Journal of Natural Gas Chemistry 16(2007)7077

Article

Ab Initio Calculation of Room Temperature Ionic Liquid

1-Ethyl-3-Methyl-Imidazolium Chlorocuprate (I)
Renqing L
u1 ,

Hejin Tangbo2 ,

Zuogang Cao1

1. College of Chemistry and Chemical Engineering, China University of Petroleum (East China), Dongying 257061, Shandong,
China; 2. College of Chemistry and Chemical Engineering, Shanghai University of Engineering Science, Shanghai 201620, China
[ Manuscript received July 26, 2006; revised August 28, 2006 ]

Abstract:
The Hartree-Fock method has been employed to investigate the electronic structures of

+
+
EMIM+ (1-ethyl-3-methyl-imidazolium+ ), CuCl
2 , Cu2 Cl3 , CuCl3 , EMIM -CuCl2 , EMIM -Cu2 Cl3 ,
2

2
+
+
and EMIM -CuCl3 pairs. Full optimization and frequency analyses of EMIM , CuCl2 , Cu2 Cl3 , CuCl3 ,

2
+
+
eight initial EMIM+ -CuCl
geometries have been carried
2 , six EMIM -Cu2 Cl3 , and four EMIM -CuCl3
out using Gaussian-94 soft-package at 6-31+G(d,p) basis set level for hydrogen, carbon, nitrogen, chlorine
atoms and Hay-Wadt effective core potential for copper atom. The electronic structures of lowest energy

2
+
+
+
of EMIM+ -CuCl
have
2 , EMIM -Cu2 Cl3 , EMIM -CuCl3 , single EMIM , CuCl2 , Cu2 Cl3 , and CuCl3

+
been comparatively studied. The calculated results showed that EMIM -CuCl2 pair conformer of lowest
energy was five ring parallel to ClCuCl with 3.2
A distance, EMIM+ -CuCl2
3 pair conformer of lowest
2
energy was five ring parallel to CuCl3 plane with 3.4
A distance, and the optimized EMIM+ -Cu2 Cl
3 pair
conformer of lowest energy was five ring perpendicular to ClCuClCuCl plane with 3.0
A distance
between the terminal Cl atoms and the 5-ring of EMIM+ . The cohesion between cations and anions
is brought about by CH Cl hydrogen bonds that are reinforced by charge assistance. The frequency
analyses suggested that all stationary points are minimum because of no appearing of imaginary frequency.
The assigned frequencies were in agreement with the experimental report. The low energy of interaction
because of the bulky asymmetry of EMIM+ and the charge dispersion of cation and anion leads to the low

2
+
+
melting point of the ionic liquids, EMIM+ -CuCl
2 , EMIM -Cu2 Cl3 , and EMIM -CuCl3 . The interac
2
+
+
tion energy of EMIM+ -CuCl
,
EMIM
-Cu
Cl
,
and
EMIM
-CuCl
is
309.0
kJ/mol,
316.8
kJ/mol, and
2
2
3
3
320.2 kJ/mol, respectively. The relationship of interaction energy via distance between cations and anions
was also investigated by single point energy scan.
Key words: ionic liquid; Hartree-Fock; 1-ethyl-3-methyl-imidazolium; chlorocuprate (I)

1. Introduction
Ionic liquids are the versatile green media for
several applications in chemical synthesis, enzymatic
catalysis, and engineering processes [17]. Ionic
liquids are based on organic cations (e.g. imidazolium, pyridinium, ammonium, phosphonium, triazolium derivatives) and anions, and their choice allows the tuning of physicochemical properties. It is
thus important to understand the interaction between
cation and anion at the molecular level. Significant

information can be gained by modern physical spectroscopy. Molecular simulations also provide important information with regard to the behavior of ionic
liquid cation-anion pair. Molecular dynamics (MD)
and Monte Carlo (MC) methods, which are based on
the empirical representations of the potential energy,
have been employed to investigate the fundamental
physicochemical properties of various imidazoliumderivatives-based ionic liquids [820], but the fundamental interactions and electronic structures between
the selected compounds of anions and cations can be

Corresponding author. Tel: +86-546-8392287 (O); Fax: +86-546-8391971; E-mail: lvrq2000@163.com (R. L
u).

Journal of Natural Gas Chemistry Vol. 16 No. 1 2007

described only by quantum chemical methods. The

quantum chemical calculations have been used in various physical investigations. Several quantum chemical studies of imidazolium-derivatives-based ionic liquid with different anions, such as PF
6 [21,22,23],
2

FeCl
and
FeCl
,
FeCl
and
Fe
Cl
2
3
4
4
7 [24], AlCl4

and Al2 Cl
[22,28,29], F , Br [28],
7 [25,26,27], Cl

AuCl4 and Au2 Cl7 [26], SnCl

3 and Sn2 Cl5 [30],

BF4 [31], CF3 COO , C3 F7 COO , CF3 SO

3 and

C4 F3 SO3 [32], InCl4 [33,34] and GaCl4 [35], were reported. The primary room temperature ionic liquids
based on the mixtures of various metal chloride and
imidazolium chloride were widely studied. These mixtures have a wide range of compositions. Considering
the use of ionic liquids as reaction media at a temperature as low as possible and the known activity of
Cu+1 in reactions involving carbon monoxide, olefins
as well as in applications of batteries, etc., the existence of chlorocuprate (I) salts as liquids at and below
room temperature may be of practical importance.
The studies of room temperature ionic liquid-based
CuCl [3638] showed that the composition range of
the mixture was wide, and the various forms of anions were discussed. Solution equilibrium data for
(nm)
] species, m=15 and n=19, have
[Cum Cln
been reported [3640]. Similar species may be postulated to exist in the liquid chlorocuprate (I) salts.
Equilibria such as

71

of this investigation is to determine the interaction

+
of EMIM+ and CuCl
and Cu2 Cl
2 , EMIM
3 , and
2
+
EMIM and CuCl3 in the gas phase to compare
the lowest energy models and electronic structures by
Hartree-Fock method.
2. Calculation methods
All calculations have been performed using
Hartree-Fock method as implemented in Gaussian 94
soft-package [41], and 6-31+G(d, p) basis sets level for
hydrogen, carbon, nitrogen, chlorine atoms taken consideration of diffuse functions and polarization functions. Considering the computational cost and the
substantial relativistic effect of heavy atoms, the HayWadt effect core potentials [42] were employed to Cu
atom. The core orbitals replaced by the effective potentials are 1s, 2s, 2p, 3s, and 3p and the valence
orbitals are 3d, 4s, and 4p. No constraints have been

used for model optimization except CuCl

2 , Cu2 Cl3
2
and CuCl3 with Dh , C2v , and D3h symmetry, respectively. Geometry optimizations have been carried
out to a minimum for all initial structures. The frequency analysis was computed using second analytical derivatives to check the saddle point or minimum
point by appearing imaginary frequency or none. Zero
point energy (ZPE) corrections have been calculated
for all optimized structures.

CuCl
2 + Cl CuCl3

CuCl
2 + CuCl Cu2 Cl3

Cu2 Cl
3 + Cl 2CuCl2

would be shifted by the addition of chloride ion

donors or copper (I) chloride as the chloride ion acceptor. Spectroscopic evidence [3638] has been presented for species such as CuCl2
in the chloride3
rich (basic), Cu2 Cl
in
the
chloride-poor
(acidic), and
3
CuCl
in
the
neutral
CuCl
room
temperature
ionic
2
liquids. A simple postulate suggests that the structure of CuCl
2 possess Dh symmetry with linear
ClCuCl bonds, the structure of Cu2 Cl
3 possess
C2v symmetry with linear ClCuCl bonds at twocoordinate copper (I) and a bent Cu-Cl-Cu bridge because of the lone pairs on the bridging chloride, and
the structure of CuCl2
ion possess D3h symmetry
3
with trigonal-planar three-coordinate copper (I).
In this theoretical study, ab initio calculations are
employed to determine the molecular structures of
+
neutral ionic liquid EMIM+ -CuCl
2 , acidic EMIM
2
+
Cu2 Cl3 , and basic EMIM -CuCl3 . The objective

3. Determination of initial structures

This article is concerned with the Hartree-Fock
method studies of cation-anion pair interaction of
neutral, acidic, and basic ionic liquids, EMIM+ and
+
+
CuCl
and Cu2 Cl
and CuCl2
2 , EMIM
3 , EMIM
3 ,
respectively. As a first step in the specification

2
of cation-anion pair, CuCl
2 , Cu2 Cl3 , and CuCl3
were placed in various positions around the ethyl side
chain, and the methyl group was placed adjacent to
the ring, opposite sides, and above and below the imidazolium ring. The several forms of hydrogen bonds
between different hydrogen atoms of EMIM+ and

2
chlorine atoms of CuCl
2 , Cu2 Cl3 , and CuCl3 were
taken into account. The first form is single hydrogen
bond that involved one hydrogen of EMIM+ and one

2
chlorine of CuCl
2 , Cu2 Cl3 or CuCl3 , the second
form is the ring structures formed by two hydrogen
bonds between two hydrogen atoms of EMIM+ and

2
two chlorine atoms of CuCl
2 , Cu2 Cl3 , and CuCl3 ,
and the last form is three center, bifurcated or tri-

72

Renqing L
u et al./ Journal of Natural Gas Chemistry Vol. 16 No. 1 2007

furcated hydrogen bonds reported by other studies

[43,44] as displayed in Figure 1. In Figure 1, A-H
represents weak acid or hydrogen bond donor and B
represents the weak base or hydrogen bond acceptor.
The eight initial geometries of EMIM+ -CuCl
2 , six
initial geometries of EMIM+ -Cu2 Cl
,
and
four
ini3
2
+
tial geometries of EMIM -CuCl3 were established
for optimization.

The diagrams of most stable optimized geome

2
+
tries for EMIM+ , CuCl
2 , Cu2 Cl3 , CuCl3 , EMIM

2
CuCl2 , EMIM+ -Cu2 Cl3 , and EMIM+ -CuCl3 are
shown in Figure 2. The partial bond lengths and bond

+
angles of EMIM+ , CuCl
2 and EMIM -CuCl2 are

presented in Table 1, and those of Cu2 Cl3 , CuCl2

3 ,

2
+
+
EMIM -Cu2 Cl3 , and EMIM -CuCl3 are listed in
Table 2.

4. Results and discussion

4.1 All the optimized geometries and their stability

Figure 1. Forms of three center, bifurcated, and trifurcated hydrogen bonds

+
+
Figure 2. The 3D geometries of EMIM+ , CuCl
2 , Cu2 Cl3 , CuCl3 , EMIM -CuCl2 , EMIM -Cu2 Cl3 , and
pairs
EMIM+ -CuCl2
3

73

Journal of Natural Gas Chemistry Vol. 16 No. 1 2007

Table 1. Partial bond lengths and bond angles of

+
EMIM+ , CuCl
2 , and EMIM -CuCl2 pair
Bond

Bond length(
A) and bond angle(o )
EMIM+

CuCl
2

EMIM+ -CuCl
2

Cu21 Cl20

2.180

2.170

Cu21 Cl22

2.180

2.187

C2 H6

1.065

1.069

C9 H13

1.078

1.080

C10 H14

1.078

1.080

Cl22 H14

3.018

Cl22 H6

2.849

Cl20 H13

3.091

Cl20 Cu21 Cl22

180.0

174.1

The calculated Cl20 Cu21 and Cu21 Cl22 bond

lengths of single CuCl

2 are 2.180 A and 2.180 A,

respectively, and the Cl20 Cu21 Cl22 bond angle is 180o . The electron configuration of Cu(I)
is 1s2 2s2 2p6 3s2 3p6 3d10 and the virtual valence orbitals are 4s and 4p. When two Cl ions coordinate with Cu(I) ion, the one 4s orbital and one 4p
orbital of the centric ion hybridize to form two sp
hybrid orbitals, and its bond angle is 180o . This results in the linear configuration of complex CuCl
2.
The calculated Cl23 Cu21 , Cu21 Cl20 , Cl20 Cu22 ,
and Cu22 Cl24 bond lengths of single Cu2 Cl
3 are
2.145
A, 2.255
A, 2.255
A, and 2.145
A, respectively,
and the C23 Cu20 Cl20 , Cu21 Cl20 Cu22 , and
Cl20 Cu22 Cl24 bond angles are 177.8o , 114.0o , and
177.8o respectively. The electron configuration of
Cl20 anion is 1s 2 2s 2 2p 6 3s 2 3p 6 .

2
+
+
Table 2. Partial bond lengths and bond angles of Cu2 Cl
pairs
3 , CuCl3 , EMIM -Cu2 Cl3 , and EMIM -CuCl3

Bond

Bond length(
A) and bond angle(o )
Cu2 Cl
3

EMIM+ -Cu

2 Cl3

Bond

Bond length(
A) and bond angle(o )
CuCl2
3

EMIM+ -CuCl2
3

Cl23 Cu21

2.145

2.150

Cu20 Cl21

2.350

2.354

Cu21 Cl20

2.255

2.253

Cu20 Cl22

2.350

2.347

Cl20 Cu22

2.255

2.240

Cu20 Cl23

2.350

2.352

Cu22 Cl24

2.145

2.156

C16 H19

C10 H14

1.080

C10 H15

C5 H7

1.067

C5 H7

C2 H6

1.070

C4 H8

C9 H13

1.078

C9 H12

Cl23 H14

2.883

Cl23 H7

3.688

Cl23 H7

3.084

Cl23 H8

3.688

Cl24 H6

2.667

Cl22 H12

2.578

Cl24 H13

2.961

Cl22 H13

3.792

Cl23 Cu21 Cl20

177.8

179.5

C9 H13

Cu21 Cl20 Cu22

114.0

102.4

Cl21 H15

2.580

Cl20 Cu22 Cl24

177.8

178.0

Cl21 H19

3.533

The orthogonal 3p orbitals and repulsive electrons

lead to the V configuration of the complex Cu2 Cl
3.
The calculated Cl23 Cu20 , Cl21 Cu20 , and Cl22
Cu20 bond lengths of single CuCl2
is 2.350
A, and
3
the Cl23 Cu20 Cl21 , Cl23 Cu20 Cl22 , and Cl21
Cu20 Cl23 bond angles is 120.0o . The virtual valence orbitals of Cu(I) are 4s and 4p. When three
Cl ions coordinate with Cu(I) ion, the one 4s orbital
and two 4p orbitals of centric ion hybridize to form
three sp 2 hybrid orbitals, and its bond angle is 120o .
The calculated partial bond lengths of the EMIM+
cation C2 H6 , C9 H13 , and C10 H14 are 1.065
A,

1.078 A, and 1.078 A, respectively. The 5-ring of

EMIM+ is planar. C2 , C5 , C4 , N1 , and N3 atoms undergo sp 2 hybridization to form three hybrid orbitals

for three covalent bonds, whereas the five atoms supply six electrons to form delocalized and conjugated
56 bond, which is perpendicular to the five ring plane.
All the eight initial geometries of EMIM+ -CuCl
2 , six
initial geometries of EMIM+ -Cu2 Cl
,
and
four
ini3
2
+
tial geometries of EMIM -CuCl3 were optimized,
and the frequency analyses showed that all the attained structures were minimum points. Although the
difference of initial structures is remarkable, the obtained optimization geometries exhibit similar structures. CuCl
2 anion is parallel to the five ring plane
of EMIM+ cation, and the distances between cationanion pair is about 3.2
A. Cu2 Cl
3 anion is vertical to
the five ring plane of EMIM+ cation, and the distances between terminal chlorine atoms and 5-ring

74

Renqing L
u et al./ Journal of Natural Gas Chemistry Vol. 16 No. 1 2007

plane of EMIM+ is about 3.0

A. CuCl2
3 anion is parallel to the five ring plane of EMIM+ cation, and the
distances between cation-anion pair is about 3.4
A.
Because of the similar composition of initial geometries, the most stable structures of EMIM+ -CuCl
2,
2
+
EMIM+ -Cu2 Cl
,
and
EMIM
-CuCl
could
be
de3
3
cided in terms of heat of formation. The 3D structures
of lowest energy are displayed in Figure 2. It can be
found that Cu21 Cl20 and Cu21 Cl22 bond lengths
are 2.170
A and 2.187
A, respectively, C2 H6 , C9
H13 , and C10 H14 bond lengths are 1.069
A, 1.080
A,
+
and 1.080
A, respectively, for EMIM -CuCl
.
The
2
hydrogen bonding distances between Cl22 and H14 ,
Cl22 and H6 , Cl20 and H13 are 3.018
A, 2.849
A,
and 3.091
A, respectively. The bond angle of Cl20
o
Cu21 Cl22 for single CuCl
2 anion is 180 , and the
Cl20 Cu21 Cl22 bond angle of EMIM+ -CuCl
2 pair
is 174.1o . The Cl23 Cu21 , Cu21 Cl20 , Cl20 Cu22 ,
and Cu22 Cl24 bond lengths of EMIM+ -Cu2 Cl
3 are
2.150
A, 2.253
A, 2.240
A, and mbox2.156
A, respectively, and the hydrogen bonding distances between Cl23 and H14 , Cl23 and H7 , Cl24 and H6 ,
and Cl24 and H13 are 2.883
A, 3.084
A, 2.667
A,

and 2.961 A, respectively. The Cl23 Cu21 Cl20 ,

Cu21 Cl20 Cu22 , and Cl20 Cu22 Cl24 bond angles of Cl20 Cu21 Cl22 for single Cu2 Cl
3 anion are
177.8o , 114.0o , and 177.8o , respectively, and the corresponding bond angles of EMIM+ -Cu2 Cl
3 pair is
179.5o , 102.4o , and 178.0o , respectively. It can also be
seen that Cl23 Cu20 , Cl21 Cu20 , and Cl22 Cu20
bond lengths of EMIM+ -CuCl2
are 2.352
A, 2.354
3

A, and 2.347 A, respectively, the hydrogen bonding

distances between Cl21 and H15 , Cl21 and H19 , Cl23
and H7 , Cl23 and H8 , Cl22 and H12 , and Cl22 and
H13 are 2.580
A, 3.533
A, 3.688
A, 3.688
A, 2.578
A,
and 3.792
A, respectively. The Cl21 Cu20 Cl22 ,
Cl22 Cu20 Cl23 , and Cl23 Cu20 Cl21 bond angles of single CuCl2
anion are 120.0o , and the cor3
responding bond angles of EMIM+ -CuCl2
pair are
3
179.1o , 174.6o , and 177.9o , respectively. The change

of bond lengths and bond angles for CuCl

2 , Cu2 Cl3
and CuCl2
may be ascribed to the hydrogen bond
3
formation between H14 , H6 , and H13 atoms of EMIM+
and chlorine atoms of CuCl
2 ; H14 , H6 , H7 , and H13
+
atoms of EMIM and chlorine atoms of Cu2 Cl
3 ; and
H15 , H19 , H7 , H8 , H12 , and H13 atoms of EMIM+
and chlorine atoms of CuCl2
3 . The adjacent atoms in
+
+
the EMIM+ -CuCl
,
EMIM
-Cu2 Cl
2
3 , and EMIM 2
CuCl3 are only of two types, namely hydrogen and
chlorine atoms, and the hydrogen atoms are bound

only to carbon atoms; therefore, the role of C

H Cl interactions can be used to test the cohesion
between cation and anion. Interactions of this type
are expected to be weak because of the low acidity of
the C-H system. However, the number of potential
hydrogen atoms and chlorine atoms is very large in
the ionic liquid systems and this contributes to the
physicochemical properties of the ionic liquid. Furthermore, hydrogen bonds such as CH Cl may
have a critical effect on ionic liquid cohesion when
it is reinforced by the different polarity of donors
and acceptors, i.e, when these weak electronic interactions are charge assisted [45]. Charge assistance
is provided in ionic liquids because the donor is positively charged and the acceptor is negatively charged.
This means that EMIM+ cation has +1 charge, and
this is responsible for the + increase of CH+ ,

whereas CuCl
2 , Cu2 Cl3 anions have 1 charge and
2
CuCl3 has 2 charge, and this is responsible for the
increase of CuCl . The NBO charge analysis of Cl20 , Cl22 , H14 , H6 , and H13 for EMIM+ CuCl
2 pair is 0.825, 0.824, +0.283, +0.273, and
+0.264, respectively, and that of Cl23 , Cl24 , H14 , H6 ,
H7 , H13 for EMIM+ -Cu2 Cl
3 pair is 0.541, 0.524,
+0.208, +0.198, +0.244, and +0.219, respectively.
The NBO charge analysis of Cl21 , Cl22 , Cl23 , H15 ,
H19 , H7 , H8 , H12 , and H13 for EMIM+ -CuCl2
pair
3
is 0.909, 0.910, 0.918, +0.303, +0.270, +0.278,
+0.275, +0.300, and +0.243, respectively, which verify the point of view of charge assistance. The NBO
charge analysis of Cl20 and Cl22 for single CuCl
2 is
0.840 and 0.840, respectively, and it means that
partial electrons of CuCl
2 may transfer to the five
ring of EMIM+ confirmed by the NBO charge of N1
(0.432) and N3 (0.431) for single EMIM+ . But
this is contrary to the N1 (0.455) and N3 (0.453)
for EMIM+ -CuCl
2 pair. The NBO charge analysis
of Cl23 and Cl24 for single Cu2 Cl
3 is 0.815 and
0.815, respectively, and it means that partial elec+
trons of Cu2 Cl
3 may transfer to five ring of EMIM
confirmed by the NBO charge of N1 (+0.387) and
N3 (0.019) for single EMIM+ , and it is contrary
to the N1 (0.636) and N3 (0.191) for EMIM+ CuCl
2 pair. The NBO charge analysis of Cl21 , Cl22 ,
and Cl23 for single CuCl2
is 0.931, and it means
3
that partial electrons of CuCl2
3 may transfer to five
ring of EMIM+ confirmed by NBO charge of N1
(0.435) and N3 (0.435) for single EMIM+ , and
it is contrast to the N1 (0.456) and N3 (0.458)
for EMIM+ -CuCl2
pair. It was shown that when
3

Journal of Natural Gas Chemistry Vol. 16 No. 1 2007

assisted by charge between anions and cations, the

hydrogen bonds may play a significant role for the
interaction of ionic liquids. The +1 charge dispersion
among the all atoms of EMIM+ cation, the 1 charge
dispersion among the three atoms of CuCl
2 anion, the
1 charge dispersion among the five atoms of Cu2 Cl
3,
and the 2 charge dispersion among the four atoms
of CuCl2
lead to lower electrostatic interaction be3
tween bulky cation and anion. The asymmetry of
bulky EMIM+ cation may also lead to the loose packing of cation-anion pair to decrease the interactions.
The negligible vapor pressure may be assigned to the
hydrogen bond formation.
4.2 Frequency analyses and assignments
The initial geometries of EMIM+ , CuCl
2,

+
+
Cu2 Cl3 , CuCl3 , EMIM -CuCl2 , EMIM -Cu2 Cl
3,
and EMIM+ -CuCl2
were
optimized
at
HF/63
31+G(d,p) level. The principal scaled vibration frequencies near 3094 cm1 , 3092 cm1 , 2966 cm1 ,
2923 cm1 , 2911 cm1 , 2883 cm1 , 1580 cm1 ,
1572 cm1 , 1463 cm1 , 1462 cm1 , 1392 cm1 ,
1153 cm1 , 632 cm1 , and 605 cm1 for EMIM+

+
+
CuCl
2 , EMIM -CuCl2 , and EMIM -CuCl2 pairs
are assigned to CH ring stretching, CH ring stretching, CH3 (N) stretching, CH2 stretching, CH3 stretching, CH3 (C) stretching, ring stretching, ring bending, CH3 bending, CH2 bending, CCH bending, ring
stretching, and ring out of plane bending [46]. In
comparison with single EMIM+ , several corresponding scaled vibration frequencies exhibit red shift, the
shift of vibrational frequencies may be caused by the
hydrogen bonding interaction between EMIM+ and

2
CuCl
2 , Cu2 Cl3 , and CuCl3 .
4.3 The cation-anion pair interaction energy
The heat of formation, zero point energy (ZPE),
zero point corrected heat of formation (ZPCHF) of

+
EMIM+ , CuCl
2 , Cu2 Cl3 , CuCl3 , EMIM -CuCl2 ,

+
EMIM+ -CuCl
2 , and EMIM -CuCl2 were calculated,
and the scaling factor of 0.9135 [47] was applied for
the zero point energy. The interaction energy be
+
tween EMIM+ and CuCl
2 , EMIM and Cu2 Cl3 , and
EMIM+ and CuCl2
3 was computed as follows:
H = {EZPCHF (pair) [EZPCHF (EMIM+ )
+EZPCHF (single)]}
The interaction energy is 309.0 kJ/mol for

+
EMIM+ -CuCl
2 , 316.8 kJ/mol for EMIM -Cu2 Cl3 ,

75

and 320.2 kJ/mol for EMIM+ -CuCl2

3 , and the low
interaction energy gives rise to low melting point.
4.4 The interaction energy via distance be
tween EMIM+ and CuCl
2 , Cu2 Cl3 , and
2
CuCl3
In the Hartree-Fock (HF) level theory, the lowest energy forms among eight initial geometries of
+
EMIM+ -CuCl
2 , four initial geometries of EMIM 2

2
CuCl3 are the conformers of CuCl2 and CuCl3
that are parallel to the 5-ring of EMIM+ , so the dis2
tances between 5-ring and CuCl
as coor2 , CuCl3
dinates were employed to investigate the interaction.
The Cu2 Cl
3 plane that is perpendicular to 5-ring is
considered as the most stable conformer of EMIM+ Cu2 Cl
3 , and their interaction energy was compared
with the distance between terminal chlorine atoms of
+
Cu2 Cl
3 and 5-ring plane of EMIM . Single point energy scan at the HF/6-31+G(d,p) for all atoms except
Cu at effective core potential was executed to describe
the energy change curve with distances as shown in
Figure 3. It can be observed that the distance of low2
+
est energy of EMIM+ -CuCl
2 , EMIM -CuCl3 , and

EMIM -Cu2 Cl3 is 3.3 A, 3.4 A, and 3.0 A, respectively, which are in accordance with the above optimized results. Considering the reported ionic liquid
structure such as EMIM+ -AuCl
4 [48] and the optimized structures of lowest energy, it is reasonable
to assume that the distribution of EMIM+ -CuCl
2,
2

+
+
EMIM -CuCl3 , and EMIM -Cu2 Cl3 pairs may be
parallel to each other.
5. Conclusions
+
The neutral EMIM+ -CuCl
2 , acidic EMIM
2
+
Cu2 Cl3 , and basic EMIM -CuCl3 ionic liquids were
investigated by computational quantum method at
HF/6-31+G(d,p) level. The single EMIM+ , CuCl
2,
2

+
Cu2 Cl
3 , CuCl3 , and eight initial EMIM -CuCl2 ,

+
+
six initial EMIM -Cu2 Cl3 , and four initial EMIM CuCl2
pair geometries were optimized and the fre3
quency analysis was performed. The calculated results suggested that the asymmetry of EMIM+ and
the charge delocalization of EMIM+ and CuCl
2,

2
Cu2 Cl3 , and CuCl3 are responsible for the low melting point of the ionic liquids. The interactions be
2
tween EMIM+ and CuCl
2 , Cu2 Cl3 , CuCl3 is caused
by the hydrogen bonds between the hydrogen atoms

of EMIM+ and chlorine atoms of CuCl

2 , Cu2 Cl3 , and
2
CuCl3 reinforced by charge assistance. The inter-

76

Renqing L
u et al./ Journal of Natural Gas Chemistry Vol. 16 No. 1 2007

+ and terminal
Figure 3. The energy vs distance between 5-ring of EMIM+ and CuCl
2 (a), 5-ring of EMIM
+ and CuCl2 plane (c)
chlorine atoms of Cu2 Cl
(b),
and
5-ring
of
EMIM
3
3

+
action energy is 309.0 kJ/mol for EMIM+ -CuCl
2 , 316.8 kJ/mol for EMIM -Cu2 Cl3 , and 320.2 kJ/mol for
2

+
+

EMIM -CuCl3 . The optimized distances are 3.3

A for EMIM -CuCl2 , 3.4
A for EMIM+ -CuCl2
3 , and 3.0A

+
for EMIM -Cu2 Cl3 . The negligible vapor pressure may be attributed to the formation of hydrogen bonds.

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