Chemical Physics 326 (2006) 551562

www.elsevier.com/locate/chemphys

Optical properties of the conducting salt (DOEO)4HgBr4 TCE

A. apinski
a

a,*

, A.I. Kotov

Institute of Molecular Physics, Polish Academy of Sciences, ul. Smoluchowskiego 17, 60-179 Poznan, Wielkopolska, Poland
b
Institute of Problems of Chemical Physics, RAS, Chernogolovka 142432, Russia
Received 5 January 2006; accepted 15 March 2006
Available online 18 March 2006

Abstract
A new charge transfer (DOEO)4HgBr4 TCE salt based on [(1,4-dioxane-diyl-2,3-ditio)ethylenedioxytetrathiafulvalene] (DOEO) and
[HgBr4]2 anion was synthesized and characterized by spectral analysis. The structure consists of alternating organic and inorganic layers. The inorganic layers are formed by [HgBr4]2 anions and 1,1,2-trichloroethan (TCE) solvent molecules. The organic layers are built
of dimerized DOEO stacks. Polarized reectance (from 500 to 18,000 cm1) and Raman spectra of single crystals were studied down to
the liquid helium temperature. An electronic dispersion in IR spectra was analyzed in terms of the Lorentz model and optical transport
parameters were determined. The proposed assignment of vibrational features of (DOEO)4HgBr4 TCE salt was based on ab initio calculations of the normal modes of DOEO0, DOEO+, and TCE molecules. The analysis of the spectra in terms of the isolated dimer model
yields reliable estimates of DOEO electronmolecular vibration (emv) coupling constants.
 2006 Elsevier B.V. All rights reserved.
Keywords: DOEO salt; Infrared spectra; Raman spectra; Normal mode analysis, emv coupling constants

1. Introduction
Most of presently known organic conductors and superconductors were prepared using the [bis(ethylenedithio)tetrathiafulvalene] (BEDT-TTF or ET) and various acceptors.
In the search for new interesting materials the chemical
modication of ET is a way to new donors for highly conducting and even superconducting organic materials [15].
Recently, two new derivatives of ET were synthesized where
one or two ethylene groups are replaced by 1,4-dioxane
rings: [(1,4-dioxane-diyl-2,3-ditio)ethylenedithiotetrathiafulvalene] (DOET) and [(1,4-dioxane-diyl-2,3-ditio)tetrathiafulvalene] (BDDT), respectively [69]. The crystal
structures of DOET and BDDT salts consist of b-type
columns of donor molecules in which donors are stacked
with avoiding the steric hindrance of the bulky dioxane
rings [710]. In order to investigate the interaction in the
stacking column, related to the size of the terminal ethyl-

Corresponding author. Tel.: +48 61 86 95 279; fax: +48 61 86 84 524.

E-mail address: lapinski@ifmpan.poznan.pl (A. apinski).

0301-0104/$ - see front matter  2006 Elsevier B.V. All rights reserved.
doi:10.1016/j.chemphys.2006.03.018

enedichalcogeno group, the new derivative [(1,4-dioxanediyl-2,3-ditio)ethylenedioxytetrathiafulvalene] DOEO has

been synthesized; DOEO molecule has smaller oxygen
atoms in the terminal 6-membered ring [11].
Recently, the new organic conductor (DOEO)4HgBr4 TCE based on unsymmetrical donor DOEO was synthesized. The detailed crystallographic investigations of
this salt were carried out by Bardin et al. [12] for two different temperatures: 293 and 30 K. The crystal structure
consists of conducting donor layers of the b-type packing
alternating along the c-axis with insulating layers formed
by [HgBr4]2 anions and solvent TCE molecules. In the
conducting layers, parallel to the (ab) plane, the DOEO
molecules are arranged in dimerized stacks parallel to the
b-axis with head-to-tail packing mode. Close S  S contacts, shorter than the sum of the van der Waals radii,
are only observed inside a ribbon along the [4 1 0] and
4 1 0 directions at room temperature, whereas at 30 K
the contacts are present between and inside the ribbons.
At room temperature the unit cell of (DOEO)4HgBr4 TCE
crystal is orthorhombic, space group Pbcn, with
, b = 17.632(4) A
, c = 35.657(7) A
,
a = 11.859(2) A

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A. apinski, A.I. Kotov / Chemical Physics 326 (2006) 551562

3, Z = 4; the distance inside the DOEO

V = 7456(3) A
, whereas distance between the
dimer equals to 3.64 A

dimers 3.79 A. At 30 K the main crystallographic data

,
are: orthorhombic, space group Pbcn, a = 11.6894(1) A

b = 17.3827(1) A, c = 35.6046(3) A, V = 7234(3) A3,

Z = 4; the distances inside and between the DOEO dimers
, respectively. At room temperaequal to 3.57 and 3.76 A
2
ture the [HgBr4] anions, solvent molecules, and ethylene
groups in DOEO molecules are disordered. There are tetrahedral [HgBr4]2 ions in three possible crystallographic different positions at 293 K (An = 87%, An 0 = 11%, and
An00 = 2%) and in two positions at 30 K (An = 98%,
An 0 = 2%, and An00 = 0%) [12]. Moreover, ethylene groups
are ordered at low temperature.
The electrical behavior of (DOEO)4HgBr4 TCE
reported by Bardin et al. showed a curious phenomenon
[12]. The room temperature dc conductivity of a single
crystal (DOEO)4HgBr4 TCE salt measured along the adirection within ab-plane was found to be rRT = 5 S/cm,
while perpendicular to this plane it was found to be almost
ve orders of magnitude less. On cooling, in both experimentally measured directions, the resistivity increases until
a maximum is reached around 140 K, becomes metallic in
the lower temperature region, and nally undergoes an
insulating transition around 50 K. The anomaly observed
at around 140 K can be caused by the impurity and/or
the disorder of the counter anion and ethylene groups.
However, the mechanism and the origin of this anomaly
in the resistivity are still open to question.
In the present work, we investigated polarized reectance spectra, Raman spectra and proposed the assignment
of the fundamental vibrations of DOEO molecule. We also
estimated in terms of the isolated dimer model electron
molecular vibration (emv) coupling constants for DOEO
molecule. The aim of these investigations is to obtain information on physical properties of investigated compound in
the large spectral and temperature ranges and combine
these results with the crystal structure and other physical
properties of the investigated CT salt. These studies should
also enrich a modest bibliography on the optical properties
of the organic materials based on the unsymmetrical
p-donors.
2. Experimental
The crystals of the (DOEO)4HgBr4 TCE salt were prepared by electrochemical oxidation of DOEO in 1,1,2-trichloroethan (TCE) using the (C4H9)4NHgBr3 mixture as a
supporting electrolyte at constant current of 0.8 lA and
20 C under argon atmosphere. The samples had a shape
of plates with plane and reecting faces. Typical dimensions
of the single crystals selected for spectral investigations were
about 1.3 mm 0.8 mm 0.02 mm. The biggest face of the
sample coincides with (0 0 1) plane, which is parallel to the
two-dimensional conducting layers containing DOEO
dimerized stacks. The reectance spectra from this crystal
face of the single crystal were carried out in the spectral

range from 500 to 18,000 cm1 for the light polarized parallel to the stacking direction (E//b) and for the perpendicular
orientation of the electrical vector (E//a) which is parallel to
the longest direction of the crystal. These two directions correspond to the maximum and the minimum of reected
energy, respectively. Moreover, the spectrum was recorded
for the diagonal direction (E//[1 1 0]), nearly parallel to the
S  S short contacts. The normal polarized reectance spectra of the (DOEO)4HgBr4 TCE salt were measured on a
Fourier transform infrared (FT-IR) Bruker Equinox 55
spectrometer equipped with a Hyperion 1000 microscope.
The KramersKronig analysis of the reectance data was
carried out to obtain the frequency dependent conductivity.
The low-frequency data were extrapolated to zero frequency
assuming a constant value; it is typical extrapolation for
semiconducting materials. Above the highest frequency
point of the experimental data the reectance were extended
as R  x2 and above 106 cm1 as R  x4. The plasmaedge-like dispersion in the reectance spectra was tted with
the Lorentz dielectric function and the temperature dependence of optical transport parameters was investigated.
Moreover, the Raman spectra were recorded down to the
liquid helium temperature from (0 0 1) face of the single crystal with a Renishaw System 1000 microspectrometer with
excitation beam from laser Lexel 3500 (k = 568 nm, less
than 1 mW power was at the sample). For low temperature
IR and Raman measurements, the samples were mounted
on a cold stage of a continuous-ow helium cryostat. The
spectral resolution of IR and Raman spectra was 2 cm1.
We also simulated the dynamics of DOEO0, DOEO+,
and TCE molecules using the commercial program Gaussian03 [13]. The calculations were carried out on an isolated
molecule to determine the response of the molecular
dynamics, which dominate in the middle infrared region.
The equilibrium geometry and vibrational transitions of
the all investigated molecules were evaluated with a
Becke-style 3-Parameter Density Functional Theory with
the LeeYangParr correlation functional (B3LYP) [14
16] using a basis set of 6-311++G(d,p). The starting point
of the optimization process was the DOEO and TCE geometry taken from X-ray data [12]. The mode description was
performed by visual inspection of the individual modes
using the GaussView program and Veda 4 program [17];
with the help of the latter program we performed calculation of potential energy distribution (PED) of normal
modes vibrations. The proposed assignment was performed
based on the experimental and theoretical data.
3. Results and discussion
3.1. Electronic structure
Fig. 1 shows the reectance spectra of (DOEO)4HgBr4 TCE salt recorded from the (0 0 1) crystal face for three
polarizations of incident light at room temperature; two of
them, perpendicular to each other, were measured for
polarization parallel to the stacking direction (E//b) and

A. apinski, A.I. Kotov / Chemical Physics 326 (2006) 551562

Fig. 1. Polarized reectance spectra of (DOEO)4HgBr4 TCE single

crystal at room temperature and the Lorentz model t (dotted line)
(upper panel) and polarized optical conductivity spectra of (DOEO)4HgBr4 TCE, as obtained by KramersKronig analysis of the reectance
spectra (bottom panel). The inset shows sum rule calculations based on the
optical conductivity data for (DOEO)4HgBr4 TCE salt.

perpendicular to it (E//a). The reectance spectrum parallel

to the diagonal direction (E//[1 1 0]), what nearly corresponds to the direction of the S  S interactions, was
recorded as well. In Fig. 1 the optical conductivity spectra
obtained by a KarmersKronig transformation of the
reectance data are presented. At room temperature, the
observed anisotropy is quite large and shows that
(DOEO)4HgBr4 TCE is Q-1D salt. The reectance and
conductivity spectra recorded for (E//b) and (E//[1 1 0])
are typical for semiconducting materials suggesting the existence of an optical energy gap; it is in agreement with electrical conductivity measurements [12]. Below the 2000 cm1
we see a broad vibrational features superimposed on electronic absorption observed at about 3000 cm1. Apart from
this electronic band another one at about 11,000 cm1 can
also be found. These bands can be attributed, by analogy
with TCNQ, ET, and BEDO-TTF (or BO) (see e.g. [18
21]), to intermolecular electronic transitions between the
neighboring DOEO molecules within the stacking directions. The maximum of these electronic transitions is
observed for direction parallel to the stacking axis (E//b),
whereas the minimum is for the polarization perpendicular
to it (E//a); it supports such interpretation. Moreover, we
performed the calculation of intramolecular excitation of

553

DOEO+ and DOEO0 at the theory level TD-B3LYP/

6-311++G(d,p) and we did not nd any transitions in the
spectral region around 11,000 cm1.
The band at 3000 cm1 corresponds to the charge transfer process DEDO0 + DOEO+ ! DOEO+ + DOEO0; its
position depends on the Coulomb repulsion energy between
two electrons on adjacent molecules, V and hopping integrals. The band at about 11,000 cm1 is attributed to the
charge transfer process DEDO+ + DOEO+ ! DOEO2+ +
DOEO0. The position of this band can be approximately
described by the value of the eective Coulomb interaction,
because two electrons reside on the same site in the nal
state. The energy of such transition is proportional to
(U = U0  V), the Hubbard parameters for on-site and
nearest-neighbor Coulomb repulsion. Assuming V to be
small, we can estimate the on-site Coulomb repulsion from
the center position of this band. For (DOEO)4HgBr4 TCE
we nd U = 11,000 cm1 (or 1.36 eV), whereas for ET and
BO salts the value of the eective Coulomb interaction is
about 10,000 cm1 [22,23] and 12,000 cm1 [19,24], respectively. The dierence between the positions of the mentioned band for ET and BO salts results from calculations
of valence force constants that the rigidity of the outer rings
of BO is larger than that of ET [25]. This can lead to a less
eective screening of Coulomb interactions and an increase
in both U0 and the frequency of this charge transfer band.
The frequencies and oscillator strengths of these chargetransfer bands are clearly related to the electronic structure
of the compound, but their interpretation is dened by three
types of interactions among the unpaired electrons occupying the highest molecular orbital (HOMO) in the solid.
These interactions are the overlap of the electronic wave
functions between sites, the Coulomb repulsion of two electrons on the same or adjacent sites, and interactions of the
electron with phonons.
The computation of electronic structure of DOEO0 and
DOEO+ has been performed by quantum chemical calculation at the DFT(B3LYP) theory level and it gives the value
of HOMO energy: 4.8 and 8.5 eV for neutral and charged
DOEO molecule, respectively. The HOMO energy for
DOEO+ is close to BO+ value 8.9 eV and ET+ (8.7 eV)
[26]. The LCAO calculations were performed using the 6311++G(d,p) basis set provided with Gaussian03 as well.
In Fig. 2 the charges on atoms for DOEO0 and DOEO+ are
presented. The electron density distribution on atoms of
the fragment of these molecules which is perpendicular to
the main plain of DOEO shows that the charges on atoms
are practically the same in both cases. The signicant
changes in the charges are only observed in the plain part
of DOEO molecule (see Fig. 2).
In order to analyze the electronic dispersion for
(DOEO)4HgBr4 TCE salt we made least-squares ts to
the experimental data of the reectance calculated from
the Lorentz dielectric function of the form [27]:
ex

x2p
x2L
2
e1
2
2
xg  x  ix=s x0  x2  ixC

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A. apinski, A.I. Kotov / Chemical Physics 326 (2006) 551562

Fig. 2. The optimized geometry (upper part) and calculated charge values on the atoms (lower part) of DOEO neutral molecule (a) and DOEO+ cation
(b).

where xp and xL are the strength of transitions, xg and x0

mean the centers frequency (related to the energy gaps), 1/s
and C are relaxation rates, and e1 is the high frequency
dielectric constant. The rst term in Eq. (1) describes the
reectance maximum at 3000 cm1, the second term includes the weak structure around 11,000 cm1, and the
third term is the contribution of all higher frequency contributions to the static dielectric constant. The ts were
made to the reectance data recorded for E//b and E//
[1 1 0] between 2000 and 18,000 cm1. The best t parameters obtained from the Lorentz model analysis of the room
temperature IR reectance spectra of (DOEO)4HgBr4
TCE are as follows: for E//b polarization xp = 7855 cm1,

xg = 2443 cm1, 1/s = 2023 cm1, xL = 3956 cm1, x0 =

11,712 cm1, C = 2863 cm1, e1 = 2.45 and for E//[1 1 0]
xp = 8018 cm1, xg = 3353 cm1, 1/s = 3047 cm1, xL =
3135 cm1, x0 = 12,980 cm1, C = 3191 cm1, e1 = 3.45;
the exemplary ts are shown in Fig. 1 (see dotted lines).
Additional information about the electronic structure of
(DOEO)4HgBr4 TCE salt can be also extracted from the
oscillator strength sum rule [27,28]. The eective number
of electrons participating in optical transitions for energies
less than hx is given by
Z
m0
m0 V m x
N eff x
rx0 dx0
2
meff
4pe2 0

A. apinski, A.I. Kotov / Chemical Physics 326 (2006) 551562

where me is the eective (band) mass of the carriers, m0 is

the free electron mass, e is the electron charge, and Vm is
the volume per molecule. For E//b and E//[110], (m0/me)Ne increases rapidly at rst and begins to level o at a value near 0.23 and then rises rapidly above 1 eV; see inset in
Fig. 1. The function rises much more slowly and smoothly
for the E//a polarization. The plateau value of (m0/me)Ne = 0.23 and the assumption of Ne = 0.5 gives me = 2.2
m0 for E//b and E//[110] polarizations; the eective masses
of holes, similar in these directions, suggest that the investigated salt belongs to the class of materials Q-1D type.
In Fig. 3 the temperature evolution of the reectance
spectra recorded for two polarizations: parallel (E//b) and
perpendicular (E//a) to the stacking direction are presented. The spectra measured down to the 140 K show typical semiconducting behavior. In the temperature region
from 140 to 30 K the low frequency reectivity for both
polarizations rises in agreement with the dc conductivity
measurements; it is due to intraband transitions of quasifree carriers and they are usual for conducting ET-compounds [2931]. Below the 140 K for the polarization E//
a the new electronic band at about 1200 cm1 is starting
to grow; this band can be related to interband transitions,
superimposed on the free-carrier tail and it may be evidence
of an electron transfer in the a-direction. Based on these
results, we can suggest that the dimensionality of our system below 140 K is closer to Q-2D type; it is in agreement
with X-ray data [12]. Additionally, one can observe the
spectral features at about 2900 cm1 in the CAH stretching
region. The intensity of these bands grows on temperature
decreasing below 140 K; it can suggest that the ordering of
ethylene groups play crucial role in the nature of phase
transition observed at around 140 K.
For E//b polarization we performed ts with one Lorentz oscillator at about 3000 cm1. Temperature depen-

Fig. 3. Temperature dependence of the reectance spectra of

(DOEO)4HgBr4 TCE measured from (0 0 1) crystal face with the electrical
vector of the polarized light perpendicular (a) and parallel to the DOEO
stacks (b).

555

dence of these transport parameters is shown in Fig. 4.

The obtained results allow us to determine the band-structure parameters for the (DOEO)4HgBr4 TCE crystals. All
parameters, within the experimental accuracy, seem to be
inuenced by the phase transition at 140 K. A small modication due to the phase transition observed at 50 K for dc
conductivity data can be only noticed for the relaxation
rate 1/s (the slope of temperature dependence changes at
about 70 K).
3.2. Vibrational features
Fig. 5 shows room temperature Raman spectra of
(DOEO)4HgBr4 TCE salt obtained for two polarizations
of incident light parallel to the a- and b-direction. The spectra were measured with the exciting laser light focused on
the (0 0 1) crystal face. Within the region of C@C stretching
one can observe two strong bands at 1494 and 1459 cm1
and one weak, broad band at about 1564 cm1. The position of these lines was determined by the decomposition
the experimental Raman spectra using standard PeakFit
program (see Fig. 5 upper panel, dotted lines); in tting
process the spectroscopic Lorentz Area function was used.
The maximum of intensity of C@C stretching bands is
observed when the electrical vector of the polarized laser

Fig. 4. Temperature dependence of the Lorentz parameters, extracted

from tting the reectance data of (DOEO)4HgBr4 TCE crystals for
polarization parallel to the stacking direction (E//b); where xp is the
strength of transition, xg means the center frequency, 1/s is the relaxation
rate, and e1 represents all higher frequency contributions to the dielectric
function.

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A. apinski, A.I. Kotov / Chemical Physics 326 (2006) 551562

Fig. 5. The experimental room temperature Raman spectra of

(DOEO)4HgBr4 TCE salt obtained for two polarizations of incident
light parallel to the a- and b-direction; the laser light was focused on the
crystal face (0 0 1). Dotted lines show the spectra decomposition on ve
components observed at 1564, 1494, 1459, 1390, and 1351 cm1 (upper
panel). In the lower panel the simulated Raman spectra of the neutral
DOEO0 molecule, DOEO+ cation, and the solvent TCE are presented.

beam is parallel to the a-direction, i.e. parallel to the long

molecular axis of DOEO. For the perpendicular polarization we can see the minimum of intensity of the band at
1494 cm1; taking into account the arrangement DOEO
molecules in crystals, this can suggest that the band
1494 cm1 should be related to central C@C stretching.
Apart from the C@C bands it is possible to nd in Raman
spectra other bands: 1390, 1351, 1164, 740, 636, 559, 505,
455, and 362 cm1.
It is well known that Raman scattering experiments are
often applied to evaluate the average charge on a molecule
(q) [32,33] and q is one of the important clues in determining the nature of the phase transition. For that reason, we
have performed temperature investigation of Raman spectra within the region of C@C stretching (see Fig. 6). One
can see, that the phase transitions at T = 50 K and at about
140 K have no inuence on the number and/or position of
Raman active bands. Taking into account the stoichiometry of investigated salt, the analyze of X-ray data done by
Bardin et al. [12], and our quantum chemical calculation
(the simulated Raman spectra are shown in the lower panel
of Fig. 5) we can strongly suggest that DOEO molecule
carries an average charge of +0.5e down to the liquid
helium temperature, thus the conduction band for dimerized structure of (DOEO)4HgBr4 TCE is eectively halflled bands (+1e per dimer).

Fig. 6. The Raman spectra of (DOEO)4HgBr4 TCE crystal within the

region of C@C stretching for dierent temperatures.

In Fig. 7 the optical conductivity spectra derived by the

KramersKronig transformation are presented. These
spectra were recorded for three polarization: E//b, E//
[110], and E//a. For each spectrum one can nd many well
dened bands. Some of them are broad and characteristically asymmetric like Fano lineshape of bands [34] with
characteristic dips observed near the absorption peak. This
eect is readily observed in (DOEO)4HgBr4 TCE for
polarization parallel to the stacking axis (E//b); in particular there are distinct antiresonance in conductivity spectra
with the dips at 1011 cm1 (near the band at 1000 cm1)
and 863 cm1 (near 852 cm1). For Q-1D systems this
eect is observed when the electric eld is polarized along
the chain and the electronic absorption overlaps the phonon frequencies; the interaction between electrons and phonons gives rise to characteristically asymmetric Fano
lineshape of bands [34]. Moreover, it is known that the
analysis of Fano-eect combined with Raman data can
lead to quantitative predictions for the various electron
phonon couplings [35].
In order to analyze the experimental IR and Raman
data we have simulated spectra for neutral DOEO0 molecule, cation DOEO+, and TCE solvent molecules (see Figs.
5 and 7). The geometrical structure of these species was
fully optimized at the level of theory B3LYP/6311++G(d,p). As a starting point in optimization process
was the position of atoms for DOEO and TCE molecules
taken from X-ray data [12]. The normal-mode analyses
were carried out for such optimized structures. The results

A. apinski, A.I. Kotov / Chemical Physics 326 (2006) 551562

Fig. 7. The optical conductivity spectra of (DOEO)4HgBr4 TCE salt

obtained for three polarizations of incident light, as obtained by
KramersAKronig analysis of the reectance spectra recorded at room
temperature from the (0 0 1) plane (upper panel). The simulated IR spectra
of the neutral DOEO0 molecule, DOEO+ cation, and the solvent TCE
(lower panel).

are listed in Table 1 along with the observed modes. The

rst two columns of this table show the wavenumbers of
the bands of (DOEO)4HgBr4 TCE found from Raman
and IR spectra. The next columns present the theoretical
wavenumbers of active bands for neutral DOEO molecule
and cation and their IR and Raman intensities; the assignment of the bands is given as well. Moreover, the appropriate band position for DOEO0 and DOEO+ were conrmed
by visual inspection of the individual modes using the program GaussView. The internal coordinates and their
description are present in Fig. 9 and Table 2. The Raman
bands are assigned with the aid of polarization dependence
and to classify the observed IR active vibrations we used
the polarized reection spectra of the (DOEO)4HgBr4 TCE single crystal.
In the optimization process we have found that the TTF
framework for the fully optimized DOEO0 is non-planar,
whereas for DOEO+ it is planar (except the outer ethylene
groups) (see Fig. 2). The similar situation has been
observed in the cation and neutral ET molecule [3739].
According to the normal-mode analysis, assuming C1
molecular symmetry, the DOEO molecule has 93 fundamental intramolecular (internal) modes of vibration.
Three of these modes related to C@C stretching are presented in Fig. 8 with the schematic atomic displacement
of carbon atoms observed in neutral molecule (a) and cation (b). For the neutral DOEO molecule two modes are
composed of ring C@C stretching (m = 1635 cm1 and
m = 1494 cm1) and one mode corresponds to central

557

C@C stretching (m = 1526 cm1). As shown in Fig. 8, the

local C@C stretching modes are more mixed in a neutral
molecule then in the cation. The rearrangement of the bond
lengths in the cationic state introduces inequality into the
force constants of these three C@C stretching vibrations
and thus, the mixing among the C@C stretching is partly
removed. A similar change in mixing between a neutral
molecule and a cation radical is experimentally conrmed
in ET salts [40]. As shown in Fig. 8 the modes related to
the C@C stretching vibration show large low-frequency
shifts when the molecule is oxidized. According to the calculation, the modes 1635, 1526, and 1494 cm1 have the
shift equals 111, 145, and 75 cm1, respectively. The main
reason for the shift of these modes comes from the change
in molecular geometry upon oxidation.
Within the region 13001600 cm1 the experimental
Raman spectra are dominated by the bands at 1564,
1494, 1459 cm1 and can be ascribed to stretching of the
C@C double bonds in the central and peripheral fragments
of the molecule. The vibrational features of C@C stretching in the infrared spectra are observed at 1540, 1368,
and 1170 cm1; for organic conductors they are normally
shifted to lower frequencies compared to their Raman
modes because they are activated by emv coupling, the
dierence increases with the coupling constant. One can
also see that vibrational spectra of (DOEO)4HgBr4 TCE
consist of the normal modes related mainly to the donor
molecule (see Fig. 7).
3.3. Electronphonon coupling
It is well known that in conducting charge transfer crystals the coupling between the electrons in the highest occupied molecular orbital (HOMO) and the totally symmetric
molecular vibrational modes of molecules and strong
bands corresponding to this interaction dominate their
IR spectra [41,42]. The symmetry arguments show that,
for non-degenerate radical electron MOs, the only nonzero linear coupling constants are those for the totally symmetric intramolecular modes [4345]. For modes of other
symmetries, the electronvibrational interaction is forbidden by the selection rules. This selection is correct only in
the case where neutral and ionized molecules belong to
one and the same symmetry type [43]. Consider the suciently fast charge transfer between a molecule and an
ion due to the action of the electromagnetic radiation, so
that the nuclear conguration does not have time to change
during the transition (after the transfer a molecule has the
conguration of an ion and an ion has the conguration of
a molecule) the molecular vibrations will arise as the result
of the relaxation to the equilibrium congurations. In this
case the symmetry type of arising vibrational modes
depends not only on the initial and the nal state symmetry, but also on the symmetry of the intermediate states
in which the transferred charge belongs to both neighboring molecules. This fact suggests that non-totally symmetric modes can also be coupled [46].

A. apinski, A.I. Kotov / Chemical Physics 326 (2006) 551562

558

Table 1
Frequencies and assignments of vibrational features of the (DOEO)4HgBr4 TCE; m, wavenumber (cm1); I, IR intensity (km/mol); A, Raman scattering
4/amu)
activity (A
Experiment (cm1)

Calculationa

Raman lines

Neutral

Optical conductivity

362

455

505

559

562

636
740

580
633
736
788
820

852
873
889
902
938
951
974
1000
1045
1057
1064
1083
1092
1128

PEDb
Cation

18
34
40
54
58
93
97
120
148
160
168
199
225
241
266
269
295
300
309
316
353
365
367
390
400
418
432
448
462
468
499
502
531
540
560
567
579
717
736
760
778
792
832
841
848
850
864
903
911
954
966
970
981
1013
1047
1061
1070
1074
1092
1130

1.3
0.2
0.7
0.5
2.9
0.1
6.3
0.0
0.0
0.6
4.8
0.9
0.7
1.2
2.0
0.6
5.9
2.9
4.4
3.1
1.0
3.1
1.0
9.0
0.7
4.8
1.3
5.2
1.9
0.6
7.4
15.4
0.4
22.1
33.3
4.6
5.6
15.1
44.9
5.8
7.5
1.1
23.7
35.2
0.4
37.0
24.1
114.9
12.2
21.0
8.2
14.7
7.6
12.7
14.0
23.3
0.6
231.0
98.2
535.6

0.4
2.1
0.5
0.3
0.7
0.6
0.6
0.7
0.3
15.8
1.1
1.9
5.0
1.9
0.5
1.1
1.6
4.9
1.0
4.4
3.2
1.3
0.8
4.0
4.3
0.4
7.9
0.8
21.0
4.0
5.2
3.4
2.0
12.5
12.0
1.8
4.3
4.8
1.0
5.6
0.4
0.9
5.2
6.9
6.3
19.9
1.4
4.9
4.2
4.9
0.8
4.7
8.9
6.7
1.8
2.8
4.5
2.4
0.1
0.8

19
40
32
51
74
83
101
117
140
167
156
190
228
245
281
270
298
319
313
303
351
365
368
406
399
431
454
449
478
466
489
495
537
533
550
571
581
723
770
762
781
846
829
836
843
856
863
903
928
963
997
978
971
1010
1048
1059
1068
1078
1096
1161

0.9
0.4
0.1
0.1
1.6
0.1
6.8
0.1
0.0
3.8
1.9
1.7
0.8
5.8
2.8
0.1
4.4
0.9
6.6
16.1
4.8
2.0
3.2
0.5
4.6
0.1
8.9
3.4
18.6
22.5
67.6
7.3
0.3
61.1
11.6
6.5
87.7
35.2
14.7
9.1
12.5
4.6
29.1
141.1
1.9
10.9
15.6
178.2
26.0
17.4
1.5
9.6
154.9
37.0
5.9
28.3
1.8
199.1
228.7
283.2

8.2
7.8
1.0
1.2
1.3
1.2
0.3
1.9
0.6
11.9
8.9
4.6
0.9
33.6
36.9
2.6
9.8
17.1
2.2
8.2
12.8
10.3
15.6
90.6
4.5
57.4
350.7
14.4
1166.1
41.4
94.0
410.0
65.8
101.0
2.0
0.6
20.0
28.2
4.4
67.0
9.2
5.2
4.4
13.4
2.6
8.3
22.5
128.6
2.7
9.0
11.3
34.2
8.0
33.2
1.8
2.2
6.8
29.6
86.1
86.1

F1F2F26F28F31 (73)
F2F3F28 (47)
F36 (84)
S4S7 (70)
F1F2F29 (69)
F34F27 (58)
F1F2F4F5 (68)
F24F26 (30)
F4F5F42F43F44 (84)
F25 (22)
S4S7B9 (37)
F24F38F39 (39)
H8 (45)
S4S7B9 (24)
F2F6F40F41F44 (56)
F4F6F42F44 (74)
B2B3 (21)
F4F5F43(23)F16F17F20 (23)

S4S7B9 (37)
B7B16 (22)
S5S6B12B14B15 (40)
H9B11B16 (53)
S6B16 (54)
K1K13 (40)
S2B6 (23)
F38F39 (57)
F40 (55)
F4F5F42F44 (75)
B5 (21)
F14F15F16F17F18F21 (27) S5S6B12B13B14 (40)
K15K16K20K21K25 (53)
B4B10 (33)
S5S6B11B16B17 (61) K1K17 (21)
F7F8F45 (27)
K13K22 (79)
K6K7 (63)
S5S6B12B13B14B15 (56)
F14F15F16F17F18F21 (32) K15K19K21 (42)
K3K8K9K12 (70)
K8K9 (49)
K16K17K20 (56)
S1S3 (34)
K3K11 (41)
S1S3 (22)
K17K19 (70)
K5K6K7K8K9 (47)
K5K6K8K9 (62)
K15K19K21 (21) S5S6B12B13B14 (22)
F4F5F43 (40) F15F16F17 (38)
K5K9 (25)
K5K9 (46)
K16K20K25 (81)

A. apinski, A.I. Kotov / Chemical Physics 326 (2006) 551562

559

Table 1 (continued)
Experiment (cm1)

Calculationa

Raman lines

Neutral

1164

Optical conductivity

1166
1180
1206
1215
1227
1248
1260
1308
1314

1351
1361
1371
1419

1390
1459
1494
1564

1435
1395
1200
1368
1540
2855
2876
2912
2930
2976

3002
3020

PEDb
Cation

1156
1194
1213
1220
1236
1245
1247
1295
1304
1337
1339
1343
1355
1430
1432
1433
1434
1494
1526
1635
2867
2880
2914
2919
2924
2986
2992
2999
2999
3001

27.4
4.7
7.0
5.0
3.8
25.7
37.6
38.6
1.5
1.2
0.1
20.4
1.7
7.9
0.0
6.1
10.0
4.0
28.4
125.9
18.7
71.9
42.9
18.9
33.6
20.8
24.8
30.7
3.5
14.2

5.5
5.8
13.1
4.0
3.7
6.6
4.5
5.6
2.1
3.2
7.2
1.8
0.9
13.8
1.7
2.4
13.4
524.6
471.9
33.2
188.0
244.8
257.2
70.3
46.8
113.6
161.2
257.1
126.6
145.1

1189
1199
1212
1218
1236
1244
1246
1292
1309
1341
1343
1351
1358
1432
1437
1437
1435
1419
1381
1524
2877
2905
2943
2925
2952
3001
3007
3026
3008
3029

39.9
25.4
11.6
3.7
2.2
33.2
57.6
95.6
0.5
413.6
8.3
1.8
0.9
20.5
16.9
10.8
14.4
1469.3
103.1
1847.1
6.8
40.8
23.7
17.4
12.4
10.1
11.4
7.8
0.6
1.6

2.4
33.7
23.6
3.9
3.6
98.3
10.9
38.3
8.8
350.8
117.1
11.7
1.4
50.2
19.3
76.7
172.1
5872.5
15167.9
2246.9
289.9
213.1
459.4
32.1
87.2
103.8
149.6
376.1
256.1
158.3

K20 (45) S6B16 (26)

F7F13 (69)
H4H7 (56)
H9H11 (82)
F7F13 (45) H4H7 (21)
H10H11 (83)
H4H7 (56)
H2H3 (76)
H1 (63)
F14F15F21 (72)
F10F12 (47)
F14F15F20F22 (61)
F8F9F10F12 (60)
H12H13 (76)
H14H15 (73)
H12H13 (64)
H14H15 (81)
K24 (73)
K23 (79)
K25 (75)
R6 (99)
R5 (87)
R7R10 (90)
R2 (85)
R7R8R9R10 (98)
R4 (88)
R1R3 (73)
R8R9 (90)
R1 (85)
R8R9R10 (98)

B3LYP/6-311++G(d,p) (scaled by 0.9614 [36]).

Value in parenthesis is the potential energy distribution (PED); contributions >20% are included. Coordinates involved in PEDs are described in
Table 2.
b

Fig. 8. Schematic atomic displacement for the C@C stretching modes observed in neutral molecule (a) and cation (b). Note: The position of these modes
are calculated using B3LYP/6-311++G(d,p) theory and scaled by 0.9614 factor [36].

A. apinski, A.I. Kotov / Chemical Physics 326 (2006) 551562

560

Fig. 9. Internal coordinates of DOEO; R, s, and r denote the bond

stretching; U, d, and b denote the bond bending.

In organic conductors formed by the TTF derivatives

the strongest electronmolecular vibration (emv) coupling
eect is observed for the totally symmetrical modes due to
C@C stretching vibrations. For example, ET and BO molecules have two C@C vibrations of both central and ring
C@C bonds: m2(ag) = 1551 cm1 and m3(ag) = 1493 cm1
[47] and m2(ag) = 1656 cm1 and m3(ag) = 1527 cm1 [26],
respectively. Moreover, it is also well known that for ET
salts the unsymmetrical stretching vibration of C@C ring

double bonds (m27(b1u) mode) induces charge ow along

the molecular axis and it can be coupled with conducting
electrons [48]. In the case of DOEO molecule we have three
unsymmetrical modes attributed to C@C stretching (see
Fig. 8) observed in the Raman experiments at 1564, 1494,
and 1459 cm1 (see Fig. 5). Moreover, strong, asymmetrical
Fano lineshape bands [34] suggests that we have interactions
between electrons and intramolecular vibrations. Therefore,
we decided to estimate, as a preliminary approach, the
strength of such interaction at linear approximation.
The emv coupling phenomena in conducting chargetransfer ET salts were analyzed in terms of various models
depending on structure of the molecular stacks. Microscopic
theories for regular stacks or stacks consisting of quasi-isolated dimers, trimers, tetramers or n-mers have been developed [49]. In the studied crystals of (DOEO)4HgBr4 TCE
the conducting layers consist of DOEO dimers with one hole
per dimer; therefore, the model of isolated dimer with one
unpaired electron, given by Rice, Yartsev, and Jacobsen

Table 2
The symbols of internal coordinates of DOEO molecule
Symbol

Coordinate

Description

Symbol

Coordinate

Description

Symbol

Coordinate

Description

K1
K2
K3
K4
K5
K6
K7
K8
K9
K10
K11
K12
K13
K14
K15
K16
K17
K18
K19
K20
K21
K22
K23
K24
K25
R1
R2
R3
R4
R5
R6
R7
R8
R9
R10
H1
H2
H3
H4
H5

s1s1
s2s2
s3s3
s4s4
s5s5
s6s6
s7s7
s8s8
s9s9
s10s10
s11s11
s12s12
s13s13
s14s14
s15s15
s16s16
s17s17
s18s18
s19s19
s20s20
s21s21
s22s22
R1R1
R2R2
R3R3
r1r1
r2r2
r3r3
r4r4
r5r5
r6r6
r7r7
r8r8
r9r9
r10r10
b2b2
b6b6
b9b9
b3b4
b4b4

CAS stretch
CAS stretch
CAS stretch
CAS stretch
CAO stretch
CAO stretch
CAC stretch
CAO stretch
CAO stretch
CAS stretch
CAS stretch
CAS stretch
CAS stretch
CAS stretch
CAS stretch
CAO stretch
CAO stretch
CAC stretch
CAO stretch
CAO stretch
CAS stretch
CAS stretch
C@C stretch
C@C stretch
C@C stretch
CAH stretch
CAH stretch
CAH stretch
CAH stretch
CAH stretch
CAH stretch
CAH stretch
CAH stretch
CAH stretch
CAH stretch
OCH bend
CCH bend
OCH bend
OCH bend
HCH bend

H6
H7
H8
H9
H10
H11
H12
H13
H14
H15
S1
S2
S3
S4
S5
S6
S7
B1
B2
B3
B4
B5
B6
B7
B8
B9
B10
B11
B12
B13
B14
B15
B16
B17
F1
F2
F3
F4
F5
F6

b7b7
b7b8
b9b10
b11b12
b13b13
b15b16
b4b4
b7b7
b12b12
b15b15
d2d2
d4d4
d5d5
d6d6
d9d9
d10d10
d12d12
U1U1
U3U3
U4U4
U7U7
U8U8
U9U9
U12U12
U13U13
U14U14
U15U15
U17U17
U18U18
U19U19
U20U20
U21U21
U22U22
U24U24
R1U15
R1U23
R2U2
R3U18
R3U21
R3U23

HCH bend
OCH bend
SCO bend
OCH bend
CCH bend
OCH bend
HCH bend
HCH bend
HCH bend
HCH bend
SCC bend
SCC bend
SCC bend
SCC bend
OCC bend
OCC bend
SCC bend
SCS bend
SCS bend
CSC bend
COC bend
OCC bend
OCC bend
SCC bend
CSC bend
SCS bend
CSC bend
SCO bend
COC bend
OCC bend
OCC bend
COC bend
SCO bend
SCS bend
CSCC tors.
CSCC tors.
CSCC tors.
COCC tors.
COCC tors.
CSCC tors.

F7
F8
F9
F10
F11
F12
F13
F14
F15
F16
F17
F18
F19
F20
F21
F22
F23
F24
F25
F26
F27
F28
F29
F30
F31
F32
F33
F34
F35
F36
F37
F38
F39
F40
F41
F42
F43
F44
F45

r1U7
r2U7
r3U7
r4U10
r5U9
r5U10
r6U10
r7U18
r8U18
r8U19
r8U20
r9U19
r9U20
r9U21
r10U19
r10U21
s2U4
s9U13
s10U10
s11U5
s11U15
s12U13
s14U12
s15U9
s10U6
s10U10
s20U23
s23U13
s10U6
s1U24
s2d2
s2d3
s11d5
s13d1
s15d9
s16d8
s16d10
s20d11
r5b6

COCH tors.
COCH tors.
COCH tors.
COCH tors.
CCOH tors.
COCH tors.
COCH tors.
COCH tors.
COCH tors.
CCOH tors.
OCCH tors.
OCCH tors.
OCCH tors.
COCH tors.
OCCH tors.
COCH tors.
CSCS tors.
OCSC tors.
COCS tors.
CSCS tors.
CSCS tors.
CSCS tors.
CSCS tors.
CSCO tors.
CSCO tors.
CSCO tors.
CSCO tors.
CSCS tors.
CSCO tors.
CSCO tors.
CSCC tors.
CSCC tors.
CSCS tors.
CSCS tors.
CSCO tors.
CSCO tors.
COCO tors.
COCC tors.
CHCH tors.

A. apinski, A.I. Kotov / Chemical Physics 326 (2006) 551562

Fig. 10. Fit of the dimer model (dotted line) to the reectance spectra of
(DOEO)4HgBr4 TCE crystals for polarization parallel to the stacking
direction (E//b) (solid line).
Table 3
Dimer model parameters for the t to the E//b reectance spectra of
, xCT = 2443 cm1,
(DOEO)4HgBr4 TCE at 300 K, d = 3.64 A
3, t = 0.23 eV, e1 = 2.45, and C = 2023 cm1
V = 7456 A
xa (cm1)

ga (cm1)

ka

Assignment

1575
1494
1460
1164

183
252
233
136

0.04
0.08
0.07
0.03

Ring C@C stretch

Ring C@C stretch
Central C@C stretch
CAO stretch, OCC, SCO bend

[50] seems to be the most appropriate. The complex dielectric function is dened within this approach by
2

ex e1

4pne2 d 2 x2tCT
x2CT 1  Dx  x2  ixC

where xCT determines the position of the charge-transfer

peak in the absence of vibrational coupling, C is an electronic relaxation rate, e1 is the background dielectric constant, t is the chain-axis transfer integral, d is the spacing
between the molecules and n = N/V is the number of dimers per unit volume (N is the total number of dimers
and V is the volume of the system). The function
X
ka x2a
Dx
x2a  x2  ixca
a
is the phonon propagator. The xa and ca refer to the unperturbed resonant frequencies of the vibrational modes and
corresponding linewidths, respectively. The ka are dimensionless coupling constants, related to the electronmolecular vibration (emv) coupling constants ga by
ka

8t2 g2a
x3CT xa

561

We have analyzed our infrared results within the

framework of this model (see Fig. 10) taking into account
the structural data [12]. In Table 3 one can see model
parameters for the t to the E//b reectance spectra of
(DOEO)4-HgBr4 TCE at 300 K; it shows an internal
inconsistency with the model: the value of the transfer
integral t of 1855 cm1 gives 2t = 3710 cm1 compared
with xCT of 2443 cm1. One of the assumptions of the
theory, however, is that xCT must be greater than or
equal to 2t. Comparing the relevant DOEO emv coupling constants with the corresponding ones measured
for TTF-based electron donor molecules: TTF itself
[51,52], bis-fused TTF (TTP) [53], tetramethyl-tetrathiafulvalene (TMTTF) [54], dibenzo-tetrathiafulvalene
(DBTTF) [55], bis-ethylendithio-tetrathiafulvalene (ET)
[56], and (BO) [26] (see Table 4) one can see that the values of coupling constants for DOEO molecule are comparable with another TTF derivatives and the most strongly
coupled modes are due to the TTF skeleton vibrations,
namely the modes related to the stretching vibrations of
both central and ring C@C bonds.
4. Conclusion
In this paper, we have presented and discussed the
optical properties of the organic conductor (DOEO)4HgBr4 TCE in wide frequency and temperature ranges.
The reection spectra in polarized light were completed
with Raman scattering investigation. A systematic analysis of the spectra allowed us to obtain important information about the electronic and vibrational structure. From
the analysis of the IR spectra in terms of the isolated
dimer model the electronmolecular vibration (emv) coupling constants for DOEO molecule in (DOEO)4HgBr4 TCE salt can be estimated. We derived the
transport parameters for crystallographic direction parallel to b-axis using simple Lorentz model in temperature
range from 300 to 4 K. Our data conrm that the crystals
are quasi-one-dimensional conducting salt down to 140 K,
whereas below this temperature dimensionality is like for
quasi-two dimensional compounds.
Acknowledgements
We are indebted to A. Girlando and M. Masino for
their help in measuring the Raman spectra and A. Gaseckiej who helped with some of measurements. This work
was supported by the Polish Committee for Scientic
Research at the research project in 20042007.

Table 4
emv coupling constants, gi (meV) of the most important C@C stretching modes m (cm1) for several radical cations based on TTF
TTF [51,52]
m

TTP [53]
gi

1505

42

1420

133

TMTTF [54]

DBTTF [55]

gi

ET [56]

BO [26]

DOEO

gi

gi

gi

gi

gi

1540
1474
1423

8
54
9

1567

32

1555

19

1460

43

1656

42

1418

133

1409

79

1414

71

1527

55

1575
1494
1460

23
31
29

562

A. apinski, A.I. Kotov / Chemical Physics 326 (2006) 551562

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