials (MEP) and energy decomposition

(ED) calculations. NBO analysis was carried out by means

of NBO 3.1 [44] program implemented in Gaussian 09.

AIM calculations were performed with the help of the AIM

2000 software [45]. MEP calculations were performed

using WFA Surface analysis suite [46]. ED calculations

were carried out with the SAPT method using the

SAPT2002 program [47].

Results and discussion

Energies and geometries

Figure 1 shows the optimized structures of H2O–ClCCF,

H2O–BrCCF, H3N–BrCCF, and the respective Ar-inserted

complexes. Clearly, the angle of halogen bond is close to

180� in all structures. The symmetry varies from Cs in

H2O–XCCF complex to C2,v in H2O–XCCArF (X = Cl

and br) complex, while it is kept as C3,v in H3N–BrCCF

and H3N–BrCCArF complexes. The interaction energies

corrected for BSSE in the complexes were collected in

Table 1. The interaction energy in H2O–BrCCF complex is

more negative than that in H2O–ClCCF one since the

positive electrostatic potential on the Br atom surface is

bigger. Ammonia is a stronger base than water, thus the

interaction energy in H3N–BrCCF complex becomes more

negative than that in H2O–BrCCF complex. When an Ar

atom is inserted into the C–F bond in XCCF, the interac-

tion energy becomes more negative, indicating that the

halogen bond is strengthened. This effect is like the C–H

hydrogen bond in FNgCCH (Ng = Ar and Kr) complexes

[27–29]. The increased value is related with the nature of

the halogen atom and the base. The Br halogen donor

brings out a little larger increase of the interaction energy

and the stronger base also has a similar effect but the effect

is prominent.

The strength of halogen bond is also reflected with

changes in geometries. Table 1 also presents the binding

distance and change of C–X bond length in the complexes.

One sees that the binding distance is shortened as an Ar

Struct Chem

123

atom is inserted into the C–F bond in XCCF. Its shortening

is 0.0615 A in H2O–ClCCArF complex, 0.0532 A in H2O–

BrCCArF complex, and 0.0564 A in H3N–BrCCArF

complex. Figure 2 shows the relationship of the interaction

energy and the binding distance. They display a good linear

relationship. The slope of the line is larger for the stronger

halogen bond. Upon complexation, the C–X bond is

lengthened. The Ar insertion causes a decrease of the C–X

bond elongation. Accompanied with the bond elongation, a

red shift is observed for the C–X stretch vibration. The red

shift of C–X stretch vibration is less prominent than that of

C–H bond in C2H2–HCCArF complex [48] due to the

larger atomic mass of X.

It has been demonstrated that the strength of Ng-H���pand C–H���F hydrogen bonds formed of benzene and HNgF

is weakened with the increase of Ng atomic number [49].

Thus, we replaced the Ar atom in the above complexes by a

Kr or Xe atom. The Kr and Xe complexes have a similar

structure with the Ar analog. With the increase of Ng

atomic number, the interaction energy becomes less neg-

ative and the binding distance grows up. This indicates that

the strength of halogen bond is also weakened with the

increase of Ng atomic number. This weakening is related

with the nature of halogen donor and acceptor. The bigger

weakening corresponds to the stronger base and weaker

halogen donor. For the heavier noble gas atom, the C–X

bond elongation becomes smaller. The respective bond

stretch exhibits a smaller shift as shown in Table 1.

The methyl group plays an important role in regulating

the strength of different types of interactions [50–52] and

the Li atom in the electron donor strengthens greatly the

halogen bond [53]. Thus, we substituted one H atom in

water or ammonia with a methyl group or a Li atom. The

structures of the respective complexes are shown in Fig. 3.

Fig. 1 Optimized structures of H2O–ClCCF, H2O–BrCCF, H3N–

BrCCF, and the respective Ar-inserted complexes

Table 1 Interaction energy (DE, kcal/mol) corrected for BSSE,

binding distance (R, A), change of C–X bond length (Dr, A), and shift

of C–X stretch vibration (Dv, cm-1) in the complexes

DE DDE DDE% R Dr Dv

H2O–ClCCF -1.98 – 2.9525 0.0019 -4

H2O–

ClCCArF

-2.97 -0.99 50 2.8910 0.0007 1

H2O–

ClCCKrF

-2.80 -0.82 41 2.9031 0.0008 -1

H2O–

ClCCXeF

-2.55 -0.57 29 2.9181 -0.0002 0

HMeO–

ClCCArFa-3.50 -0.71 25 2.8223 0.0013 -1

H2O–BrCCF -2.80 – 2.9201 0.0053 -6

H2O–

BrCCArF

-3.84 -1.04 37 2.8669 0.0039 0

H2O–

BrCCKrF

-3.64 -0.84 30 2.8790 0.0038 -3

H2O–

BrCCXeF

-3.36 -0.55 20 2.8937 0.0036 -3

HMeO–

BrCCArFa-4.56 -0.72 19 2.7913 0.0056 -3

H3N–BrCCF -3.75 – 2.9371 0.0115 -16

H3N–

BrCCArF

-5.25 -1.50 40 2.8807 0.0118 -13

H3N–

BrCCKrF

-4.95 -1.20 32 2.8967 0.0111 -15

H3N–

BrCCXeF

-4.57 -0.82 22 2.9167 0.0102 -14

H2MeN–

BrCCArFa-6.22 -0.97 18 2.7883 0.0164 -15

H2LiN–

BrCCArFa-9.66 -4.41 84 2.4971 0.0910 -124

a DDE is the difference of the interaction energy in the substituted

complex and that in the parent complex. DDE% is the increased

percentage of the interaction energy in the substituted complex relative

to that in the parent complex

Fig. 2 Relationship between the interaction energy and the binding

distance in the O���Cl (filled square), O���Br (filled triangle), and

N���Br (filled diamond) halogen-bonded complexes

Struct Chem

123

One can see that the C–X���O angle deviates from 180o in

HMeO–ClCCArF and HMeO–BrCCArF complexes. The

similar result is also found for the C–Br���N angle in

H2LiN–BrCCArF complex. When one H atom in water and

ammonia is replaced with a methyl group, the interaction

energy becomes more negative and the binding distance is

shorter. This shows that the halogen bond is strengthened

by the substitution. Accordingly, the C–X bond suffers a

bigger elongation, and the C–X stretch vibration shows a

larger red shift. The effect of methyl substitution is related

with the strength of halogen bond. The methyl group in the

stronger halogen bond leads to a larger enhancement. In the

methyl-substituted complexes, the positive charge on the

methyl group is increased, indicating that the methyl group

is electron-donating and thus it plays a positive contribu-

tion to the formation of halogen bond. The Li substituent

also brings out a similar effect on the strength of halogen

bond but its effect is more prominent. The interaction

energy is calculated to be -9.66 kcal/mol in H2LiN–

BrCCArF complex, which is increased by 84%. However,

the positive charge on the Li atom is decreased, and it

appears to be inconsistent with the Li electron-donating

and the enhancement of halogen bond. We found that the

Li atom is close to the Br atom in H2LiN–BrCCArF

complex; thus, we measured the distance of both atoms in

the complex. It is found that the distance is 2.6081 A,

which is much smaller than the sum of van der Waals radii

of Li and Br atoms (3.7 A). This means that the Br atom

has dual functions in formation of the complex: as the

electron donor and the acceptor, which can be understood

with the anisotropic distribution of electrostatic potentials

on the Br atomic surfaces.

NBO and AIM analyses

Natural bond order (NBO) analysis is an effective tool to

estimate the interaction between the lone pair orbitals of

O(N) and the antibonding orbital of C–X bond in the

complexes. Such orbital interaction is estimated with

perturbation energy. One can see from Table 2 that the

perturbation energy is increased in the Ng complexes and

becomes smaller for the heavier Ng atom. The methyl and

Li substitutions in the electron donor also increase the

perturbation energy. Figure 4 shows the relationship

between the interaction energy and the perturbation energy

in the complexes. A linear relation is observed for the

O���Cl complex, while a curve relation is found for the

O���Br and N���Br complexes. This indicates that the orbital

interaction is important in the formation of complexes.

The above orbital interaction leads to the changes in the

electron occupancy of C–X sigma-bonding and sigma-

antibonding orbitals. It can be seen from Table 2 that the

electron density of C–X sigma bond orbital is decreased

and that of C–X sigma-antibonding orbital is increased.

The latter suffers a bigger change than the former. Thus,

the latter is mainly responsible for the C–X bond elonga-

tion and the red shift.

The charge transfer happens between both subunits

accompanied with the orbital interactions. Although the

charge transfer is small in the formation of complexes, it

becomes larger in the Ng complexes. A good relationship is

observed for the interaction energy and charge transfer in

the O���Cl complex, while it is not found in the O���Br and

N���Br complexes. This shows that the charge transfer

interaction plays an important role in the formation of

O���Cl complex but has a small effect in the latter two

complexes.

Topological analysis of electron density is also a sen-

sitive method to estimate the strength of halogen bonding.

Table 2 presents the electron density and its Laplacian at

the O���X and N���X bond critical points in the complexes.

The electron density and its Laplacian are positive, thus the

observed BCPs are (3,-1) type for all the complexes. The

electron density and its Laplacian at the O���X and N���Xcontacts for all complexes fall in the proposed range of

Fig. 3 Optimized structures of HMeO–ClCCAeF, HMeO–BrCCArF,

H2MeN–BrCCArF, and H2LiN–BrCCArF complexes

Fig. 4 Relationship between the interaction energy and the pertur-

bation energy in the O���Cl (filled square), O���Br (filled triangle), and

N���Br (filled diamond) halogen-boned complexes

Struct Chem

123

0.002–0.04 and 0.02–0.15 a.u., respectively, for hydrogen

bonds [54]. Figures S1 and 5 show the linear relationship of

the interaction energy with the electron density and its

Laplacian, respectively. This indicates that both topologi-

cal parameters can measure the strength of halogen bonds

like that in hydrogen bonds [55].

MEP and ED analyses

Lots of studies [56, 57] showed that electrostatic interac-

tion plays a dominant role in halogen bonds, thus we cal-

culated the electrostatic potentials of the containing-X

molecules. Table 3 lists the most positive electrostatic

potentials (Vs,max) on the X atom surfaces. The Br atom has

a much larger positive electrostatic potential than Cl. The

Vs,max value is increased in the Ng complexes and becomes

smaller with the increase of Ng number. This is consistent

with the strength of halogen bond in the complexes, indi-

cating that the electrostatic interaction is of great impor-

tance in the halogen-bonded complexes.

To have a deeper insight into the nature of halogen

bonds in the complexes, we performed an ED analysis for

them. The halogen bonds were decomposed into five parts:

electrostatic energy (Eelst), exchange energy (Eexch),

induction energy (Eind), dispersion energy (Edisp), and

dEint-r(HF), which is the contributions to supermolecular

Table 2 Perturbation energy (E2, kcal/mol) due to the

LPO(N) ? r*(C–X) orbital interaction, charge transfer (CT, e), change

of charge on the methyl group or Li atom (Dq, e), differences between

NBO electron density (ED) in the complexes and the isolated halogen

donor in C–X sigma-bonding (Dr) and sigma-antibonding (Dr*)

orbitals, electron density (q, au), and its Laplacian (r2q, au) at the

intermolecular bond critical point (BCP) in the complexes

E2 CT Dq DrC–X Dr*C–X q r2q

H2O–ClCCF 1.32 0.0025 – -0.0006 0.0021 0.0091 0.0476

H2O–ClCCArF 1.67 0.0033 – -0.0008 0.0024 0.0105 0.0548

H2O–ClCCKrF 1.58 0.0031 – -0.0007 0.0022 0.0102 0.0535

H2O–ClCCXeF 1.48 0.0029 – -0.0007 0.0020 0.0099 0.0518

HMeO–ClCCArF 1.83 0.0031 0.0130 -0.0015 0.0034 0.0126 0.0646

H2O–BrCCF 3.08 0.0052 – -0.0009 0.0050 0.0121 0.0569

H2O–BrCCArF 3.50 0.0061 – -0.0011 0.0053 0.0134 0.0634

H2O–BrCCKrF 3.32 0.0057 – -0.0012 0.0050 0.0131 0.0619

H2O–BrCCXeF 3.14 0.0052 – -0.0012 0.0046 0.0127 0.0602

HMeO–BrCCArF 4.70 0.0077 0.0147 -0.0019 0.0081 0.0165 0.0751

H3N–BrCCF 5.95 0.0133 – -0.0016 0.0134 0.0158 0.0597

H3N–BrCCArF 7.39 0.0176 – -0.0020 0.0165 0.0180 0.0656

H3N–BrCCKrF 6.87 0.0159 – -0.0020 0.0151 0.0174 0.0640

H3N–BrCCXeF 6.31 0.0142 – -0.0020 0.0137 0.0166 0.0619

H2MeN–BrCCArF 8.54 0.0230 0.1033 -0.0029 0.0215 0.0224 0.0775

H2LiN–BrCCArF 38.72 0.0865 -0.0184 -0.0052 0.1087 0.0461 0.1058

Table 3 The most positive electrostatic potential (Vs,max, au) on the

halogen atom at the 0.001 electrons Bohr-3 isodensity surface at the

MP2/aug-cc-pVTZ level

Vs,max

ClCCF 0.0404

ClCCArF 0.0651

ClCCKrF 0.0585

ClCCXeF 0.0515

BrCCF 0.0515

BrCCArF 0.0756

BrCCKrF 0.0688

BrCCXeF 0.0618

Fig. 5 Relationship between the interaction energy and the Laplacian

at the intermolecular BCP in the O���Cl (filled square), O���Br (filledtriangle), and N���Br (filled diamond) halogen-bonded complexes

Struct Chem

123

Hartree–Fock energy beyond the second order of inter-

molecular operator. The Eind term also contains the

exchange-induction energy and the Edisp term also includes

the exchange-dispersion energy. The results are given in

Table 4. As expected, the Eelst, Eind, Edisp, and dEint-r(HF) terms

show an attractive contribution, while the Eexch term is a

repulsive contribution. The Ng insertion causes all terms

increase in magnitude; however, the Eelst term suffers the

largest effect from the Ng insertion. Furthermore, in all

complexes, the major attractive contribution to the total

attractive energy results from Eelst, while other attractive

contribution is small. This supports the conclusion that the

halogen bond is dominated by electrostatic interactions.

Conclusions

The influence of insertion of a noble gas atom on halogen

bonding in H2O���XCCNgF and H3N���XCCNgF (X = Cl

and Br; Ng = Ar, Kr, and Xe) complexes has been

investigated with quantum chemical calculations. The most

positive electrostatic potential on the X atomic surface is

increased because of the insertion of Ng atom into the C–F

bond. Thus, the insertion of Ng atom brings out an

enhancing effect on the strength of halogen bond. This

enhancement is decreased with the increase of Ng atomic

number. The substituents of methyl and Li in the electron

donor further strengthen the halogen bond. The ED anal-

yses show that the electrostatic interaction plays a domi-

nant role for the stability of the halogen-bonded complexes.

Acknowledgments This study was supported by the National

Natural Science Foundation of China (20973149), the Outstanding

Youth Natural Science Foundation of Shandong Province

(JQ201006), and the Program for New Century Excellent Talents in

University. It was also supported in part by the open project of State

Key Laboratory of supramolecular structure and materials (SKLS

SM201216) from Jilin University, China.

References

1. Bartlett N (1962) Proc Chem Soc 1962:218

2. Pettersson M, Lundell J, Rasanen M (1995) J Chem Phys

102:6423

3. Pettersson M, Lundell J, Rasanen M (1995) J Chem Phys 103:205

4. Pettersson M, Nieminen J, Khriachtchev L, Rasanen M (1997)

J Chem Phys 107:8423

5. Pettersson M, Lundell J, Khriachtchev L, Rasanen M (1998)

J Chem Phys 109:618

6. Pettersson M, Lundell J, Khriachtchev L, Isoniemi E, Rasanen M

(1998) J Am Chem Soc 120:7979

7. Pettersson M, Khriachtchev L, Lundell J, Rasanen M (1999)

J Am Chem Soc 121:11904

8. Bihary Z, Chaban GM, Gerber RB (2002) J Chem Phys 116:5521

9. Pettersson M, Khriachtchev L, Lignell A, Rasanen M, Bihary Z,

Gerber RB (2002) J Chem Phys 116:2508

10. Lundell J, Khriachtchev L, Pettersson M, Rasanen M (2000) Low

Temp Phys 26:680

11. Khriachtchev L, Pettersson M, Lundell J, Rasanen M (2001)

J Chem Phys 114:7727

12. Khriachtchev L, Pettersson M, Runeberg N, Lundell J, Rasanen

M (2000) Nature (Lond.) 406:874

13. Wong MW (2000) J Am Chem Soc 122:6289

14. Yockel S, Gawlik E, Wilson AK (2007) J Phys Chem A

111:11261

15. Avramopoulos A, Reis H, Li J, Papadopoulos MG (2004) J Am

Chem Soc 126:6179

16. Holka F, Avramopoulos A, Loboda O, Kello V, Papadopoulos

MG (2009) Chem Phys Lett 472:185

17. Avramopoulos A, Papadopoulos MG, Sadlej AJ (2002) J Chem

Phys 117:10026

18. McDowell, Sean AC (2003) J Chem Phys 118:4066

19. McDowell, Sean AC (2003) Chem Phys Lett 368:649

20. McDowell, Sean AC (2005) Chem Phys Lett 406:228

21. McDowell, Sean AC (2003) J Chem Phys 118:7283

22. McDowell, Sean AC (2003) J Chem Phys 119:3711

23. McDowell, Sean AC (2004) J Chem Phys 121:5728

24. Solimannejad M, Boutalib A (2006) ChemPhys 320:275

25. Solimannejad M, Alkorta I (2006) Chem Phys 324:459

26. Solimannejad M, Boutalib A (2004) Chem Phys Lett 389:359

27. Solimannejad M, Scheiner S (2005) J Phys Chem A 109:6137

28. Solimannejad M, Scheiner S (2005) J Phys Chem A 109:11933

29. Singh PC (2011) Chem Phys Lett 515:206

30. Politzer P, Murray JS, Clark T (2010) Phys Chem Chem Phys

12:7748

31. Metrangolo P, Carcenac Y, Lahtinen M, Pilati T, Rissanen K, Vij A,

Resnati G (2009) Science 323:1461

32. Metrangolo P, Meyer F, Pilati T, Resnati G, Terraneo G (2008)

Angew Chem Int Ed 47:6114

33. Metrangolo P, Neukirch H, Pilati T, Resnati G (2005) Acc Chem

Res 38:386

34. Auffinger P, Hays FA, Westhof E, Ho PS (2004) Proc Natl Acad

Sci USA 101:16789

35. Voth AR, Hays FA, Ho PS (2007) Proc Natl Acad Sci USA

104:6188

36. Voth AR, Khuu P, Oishi K, Ho PS (2009) Nat Chem 1:74

37. Li QZ, Liu ZB, Jing B, Li WZ, Cheng JB, Gong BA, Sun JZ

(2010) Spectrochi Acta A 77:506

38. Frisch MJ Trucks GW Schlegel HB, Scuseria GE, Robb MA,

Cheeseman JR, Scalmani G, Barone V, Mennucci B, Petersson

GA, Nakatsuji H, Caricato M, Li X, Hratchian HP, Izmaylov AF,

Bloino J, Zheng G, Sonnenberg JL, Hada M, Ehara M, Toyota K,

Fukuda R, Hasegawa J, Ishida M, Nakajima T, Honda Y, Kitao

O, Nakai H, Vreven T, Montgomery JrJA, Peralta JE, Ogliaro F,

Bearpark M, Heyd JJ, Brothers E, Kudin KN, Staroverov VN,

Kobayashi R, Normand J, Raghavachari K, Rendell A, Burant JC,

Iyengar SS, Tomasi J, Cossi M, Rega N, Millam JM, Klene M,

Knox J. E, Cross J. B, Bakken V, Adamo C, Jaramillo J, Gom-

perts R, Stratmann RE, Yazyev O, Austin AJ, Cammi R, Pomelli

C, Ochterski JW, Martin RL, Morokuma K, Zakrzewski VG,

Table 4 Energy decomposition in the complexes. All are in kcal/mol

Eelst Eexch Eind Edisp dEint-r(HF) Eint

sapt

H2O–ClCCF -2.79 3.07 -0.50 -1.61 -0.25 -2.08

H2O–ClCCArF -4.07 3.77 -0.71 -1.78 -0.36 -3.15

H2O–BrCCF -4.97 5.66 -0.99 -2.02 -0.47 -2.79

H2O–BrCCArF -6.24 6.35 -1.31 -2.18 -0.61 -3.99

H3N–BrCCF -10.51 12.72 -2.11 -3.17 -1.11 -4.18

H3N–BrCCArF -11.68 12.84 -2.45 -3.18 -1.31 -5.78

Struct Chem

123

Voth GA, Salvador P, Dannenberg JJ, Dapprich S, Daniels AD,

Farkas O, Foresman JB, Ortiz JV, Cioslowski J, Fox DJ (2009)

Gaussian 09, Revision A.02. Gaussian Inc., Wallingford

39. Møller C, Plesset MS (1934) Phys Rev 46:618

40. Riley K, Merz KM (2007) J Phys Chem A 111:1688

41. Solimannejad M, Scheiner S (2008) J Phys Chem A 112:4120

42. Alkorta I, Blanco F, Solimannejad M, Elguero J (2008) J Phys

Chem A 112:10856

43. Boys SF, Bernardi F (1970) Mol Phys 19:553

44. Reed AE, Curtiss LA, Weinhold F (1988) Chem Rev 88:899

45. Biegler-Konig F (2000) AIM2000. University of Applied Sci-

ences, Bielefeld

46. Bulat FA, Toro-Labbe A, Brinck T, Murray JS, Politzer P (2010)

J Mol Model 16:1679

47. Bukowski R, Cencek W, Jankowski P, Jeziorski B, Jeziorska M,

Kucharski SA, Misquitta AJ, Moszynski R, Patkowski K, Rybak

S, Szalewicz K, Williams HL,P. Wormer ES (2003) SAPT2002:

An Ab initio program for many-body symmetry-adapted pertur-

bation theory calculations of intermolecular interaction energies.

Sequential and Parallel Versions. University of Delaware,

Newark

48. Cheng JB, Wang YL, Li QZ, Liu ZB, Li WZ, Gong BA (2009)

J Phys Chem A 113:5235

49. Liu XF, Li QZ, Li R, Li WZ, Cheng JB (2011) Spectrochi Acta A

84:68

50. Li QZ, Wu GS, Yu ZW (2006) J Am Chem Soc 128:1438

51. Li QZ, An XL, Luan F, Li WZ, Gong BA, Cheng JB (2008)

J Phys Chem A 112:3985

52. Li QZ, Jing B, Liu ZB, Li WZ, Cheng JB, Gong BA, Sun JZ

(2010) J Chem Phys 133:114303

53. Cheng JB, Li R, Li QZ, Jing B, Liu ZB, Li WZ, Gong BA, Sun JZ

(2010) J Phys Chem A 114:10320

54. Koch U, Popelier PLA (1995) J Phys Chem 999:747

55. Lipkowski P, Grabowski SJ, Robinson TL, Leszczynski J (2004)

J Phys Chem A 108:10865

56. Clark T, Hennemann M, Murray JS, Politzer P (2007) J Mol

Model 13:291

57. Politzer P, Lane P, Concha MC, Ma YG, Murray JS (2007) J Mol

Model 13:305

Struct Chem

123