Journal of Molecular Structure 786 (2006) 157167

www.elsevier.com/locate/molstruc

Matrix effect on triatomic CO2 molecule: Comparison

between krypton and xenon
P.R. Dahoo a,*, A. Lakhlifi 1,b, H. Chabbi c, J.M. Coanga d
a

Laboratoire de Magnetisme et dOptique de lUniversite de, Versailles,UMR CNRS 8634-45 Avenue des Etats-Unis, 78035 Versailles Cedex, France
b
Laboratoire dAstrophysique de lObservatoire de Besancon-UMR, CNRS 6091-41 bis, Avenue de lObservatoire-BP
1615-Universite de Franche-Comte, 25010 Besancon Cedex, France
c
Laboratoire de Physique Moleculaire et Applications-UPR CNRS 136 -associe aux, Universites Paris VI et Paris XI-Universite P.
et M. Curie, Tour 13, Bote 76, 4 Place Jussieu, 75252 Paris Cedex 05, France
d
Department of Physics, University of Versailles,-45 Avenue des Etats-Unis, 78035 Versailles Cedex, France
Received 3 September 2005; accepted 27 September 2005
Available online 28 November 2005

Abstract
Vibrational energies for low-lying levels of CO2 trapped in rare gas matrices are determined for four isotopic species by applying a theoretical
model allowing contact transformation method to be applied as perturbation technique to the molecule trapped in a distorted lattice structure.
Results are given for molecules trapped in krypton and xenon. For the latter, both face-centered-cubic (fcc) and hexagonal-closed-packed (hcp)
structures are shown to be possible. New harmonic and anharmonic constants are determined that allows calculation of matrix dependent
calculated energy levels. It is shown that if distortion of the lattice is calculated for one isopotomer, then it can be used to calculate vibrational
energies of other trapped isotopic species. Changes are more significant for harmonic potential constants than for third order anharmonic ones.
Calculated energy levels compare well with observed ones. Predictions of unobserved ones for the latter isotope and other species are also made.
The values calculated for 13C16O2 are consistent with LIF experimental results.
q 2005 Elsevier B.V. All rights reserved.
Keywords: Moleculematrix; Transformation perturbation technique; Vibrational energy

1. Introduction
Matrix isolation is a technique that was developed by G. C.
Pimentel and co-workers [13] to stabilize short lived species
in inert rigid matrix. It was primarily intended to fix the species
so that they could be studied at will by direct spectroscopic
observation, generally in the near infrared region. However,
one observes, even at temperatures as low as 5 K, spontaneous
changes in the observed spectrum on different time scales
dependent on the species and the phenomenon underlying this
change. For instance, in the case of NH3 and H2O trapped in
argon matrix, Abouaf and co-workers [46] have shown that
spin conversion connected to the nuclear spin of H atoms are
responsible for the temporal evolution of observed spectra. In

* Corresponding author. Fax: C33 1 3925 46552.

E-mail address: prd@carnot.physique.uvsq.fr (P.R. Dahoo).
1
Also at: Departement dOrganisation et Genie de la Production-Institut
Universitaire de Technologie of Belfort-Montbeliard

0022-2860/$ - see front matter q 2005 Elsevier B.V. All rights reserved.
doi:10.1016/j.molstruc.2005.09.045

the case of NO trapped in Ne and N2 matrices, Legay and

Legay-Sommaire et al. [79] came to the conclusion that
changes in the observed spectrum are due to diffusion of the
trapped molecules in the matrices, leading to the formation of
dimers easily stabilized by the opened shell character of the
electronic structure of NO. The observed spectra, although less
dense and apparently more simplified than gas phase ones,
could only be resolved after a rigorous analysis which imply a
thorough knowledge of the matrix effect on the trapped species.
As for infrared (IR) spectral perturbations observed as shifts
(vmatrixKvgas) in matrix experiments, they were interpreted
qualitatively in terms of the tight cage effect for blue shifts and
loose cage effect for red shifts by Pimentel and Charles [10] but
elaborate theoretical models were needed to quantitatively
calculate these shifts. The matrix effect can be implicitly
determined by adjusting the force constants so that calculated
IR frequencies fit to observed ones as in molecular physics
field. The difficulty is that observed values are few at low
temperatures as only fundamental modes and some overtones
are observed. This method has been applied by Overend et al to
study ClCN in Ar, Ne and CH4 matrices [11] and N2O in N2
matrix [12] and they conclude that only harmonic constants are

158

P.R. Dahoo et al. / Journal of Molecular Structure 786 (2006) 157167

significantly perturbed by the matrices. Matrix effect has been

accounted for explicitly by considering the intermolecular
potential between the trapped molecule and the undistorted
matrix atoms effectively interacting with the trapped species.
This potential is then treated as a perturbation to the
intramolecular potential driving the nucle vibrational motions
at the same level as the anharmonic terms. Buckingham [13
15] derived the corresponding shift for diatomics from first and
second order perturbation theory and Charles and Lee [16]
applied the results to CO, a diatomic whose rotation is hindered
in matrices. They concluded that one must consider a distorted
trapping site to account for the shifts, the distortion being more
important in a direction parallel to the molecular internuclear
axis and Lee [17] added that this distortion is the main cause of
the barrier to the rotation of the molecule, especially in Ar and
Kr. In the case of diatomics such as hydracids that can still
rotate in matrices, Friedmann and Kimel [18,19] adopted a
different point of view and consider that two effects contribute
to the observed shifts, a vibrational one to which is superimposed a rotational one due to rotation-translation coupling,
treated as a perturbation to the vibrational hamiltonian, the
matrix still being considered to be undistorted. Distortion of
matrix atoms around the trapped molecule has been explicitly
considered for hydrides, diatomics and polyatomics, that can
rotate in matrices by Kono and Lin for hydracids [18,19] and
by Girardet and Lahklifi for NH3 [2023] and CH4 [24]. The
distortion of the matrix atoms around the trapped molecules is
determined by the Green functions technique [25,26], a method
which allows the overall minimization of the total potential
energy of the moleculematrix system. In the case of molecules
for which rotation is hindered, Lakhlifi et al determined the
matrix effect on O3 [27] and C3 [28] molecules. These theories,
mixing both analytical and numerical procedures, based on the
site inclusion model in a matrix distorted around the trapped
molecule have been successful in interpreting most of the
experimental features concerning specific vibrational transitions. Numerical methods through molecular dynamics (MD)
have also been developed to determine matrix distortion effects
around matrix trapped species. Thus by a numerical method
based on a simulated annealing algorithm, Winn [29,30]
determines two different possible trapping sites for OCS in
argon matrix, one with the matrix still preserving its crystalline
structure and the other one corresponding to an amorphous
structure around OCS, a result confirmed experimentally by
Roubin et al. [31,32] through Extended X-ray absorption fine
structure (EXAFS) studies of OCS which is shown to occupy
slightly distorted double substitutional sites in both argon and
xenon in the matrices. One may note that L. M. Raff use the
velocity reset method to determine matrix distortion around
trapped molecules [3335] but this method is applied to study
the dynamics related to chemical reactions induced by
photolysis in matrices. Theoretical methods concerning matrix
isolation studies have been regularly and continuously
reviewed for over 50 years, by A. J. Barnes [36], C.Girardet
et D.Maillard [37], H. J. Jodl [38], V. A. Apkarian and
N. Schwentner [39] and V.E. Bondybey, M.Rasanen and
A.Lammers [40].

The work presented in this paper follows that developed by

P.R. Dahoo et al. [41,42] to interpret matrix effect on molecules
for which rotation is quenched or hindered and has been
applied to triatomics, CO2 and O3. The model combines
methods commonly used in solid state physics to determine the
distortion of an ideal lattice by a trapped molecule [25], with
those regularly used to study gas phase theoretical spectroscopy, that is use of contact transformation as perturbation
technique [43] to calculate vibrational energy levels. The
model contrary to those developed earlier for polyatomics is
not built for a specific transition but can be applied to study any
vibrational transition.
It was shown by applying the site inclusion model in a
distorted lattice, that the matrix effect on the vibrational energy
levels of the trapped species could be quantitatively determined
just as was suggested by Charles and Lee for CO molecule [16]
after distorting the lattice around the trapped molecule. The
energy levels, after a renormalization procedure, could then be
calculated from perturbation theory for a polyatomic molecule,
just as Buckingham [1315] calculated for a diatomic. In
the theoretical model described below one assumes, because of
the size of the molecule compared to the site diameter, that the
trapped species are so tightly held that rotation is prohibited
leading to the absence of rotational structure in the spectra. The
vibrational energy levels of the trapped molecule can then be
computed following methods commonly used by molecular
spectroscopists in gas phase theory. Thus it was shown that O3
and CO2 are trapped in single and double substitutional sites in
argon matrix. In krypton and xenon, O3 is trapped in single and
double substitutional sites. The lattice structure can be either
fcc or hcp in argon and krypton for single substitutional sites
and only fcc for xenon matrix. Once the trapping site is
determined, the potential in which the molecule moves can be
calculated so that the effect of electric field, gradient of the
potential on the molecules electronic cloud can be computed.
In reference [41], the splitting of the n2 vibrational mode of C
O2 in argon matrix was interpreted on the basis of a double
trapping site in the matrix. The results obtained on CO2 thus led
to the inversion of results of Irvine et al [44] about the nature of
the trapping sites correlated to the lines observed. Those
calculated for O3 [42,45] gave more insight in the phenomena
governing the temperature effect on line width broadening for
both trapping sites in RG matrices.
In a recent work on laser induced fluorescence (LIF) of CO2
trapped in xenon and krypton matrices, Chabbi et al [46]
showed that in krypton matrix, one observes vibrational
stimulated emission (VSE) differently from an emission
which is not stimulated in xenon matrix. In an attempt to
analyze these results, this work has been undertaken in order to
determine not only the vibrational levels for identification of
the observed emissions, but also how the molecule couples to
Kr and Xe matrices. Moreover the model has been applied to
four isotopic species of CO2 (12C16O2 (626), 13C16O2 (636),
16 12 18
O C O (628), 16O13C18O (638)) for which some observed
frequencies are available when the molecule is trapped in
krypton and xenon matrices [47,48]. The matrix distortion is
determined for the 626 and 636 isopotomers and from

P.R. Dahoo et al. / Journal of Molecular Structure 786 (2006) 157167

the distorted lattice, the vibrational shifts are computed for the
628 and 638 isopotomers. Results are given for fcc and hcp
lattice structures distorted around CO2 trapped in single (S1)
substitutional sites. The choice of S1 is consistent with the fact
that no splitting of the n2 vibrational mode is observed
experimentally.
The interest of this paper is also to show that if one can
calculate the distortion of the host matrix for an isopotomer
which is abundant, then this distortion which ought to be
the same for isopotomers because they differ only in mass
and not in electric properties, can be used to calculate the
matrix effect on the less abundant isopotomers for which
observed values are scarce. The model has thus been
applied to predict the shifts of the isotopic species. Note
that the site inclusion model can also show which trapping
sites may be stabilized at deposition temperatures lower
than the optimum as shown in reference [48].
In Section 2, we give a brief recall of the model as was
given, in reference [42], in the spectroscopic study of ozone
trapped in RG matrices. Section 3 gives the calculated
vibrational frequencies of the trapped species, up to about
3000 cmK1, in both the fcc and hcp distorted lattice structures.
A discussion about the results then follows to analyze
spectroscopic experimental results.
2. Theoretical model
In the theoretical model described thereafter, one
assumes, because of their sizes compared to the site
volume, that the trapped species are held so tightly that
rotation is prohibited leading to the absence of rotational
structure in the spectra compared to gas phase ones. Then
the vibrational energy levels of the molecule trapped in a
RG matrix are the eigenvalues obtained by solving the
Schrodinger equation for the molecular system coupled to
the matrix with the orientational and translational degrees of
freedom frozen at their static equilibrium in the distorted
lattice structure. In gas phase, the vibrational energies are
determined within the BornOppenheimer approximation.
The theoretical model described in reference [42] determines how the matrix modifies this potential so as to induce
small shifts on the vibrational levels of the embedded
molecule. Then from the transformed hamiltonian of the
molecule, one can compute vibrational energy levels by
solving the corresponding Schrodinger equation, using
contact transformation perturbation technique as in gas
phase theories.
The main aspects of the theoretical model are as follows:
(1) It is based on a site inclusion model, which consists in
replacing one, two or more RG atoms in a fcc or hcp lattice
structure by the trapped molecule [20,37]. The parameters
necessary to describe the RG atom positions and the
molecule with its atoms are recalled on Fig. 1 for the
CO2molecule.
(2) It is assumed that the total potential energy of the trapped
moleculematrix system can be evaluated by pairwise

159

Fig. 1. Geometrical characteristics and absolute (X,Y,Z) and molecular (x,y,z)

frames respectively; (q0, f0, cZ0) and (qj, fj, cZ0) are the Euler angles for the
center of mass and matrix atom j. xl (lZ0 or j) are the vectors defining
the displacements of the center of mass or that of the rare gas atom j. rij is the
distance between the atom i of CO2 and the rare gas atom j; R0,j and ri are the
vectors defining the position of the rare gas atom j and the atom i of CO2 from
the center of mass and aj is the vector defining the position of the rare gas atom j
from the site center.

potentials. It is written as
X
X
VMj r0j C
Vjj 0 rjj0 ;
VZ
j

(1)

jj 0 ;j 0Oj

where the term VMj characterizes the molecule-RG atom

interaction which itself is written as the sum of LennardJones (LJ) 12-6 atomatom potentials characterizing the
repulsion-dispersion contributions and an induction part
due to the interaction between the molecular permanent
electric multipoles (mM, QM,.) and their corresponding
electric field EMj acting on the jth RG atom (the expression
of this part is detailed in Appendix A); r0j being the
distance vector between the centre of mass of the molecule
and the jth matrix atom. The second term represents the
matrixmatrix interactions in which Vjj 0 is the LJ potential
energy between the jth and j 0 th RG atoms located at the rj
and rj 0 positions with respect to the absolute frame tied to
the crystal as shown in Fig. 1. These parts are detailed in
Eqs. (2) and (3) of Ref. [41].
(3) The distortion of the matrix atoms around the trapped
molecules is determined by the Green functions technique
[25,26], a method which allows an overall minimization of
the total potential energy of the moleculematrix system.
This method has been described elsewhere (Eqs. (4) and
(5)) [27] and the matrix atoms displacement can be
calculated from the following formula:
!
X
XX
xk Z
Gkk 0 Fk 0 C
Hk 0 l Glm Fm
(2)
k0

where xk is the displacement of atom k (kZ0 for the center

of mass of the trapped molecule and j for the other matrix

160

P.R. Dahoo et al. / Journal of Molecular Structure 786 (2006) 157167

atoms), G is the Greens tensor, that is the greens function

matrix which is the inverse of the matrix force constants
for the perfect crystal and F and H are, respectively, the
first rank and second rank tensor connected to the force and
the force constant experienced by the molecule or a matrix
atom due to the inclusion. Note that the method is self
consistent since xk depends on the evaluation of xk
(4) Application of the BornOppenheimer approximation
allows one to separate the study of high frequency
modes (vibrational modes) from low frequency ones
(libration and lattice vibrations) [49]. Then, considering
the matrix atoms and the centre of mass of the trapped
molecule as being fixed with respect to the atoms of the
molecule, the vibrational motion of the latter inside the
matrix is studied [27]. Note that the use of pairwise atom
atom interaction potentials allows one to study the matrix
environment effect on the vibrational motions because this
effect can be evaluated for each vibrating atom of the
trapped molecule.
As experiments show vibrational shifts to be small, VM({xs,
U },{Q}), the vibrational part of the interaction potential
dependence in terms of normal coordinates Q, is expanded up
to second order only, in terms of dimensionless normal
coordinates q, as
X
XX
VM fxS ; Ue g; fqg Z
bi qi C
bij qi qj ;
(3)
e

jRi

where bi and bij are the first and second derivatives of VM with
respect to the dimensionless normal coordinates q. One may
note that these terms consist of two contributions, one
originating from the displacement of matrix atoms from their
equilibrium positions in the ideal lattice (the static electric field
given in Appendix A) and the other from the polarization of the
matrix atoms under the influence of the electric field due to the
multipole moments of the vibrating molecule (the dynamic
field as described in Appendix A).
Then the nuclei of the trapped molecule, because of the
matrix effect, are moving in a mean force field, gradient of a
perturbed potential U({q}) given by Eq. (14) of Ref. [41] and
whose minimum corresponds to a new stable equilibrium
configuration of the nuclei. Defining the origin of U({q}) at this
minimum, and after applying an orthogonal transformation to
the transformed Hamiltonian of the vibrating trapped molecule
to eliminate cross terms bij (isj), one can write the
Hamiltonian as
vib
Z H00 C Ha0 ;
HM

H00 Z
Ha0 Z


1 X 0
02
ui pi C qi02 ;
2 i
X
ijk

0
kijk
qi0 qj0 qk0 C

0
kijkl
qi0 qj0 qk0 ql0 C/

(4)

ijkl

In the above expressions, the first term H00 is the harmonic

contribution of the vibrational energy (the harmonic oscillator

operator) in the matrix. qi0 and pi0 are the ith vibrational normal
coordinate operator and its conjugate momentum and ui0 is the
frequency corresponding to the ith oscillator. Ha0 describes the
anharmonicities of vibrations with the corresponding force
0
0
constants kijk
and kijkl
(5) The vibrational energy levels of the trapped molecule are
determined by using the contact transformation technique
applied to the above Hamiltonian, as in gas phase
spectroscopic study. That is, perturbation theory is applied
to Ha0 using wave functions of H00 as zeroth order basis,
following the contact transformation method. The net
distortion of the lattice structure is thereafter determined
by adjusting the calculated vibrational frequencies of
fundamental bands to observed ones.
(6) Finally, the vibrational energy levels are calculated by
taking into account FermiDennison resonances when
necessary [50]. The expression of the vibrational energy,
up to the fourth order is written as

X 
d
Gv Z
u i vi C i
2
i
C

X
i%j




dj
d
xij vi C i
vj C
C xl2 l2 l2 ;
2
2

(5)

where ui are the zeroth order vibrational frequencies of

degeneracy di (d1Zd3Z1 and d2Z2) and xij are the
anharmonic constants expressed in terms of cubic and
quartic potential constants kijk and kijkl [43] and l is the
quantum number related to the internal angular momentum
of the degenerate vibration v2. As results will be given for
gas phase and matrix dependent terms, the subscripts will
be dropped in Section 3 and the appendices. The
expressions of the anharmonic constants are given in
Appendix B.

3. Results and discussion

3.1. Experimental considerations
The final distortion of the rare gas lattice is determined by
adjusting the observed frequencies of fundamental transitions
to the calculated ones. One needs to choose the trapping site of
the molecule and the lattice structure of the matrix to calculate
this distortion. This step may follow the experimental study
because trapping sites depend on the experimental conditions
such as deposition temperature, deposition rate or dilution.
Experimentally, only strong transitions are observed and
generally the number of corresponding lines are few (about
10 lines) compared to gas phase spectra which are denser
because of rotational lines. For isotopic species, spectroscopic
study have to be performed on thick optical density matrices.
The observed frequencies reported in this work in Tables 410
are taken from Ref. [48], and have been measured from fourier
transform infrared (FTIR) spectroscopy of trapped CO2

P.R. Dahoo et al. / Journal of Molecular Structure 786 (2006) 157167

molecules in krypton and xenon matrices following the

experimental method described in reference [41]. In the case
of krypton, only one trapping site is observed, differently from
the argon matrix case for which two trapping sites are depicted.
For xenon, the number of monomer vibrational absorption lines
depends on the deposition temperature of the matrix. For
temperatures lower than 35 K (optimum deposition temperature for xenon), only one line is observed for n2 and n3 modes
whereas for a deposition temperature of 35 K, two lines are
observed for each mode. Because no degeneracy lifting of the
y2 mode occurs in both cases, these lines have been attributed
to single substitutional trapping sites in a fcc lattice in the Kr
matrix and in a fcc and a hcp lattice for the Xe matrix.
Following these results, calculations have been performed for a
single trapping substitutional site termed S1 in a fcc and a hcp
lattice.
3.2. Calculated equilibrium configurations
The first step before adjusting the distortion of the matrix
atoms is to fix the trapped molecule at the equilibrium
configuration determined by the static site inclusion model in a
distorted lattice as described in Section 2. The displacements of
the surrounding atoms are not all equivalent and in general
atoms closer to those of the trapped molecule are repelled in a
direction determined by the local symmetry of the molecule
matrix system.
Let us recall that for both fcc and hcp lattice structures, the
initial position of the trapped molecule corresponds to its
centre of mass fixed at the site center and its axis of least
moment of inertia parallel to the OZ axis tied to the lattice. For
the fcc crystal the latter is aligned along the C4 symmetry axis
of the trapping site, whereas for the hcp lattice structure, it is
aligned along the C3 symmetry axis of the trapping site. The
parameters used in the potential energy calculations are given
in Table 1. Calculations show that in the fcc lattice, the
resulting equilibrium orientations of the molecule are qeZp/2,
feZ0 and p/2 for the molecule directed along the X and Y
axes, respectively, and qeZ0 for the molecule directed along
the Z axis. The distortion of the atoms around the molecule
corresponds to a contraction of the site in the plane
perpendicular to the molecular z axis in both krypton and
xenon, that is to 4 and 7% of the site diameter, respectively. In
the planes containing the z axis, the distortion corresponds to a

161

slight dilatation parallel to z (less than 0.5%) and a contraction

perpendicular to z (2% in krypton and 5.5% in xenon). For the
hcp lattice,calculations show that in both krypton and xenon,
the molecule is parallel to the Z axis (C3 symmetry axis of the
trapping site). As for the distortion, the site contracts (2 and
4%, respectively) in the plane perpendicular to the molecular z
axis and dilates (!0.5%) in the direction parallel to the z axis.
These results are in agreement with the conclusions of Charles
and Lee [16] concerning the diatomic CO. The distortion is of
cylindrical shape around the CO2 molecule. The equilibrium
position of the molecule corresponds to its center of mass at the
site center in the two lattices. The calculated energies are
however different, that is K1990 and K1400 cmK1 for
krypton and K2570 and K2340 cmK1 for xenon, respectively,
in fcc and hcp lattices. These results show a difference of 590
and 230 cmK1 for the two lattices and hence CO2 in S1 is more
stable in fcc than in hcp lattice, but in xenon, hcp lattice
structure is more favourable than in krypton.
3.3. Vibrational energy
The results of the calculations performed on the four
isotopic species considered (12C16O2,13C16O2,12C16O18O,
13 16 18
C O O) are given in Tables 213. From those given in
Tables 2 and 3 for the vibrational potential constants up to
fourth order, one may note that fourth order terms are
unchanged for the four isotopic species. Since vibrational
energy levels are determined up to second order only (Eq. (5)
of part II), only the changes in the harmonic potential constants
effectively contribute to the shift of the vibrational energy
levels calculated from Eq. (5). To take into account the changes
in third order potential constants, one needs to compute the
vibrational energies up to third order expansion in the
vibrational quantum numbers. We have not considered third
order terms because the differences between the observed and
calculated values for matrix shifted vibrational energies are
comparable to those corresponding to gas phase energy values
as shown in Tables 411. Note that, following Rothman et al.
[51], we are using HITRAN notation for the labelling of the
energy levels. For levels perturbed by Fermi resonance, such as
1000 and 0200 for instance, the labelling is 1000 (1) and 1000
(2), where number (1) is assigned to the highest of the two
levels. Finally, the calculated energy values are consistent with
radiative transitions observed in LIF experiments on 13C16O2

Table 1
Data used in our calculations. Pure Lennard-Jones 12-6 potential parameters (see Eqs. (2) and (3) of Ref. [1]), isotropic polarizability of krypton and xenon atoms and
their interdistance in the matrix, and also internal distances, dipole and quadrupole moments of the rigid linear CO2 molecules
Atoms

Kr

Xe

Internal
characteristics

CO2 CO

3 (cmK1)a
)a
s (A

a (A)b
3 )b
a (A

125.0
3.65
4.00
2.48

157.1
3.97
4.31
4.04

29.8
3.21

39.9
2.88

qeM A
me M c Dc
Qe M c DAC

1.162
0
K4.3

a
b
c

From Ref. [56] and references therein.

From Ref. [57].
From Ref. [58].

162

P.R. Dahoo et al. / Journal of Molecular Structure 786 (2006) 157167

Table 2
Quadratic, cubic and quartic potential constants (cmK1) for 13 C16 O2,13C16O18O,12C16O2, and 12 C16 O18O molecules trapped in S1 sites of xenon matrices and their
values in the gas phase
13

Site
k11
k2a2a
k2b2b
k33
k111
k113
k12a2a
k12b2b
k133
k2a2a
k2b2b3
k333
k111
k112a2
k112b2b
k1133
k2a2a2a
k2a2a33
k2b2b2b
k2b2b33
k3333

13

CO2

fcc S1

hcp S1

Gas

678.40
323.13
323.13
1157.19
K45.61

677.95
323.73
323.73
1157.94
K45.58

676.98
326.98
326.98
1164.05
K45.56

72.48
72.48
K242.07

72.43
72.43
K241.97

72.36
72.36
K241.84

1.87
K9.83
K9.83
18.97
2.14
K26.02
2.14
K26.02
5.93

1.87
K9.83
K9.83
18.97
2.14
K26.02
2.14
K26.02
5.93

1.87
K9.83
K9.83
18.97
2.14
K26.02
2.14
K26.02
5.93

C16 O18O

12

fcc S1

Gas

659.43
320.55
320.55
1148.88
K43.65
K4.89
71.62
71.62
K240.68
6.66
6.66
K8.23
1.62
K10.95
K10.95
18.97
2.48
K26.16
2.48
K26.16
6.29

657.20
324.22
324.22
1154.93
K42.58
K5.06
71.36
71.36
K240.22
6.68
6.68
K8.34
1.62
K10.95
K10.95
18.97
2.48
K26.16
2.48
K26.16
6.29

12 16

C O18O

CO2

fcc S1

Gas

678.40
332.47
332.47
1190.83
K45.61

676.98
336.58
336.58
1198.14
K45.56

74.59
74.59
K249.16

74.47
74.47
K248.93

1.87
K10.13
K10.13
18.97
2.27
K27.57
2.27
K27.57
6.28

1.87
K10.13
K10.13
18.97
2.27
K27.58
2.27
K27.58
6.28

fcc S1

Gas

659.11
330.22
330.22
1182.11
K43.90
K4.33
73.16
73.16
K243.60
K6.47
K6.47
7.78
1.81
K10.73
K10.73
18.77
2.42
K25.64
2.42
K25.64
6.22

657.60
336.86
336.86
1189.26
K43.85
K4.46
73.01
73.01
K243.33
K6.50
K6.50
7.87
1.81
K10.73
K10.73
18.77
2.42
K25.64
2.42
K25.64
6.22

Table 3
Quadratic, cubic and quartic potential constants (cmK1) for 13 C16 O2, 13 C16 O18O, 12 C16 O2, and 12 C16 O18O molecules trapped in S1 sites of krypton matrices and
their values in the gas phase
13

Site
k11
k2a2a
k2b2b
k33
k111
k113
k12a2a
k12b2b
k133
k2a2a
k2b2b3
k333
k111
k112a2
k112b2b
k1133
k2a2a2a
k2a2a33
k2b2b2b
kb2b33
k3333

13 16

C O18O

CO2

fcc S1

Gas

678.95
323.60
323.60
1159.85
K45.58

676.98
326.98
326.98
1164.05
K45.56

72.42
72.42
K242.00

72.36
72.36
K241.84

1.87
K9.83
K9.83
18.97
2.14
K26.02
2.14
K26.02
5.93

1.87
K9.83
K9.83
18.97
2.14
K26.02
2.14
K26.02
5.93

12

12 16

C O18O

CO2

fcc S1

Gas

660.15
320.75
320.75
1151.45
K43.11
K4.98
71.47
71.47
K240.46
6.66
6.66
K8.27
1.62
K10.95
K10.95
18.97
2.48
K26.16
2.48
K26.16
6.29

657.20
324.22
324.22
1154.93
K42.58
K5.06
71.36
71.36
K240.22
6.68
6.68
K8.34
1.62
K10.95
K10.95
18.97
2.48
K26.16
2.48
K26.16
6.29

trapped in krypton. The values reported in Ref. [46,48] refer to

two lines corresponding to transitions between vibrational
energy states of 13C16O2 in the infrared region generally termed
16 mm and measured at 622 cmK1 for 1110 (2)/1000 (2) and
611 cmK1 for 1000 (2)/0110 (1). These values are reported
with a relative uncertainty of 0.5%, which is consistent with the

fcc S1

Gas

679.30
333.10
333.10
1193.95
K45.58

676.98
336.58
336.58
1198.14
K45.56

74.53
74.53
K249.05

74.47
74.47
K248.93

1.87
K10.13
K10.13
18.97
2.27
K27.57
2.27
K27.57
6.28

1.87
K10.13
K10.13
18.97
2.27
K27.58
2.27
K27.58
6.28

fcc S1

Gas

659.80
330.65
330.65
1185.10
K43.87
K4.39
73.08
73.08
K243.47
K6.48
K6.48
7.82
1.81
K10.73
K10.73
18.77
2.42
K25.64
2.42
K25.64
6.22

657.60
336.86
336.86
1189.26
K43.85
K4.46
73.01
73.01
K243.33
K6.50
K6.50
7.87
1.81
K10.73
K10.73
18.77
2.42
K25.64
2.42
K25.64
6.22

values calulated at 623.8 and 613.9 cmK1. In the case of xenon

matrix deposited at 14 K (below 35 K) which means only one
trapping site, corresponding to S1 in a fcc lattice, Ref. [46,48]
reports only a fluorescence observed in the 16 mm region. If
one admits a similar relaxation mechanism for radiative
transitions in krypton and xenon, then one may predict

P.R. Dahoo et al. / Journal of Molecular Structure 786 (2006) 157167

163

Table 4
Calculated and observed vibrational level scheme (cmK1) for 13CO2 molecule trapped in krypton matrix and in gas phase up to 2285 cmK1
Matrix structure

fcc

Gas

Band

Observed

Calculated

Obscalc

Observed

Calculated

Obscalc

0 00
1 11
0 33
1 11
1 00
0 22
1 00
0 11

2275.10

2275.08
2031.08
1926.83
1879.52
1370.51
1284.15
1255.76
641.87

C0.02

2283.48
2037.50
1946.40
1896.93
1370.05
1297.70
1265.81
648.91

2283.50
2037.32
1946.26
1896.68
1370.21
1297.76
1265.83
648.67

K0.02
C0.18
C0.14
C0.25
K0.16
K0.06
K0.02
C0.24

1 (1)
0 (1)
0 (1)
0 (2)
0 (1)
0 (1)
0 (2)
0 (1)

641.62

K0.25

Table 5
Calculated and observed vibrational level scheme (cmK1) for 13CO2 molecule trapped in xenon matrix and in gas phase up to 2285 cmK1
Matrix structure

fcc

hcp

Gas

Band

Observed

Calculated

ObsCalc

Observed

Calculated

ObsCalc

Observed

Calculated

ObsCalc

0 00
1 11
0 33
1 11
1 00
0 22
1 00
0 11

2269.35

2269.77
2028.78
1924.13
1877.14
1369.19
1282.35
1254.35
640.97

K0.42

2271.51

C0.22

K0.03

642.45

2271.29
2030.21
1927.72
1879.61
1369.19
1284.73
1255.71
642.16

2283.48
2037.50
1946.40
1896.93
1370.05
1297.70
1265.81
648.91

2283.50
2037.32
1946.26
1896.68
1370.21
1297.76
1265.83
648.67

K0.02
C0.18
C0.14
C0.25
K0.16
K0.06
K0.02
C0.24

1 (1)
0 (1)
0 (1)
0 (2)
0 (1)
0 (1)
0 (2)
0 (1)

640.94

C0.29

Table 6
Calculated and observed vibrational level scheme (cmK1) for 12CO2 molecule trapped in krypton matrix and in gas phase up to 2350 cmK1
Matrix structure

fcc

Gas

Band

Observed

Calculated

ObsCalc

Observed

Calculated

ObsCalc

0 00
1 11
0 33
1 11
1 00
0 22
1 00
0 11

2340.50

2340.65
2067.82
1983.25
1918.31
1385.31
1321.73
1278.79
660.65

K0.15

2349.16
2076.45
2003.28
1932.47
1388.19
1335.19
1285.41
667.38

2349.14
2076.75
2004.08
1932.90
1388.08
1335.61
1285.65
667.58

C0.02
K0.30
K0.80
K0.43
C0.11
K0.48
K0.24
K0.20

1 (1)
0 (1)
0 (1)
0 (2)
0 (1)
0 (1)
0 (2)
0 (1)

660.29

K0.36

Table 7
Calculated and observed vibrational level scheme (cmK1) for 12CO2 molecule trapped in xenon matrix and in gas phase up to 2350 cmK1
Matrix structure

fcc

Gas

Band

Observed

Calculated

ObsCalc

Observed

Calculated

ObsCalc

0 00
1 11
0 33
1 11
1 00
0 22
1 00
0 11

2334.50

2334.22
2064.23
1979.33
1914.90
1383.10
1319.12
1276.62
659.34

C0.28

2349.16
2076.45
2003.28
1932.47
1388.19
1335.19
1285.41
667.38

2349.14
2076.75
2004.08
1932.90
1388.08
1335.61
1285.65
667.58

C0.02
K0.30
K0.80
K0.43
C0.11
K0.48
K0.24
K0.20

1 (1)
0 (1)
0 (1)
0 (2)
0 (1)
0 (1)
0 (2)
0 (1)

164

P.R. Dahoo et al. / Journal of Molecular Structure 786 (2006) 157167

Table 8
Calculated and observed vibrational level scheme (cmK1) for 13 C16 O18O molecule trapped in krypton matrix and in gas phase up to 2265 cmK1
Matrix structure

fcc

Gas

Band

Observed

Calculated

ObsCalc

Observed

Calculated

ObsCalc

0 00
1 11
0 33
1 11
1 00
0 22
1 00
0 11

2257.64

2257.32
1997.41
1911.55
1853.48
1340.69
1273.32
1236.72
636.14

C0.32

2265.98
2005.46
1930.98
1869.25
1342.28
1286.98
1244.90
643.32

2266.19
2006.06
1930.21
1868.72
1342.60
1286.56
1244.63
643.16

K0.21
K0.60
C0.77
C0.53
K0.32
C0.42
C0.37
C0.16

1 (1)
0 (1)
0 (1)
0 (2)
0 (1)
0 (1)
0 (2)
0 (1)

1271.70
636.47

K1.62
C0.33

Table 9
Calculated and observed vibrational level scheme (cmK1) for 13 C16 O18O molecule trapped in xenon matrix and in gas phase up to 2265 cmK1
Matrix structure

fcc

hcp

Band

Observed

Calculated

ObsCalc

Observed

0 00
1 11
0 33
1 11
1 00
0 22
1 00
0 11

2252.92

2252.13
1995.77
1910.35
1852.08
1339.44
1272.51
1235.74
635.73

C0.79

2254.10

1 (1)
0 (1)
0 (1)
0 (2)
0 (1)
0 (1)
0 (2)
0 (1)

636.00

Calculated

Gas
ObsCalc

C0.27

Observed

Calculated

ObsCalc

2265.98
2005.46
1930.98
1869.25
1342.28
1286.98
1244.90
643.32

2266.19
2006.06
1930.21
1868.72
1342.60
1286.56
1244.63
643.16

K0.21
K0.60
C0.77
C0.53
K0.32
C0.42
C0.37
C0.16

Table 10
Calculated and observed vibrational level scheme (cmK1) for 12 C16 O18O molecule trapped in krypton matrix and in gas phase up to 2332 cmK1.
Matrix structure
Band
0

00
1 11
0 33
1 11
1 00
0 22
1 00
0 11

fcc
Observed

1 (1)
0 (1)
0 (1)
0 (2)
0 (1)
0 (1)
0 (2)
0 (1)

Calculated

Gas
ObsCalc

2323.91
2039.35
1970.53
1890.47
1360.85
1312.93
1255.92
656.09

Observed

Calculated

ObsCalc

2332.11
2049.34
1988.31
1901.73
1365.83
1325.14
1259.42
662.37

2332.13
2048.63
1989.74
1902.52
1364.76
1325.72
1260.51
662.48

K0.02
C0.71
K1.43
K0.79
C1.07
K0.58
K1.09
K0.11

Table 11
Calculated and observed vibrational level scheme (cmK1) for 12 C16 O18O molecule trapped in xenon matrix and in gas phase up to 2332 cmK1
Matrix structure
Band
0

00
1 11
0 33
1 11
1 00
0 22
1 00
0 11

1 (1)
0 (1)
0 (1)
0 (2)
0 (1)
0 (1)
0 (2)
0 (1)

fcc
Observed

Calculated
2317.95
2036.86
1968.02
1888.22
1359.24
1311.25
1254.48
655.24

Gas
ObsCalc

Observed

Calculated

ObsCalc

2332.11
2049.34
1988.31
1901.73
1365.83
1325.14
1259.42
662.37

2332.13
2048.63
1989.74
1902.52
1364.76
1325.72
1260.51
662.48

K0.02
C0.71
K1.43
K0.79
C1.07
K0.58
K1.09
K0.11

P.R. Dahoo et al. / Journal of Molecular Structure 786 (2006) 157167

165

Table 12
Harmonic frequencies and anharmonic constants (cmK1) for 13 CO2 and 13 C16 O18O molecules trapped in S1 sites of krypton and xenon matrices and their values in
the gas phase
Molecule

13

13 16

C O18O

CO2

Matrix

Krypton

Xenon

Xenon

Site structure

fcc

fcc

hcp

u1
u2a
u2b
u3
x11
x12
x13
x22
x23
x33
xl2 l2

1357.9
647.2
647.2
2319.7
K2.9
K3.5
K19.3
1.0
K11.6
K11.7
K0.8

1356.8
646.3
646.3
2314.4
K2.9
K3.5
K19.3
1.0
K11.6
K11.7
K0.8

1355.9
647.5
647.5
2315.9
K2.9
K3.5
K19.3
1.0
K11.6
K11.7
K0.8

Gas
1354.0
654.0
654.0
2328.1
K2.9
K3.5
K19.2
1.0
K11.6
K11.7
K0.8

Krypton

Xenon

fcc

fcc

1320.3
641.5
641.5
2302.9
K3.0
K4.8
K18.6
1.5
K11.4
K11.7
K1.4

1318.9
641.2
641.1
2297.8
K3.0
K4.8
K18.6
1.5
K11.5
K11.6
K1.4

Gas
1314.4
648.2
648.2
2309.9
K2.7
K4.9
K18.0
1.5
K11.6
K11.5
K1.4

Table 13
Harmonic frequencies and anharmonic constants (cmK1) for 12C O2 and 12C16O18O molecules trapped in S1 sites of krypton and xenon matrices and their values in
the gas phase
Molecule

12

12 16

CO2

Matrix

Krypton

Xenon

Site structure
u1
u2a
u2b
u3
x11
x12
x13
x22
x23
x33
xl2 l2

fcc
1358.6
666.2
666.2
2387.9
K2.9
K3.6
K20.3
1.1
K12.4
K12.5
K0.9

fcc
1356.8
664.9
664.9
2381.7
K2.9
K3.6
K20.3
1.1
K12.4
K12.4
K0.9

O18O

Gas

Krypton

Xenon

Gas

1354.0
673.2
673.2
2396.3
K2.9
K3.6
K19.7
1.1
K12.4
K12.5
K0.9

fcc
1319.6
661.3
661.3
2370.2
K2.8
K4.4
K19.2
1.3
K10.5
K12.3
K1.4

fcc
1318.2
660.5
660.5
2364.2
K2.8
K4.4
K19.2
1.3
K10.5
K12.3
K1.4

1315.2
667.7
667.7
2378.5
K2.8
K4.4
K19.0
1.3
K10.6
K12.3
K1.4

fluorescence lines to be observed at 622.8 and 613.4 cmK1

within experimental errors.

conclusions of J. Overend and L. Andrews and co-workers

about the matrix effect on the vibrational energy levels of linear
polyatomic N2O [12].

4. Conclusion
The results given in this work show that the site inclusion
model allows one to determine the corresponding trapping
site(s) and lattice structure(s) from energy considerations.
When distortion is adjusted so that observed frequencies match
calculated ones, then vibrational energy levels can be
determined for excited states. Considering the results obtained
with the triatomic molecules, linear in the case of CO2 and N2O
[52] and bent in the case of O3 [42,45], then the theoretical
model applied to calculate the vibrational energies shows that
if the distortion of the lattice is determined for one isopotomer,
then the vibrational energies can be calculated for other
isopotomers, in agreement with the conclusions Charles and
Lee [16] arrived at about the matrix effect on the vibrational
energy levels of diatomic CO. Moreover the solid rare gas
matrix changes significantly the harmonic terms of the
internuclear potential only, in agreement this time to the

Appendix A: Electric field of the dipole and quadrupole

moments of a molecule
The expression of the interaction polarization energy of the
matrix atoms and the trapped molecule is written as
1
2
K aj EMj
;
2

(6)

2
where aj is the polarizability of the jth matrix atom and EMj
is
the square of the electric field generated by the multipole
moments of the trapped molecule at the position of the jth
matrix atom.
The electric field of the trapped CO2 molecule can be
restricted to that due to the dipole m and quadrupole Q
moments only. In that case the static electric field EMj can be
written as

166

P.R. Dahoo et al. / Journal of Molecular Structure 786 (2006) 157167

1
EMj Z T$m C T$Q;
3

(7)

where T represent the second and third order tensors given by


Tab Z Va Vb

1
rMj


Z

2
3rMja rMjb KrMj
dab
;
5
rMj

(8)

xss 0

1
Z
2

)
2
4ksss
6ksss kss 0 s0
0 us
ksss 0 s0 K
K
;
us
4u2s Ku2s0

s Z 1; 3; s 0 Z 3; 1
1
k 2 u1
k 2 u3
 K
223
:
xl2 l2 ZK k2222 K
221
2
2
2
4 4u2 Ku1
4 4u22 Ku23

and

Tabg Z Va Vb Vg

1
rMj

2
5rMja rMjb rMjg KrMj
rMja dbg C rMjb dag C rMjg dab
ZK3
;
7
rMj

(9)
respectively. In the latter two expressions, the distances are
calculated in the frame tied to the molecule.
The dynamical electric field EMj(q1,q2a,q2b,q3) considered in
the calculations is given by
EMj q1 ; q2a ; q2b ; q3
1
Z T$mq1 ; q2a ; q2b ; q3 C T$Qq1 ; q2a ; q2b ; q3 :
3

(10)

The expression of the dipole moment of the vibrating trapped

molecule in terms of the normal coordinates is given in
reference [53] up to second order and that for the quadruopole
moments in Ref. [54,55].

Appendix B. Anharmonic vibrational constants

The expressions of the anharmonic vibrational constants for
linear triatomic molecules are
(
!)
2
2
ksss
8u2s K3u2s0
1
15ksss
0
xss Z
6kssss K
K
;
4
us
us 0
4u2s Ku2s0
s Z 1; 3; s 0 Z 3; 1;



2 
2 
1
k122
8u22 K3u21
k223
8u22 K3u23
6k2222 K
x22 Z
K
;
4
u1
u3
4u22 Ku21
4u22 Ku23


2
1
4k22s
u2
k22s0 ks 0 ss
us z 2
k K
C2
z Be ;
K
x2s Z
2 22ss 4u22 Ku2s
us 0
u2 2s
s Z 1; 3; s 0 Z 3; 1;

xs2 Z



1
6k k
k 0k 0
u
2
kss22 K sss s22 K sss s 22 C 2 2 zz
B
e ;
2
us
us 0
us s2

s Z 1; 3; s 0 Z 3; 1;

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