Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 117 (2014) 315–322

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Spectrochimica Acta Part A: Molecular and

Biomolecular Spectroscopy
journal homepage: www.elsevier.com/locate/saa

Theoretical vibrational spectra and thermodynamics of organic

semiconductive tetrathiafulvalene and its cation radical
V. Mukherjee a,⇑, N.P. Singh b
a
Physics, Sambalpur University Institute of Information Technology (SUIIT), Sambalpur, India
b
Department of Physics, Udai Pratap Autonomous College, Varanasi, India

h i g h l i g h t s g r a p h i c a l a b s t r a c t

 Optimized molecular structures of

PFV, TTF and TTF+ are presented.
 Theoretical IR and Raman spectra of
these molecules are presented.
 Vibrational canonical partition
function is calculated.
 Thermodynamical parameters are
calculated.
 Variation of partition function and
specific heat with temperature are
presented.

a r t i c l e i n f o a b s t r a c t s

Article history: Molecular structure in optimum geometry and vibrational frequencies of pentafulvalene [bicyclopentyl-
Received 1 May 2013 iden-2,4,20 ,40 -tetraene], tetrathiafulvalene [2,20 -bis(1,3-dithiolylidene)] and its cation are calculated. All
Received in revised form 20 July 2013 the calculations are carried out by employing density functional theory incorporated with a suitable basis
Accepted 31 July 2013
set. Normal coordinate analysis is also employed to scale the DFT calculated frequencies and to calculate
Available online 8 August 2013
potential energy distributions. The molecular structures and vibrational frequencies are compared for
both the pentafulvalene and tetrathiafulvalene molecules. The effect upon geometry and vibrational fre-
Keywords:
quencies of TTF due to charge transfer has also been studied. The vibrational partition function and hence,
Organic conductors
DFT
the thermodynamical properties, such as Helmholtz free energy, entropy, specific heat at constant vol-
IR and Raman spectra ume and enthalpy are also calculated and compared for the title molecules. The reason of conductivity
SQMFF of tetrathiafulvalene has been tried to explain on the basis of molecular geometry and normal modes.
Thermodynamics Study of vibrational partition function exhibits that below 109 K, PFV starts to condense.
Ó 2013 Elsevier B.V. All rights reserved.

Introduction poly(3-hexylthiophene), poly(p-phenylene vinylene), as well as

An organic semiconductor is an organic material with semicon-
ductor properties. Single molecules, short chain (oligomers) and
organic polymers can be semiconductors. Semiconducting small
molecules (aromatic hydrocarbons) include the polycyclic aro-
matic compounds like fulvalene derivatives, pentacene, anthra-
cene, and rubrene. Polymeric organic semiconductors include
⇑ Corresponding author. Tel.: +91 9369050014.
E-mail address: vmukherjee@suiit.ac.in (V. Mukherjee).
polyacetylene and its derivatives.
There are two major overlapping classes of organic semiconduc-
tors. These are organic charge-transfer complexes and various lin-
ear-backbone conductive polymers derived from polyacetylene.
Linear backbone organic semiconductors include polyacetylene it-
self and its derivatives. Charge-transfer complexes often exhibit
similar conduction mechanisms to inorganic semiconductors. Such
mechanisms arise from the presence of hole and electron conduc-
tion layers separated by a band gap. While such classic mecha-
nisms are important locally, as with inorganic amorphous

1386-1425/$ - see front matter Ó 2013 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.saa.2013.07.105
316 V. Mukherjee, N.P. Singh / Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 117 (2014) 315–322

semiconductors, tunneling, localized states, mobility gaps, and tion and hence, some important thermodynamical parameters
phonon-assisted hopping also significantly contribute to conduc- using statistical thermodynamics.
tion, particularly in polyacetylenes.
Typical current carriers in organic semiconductors are holes and Computational details
electrons in p-bonds. Almost all organic solids are insulators. But
when their constituent molecules have p-conjugate systems, elec- The quantum chemical calculation has been performed using
trons can move via p-electron cloud overlaps, especially by hop- the B3LYP level of theory supplemented with the standard 6-
ping, tunneling and related mechanisms. Polycyclic aromatic 31++G(d,p) basis set, using the Gaussian 03 program [14] to calcu-
hydrocarbons and phthalocyanine salt crystals are examples of this late optimized bond lengths, bond angles and vibrational frequen-
type of organic semiconductor. Mainly due to low mobility, even cies with IR intensities and Raman scattering activities. The
unpaired electrons may be stable in charge-transfer complexes. optimized geometries corresponding to the minimum on the po-
Such unpaired electrons can function as current carriers. This type tential energy surface have been obtained by solving self consis-
of semiconductor is also obtained by pairing an electron donor tent field (SCF) equation iteratively. Harmonic vibrational
molecule with an electron acceptor molecule. frequencies have been calculated using analytic second order
Fulvalene is a hydrocarbon obtained by formally cross conjugat- derivatives to confirm the convergence to minima on the potential
ing two rings through a common exocyclic double bond. The name surface and to evaluate the zero-point vibrational energies without
is derived from the similarly structured fulvenes which lack one imposing any molecular symmetry constraints. It is a well known
ring. In general, the parent fulvalenes are very unstable, for in- fact that ab initio calculations tend to overestimate the vibrational
stance, triafulvalene has never been synthesized. On the other frequencies with respect to the experimental ones. This is due to
hands stable fulvalenes can be obtained by proper substitution or several reasons, for instance, the use of finite basis set, the incom-
benzannulation. Pentafulvalene (PFV) is the member of fulvalenes plete implementation of the electronic correlation and the neglect
family consisting of two 5-membered rings, each with two double of anharmonicity effects in the theoretical treatment. However, the
bonds. Although, it belongs to D2h point group of symmetry but calculated ab initio force field can be improved by using the scaled
however, it is very unstable and can be observed at very low tem- quantum mechanical force field (SQMFF) methodology. For subse-
perature [1]. quent normal coordinate analysis (NCA), the force field obtained in
Tetrathiafulvalene (TTF), an organosulfur compound, is the sul- Cartesian coordinates and dipole derivatives with respect to atom-
fur substitution of PFV. TTF is also known as an organic semicon- ic displacements were extracted from the archive section of the
ductor and studies on this heterocyclic compound contribute the Gaussian 03 output and transformed to a suitably defined set of
development of molecular electronics. Bulk TTF itself has unre- internal coordinates (the ‘‘natural coordinates’’) which are col-
markable electrical properties but however, distinct properties lected in Table 1 by means of a modified version of the MOLVIB
are associated with salts of its oxidized derivatives, such as salts program [15,16]. In present study, the scale factors are calculated
derived from TTF+. The high electrical conductivity of TTF salts using MOLVIB program and collected in Table 1.
can be attributed to the several features, for instance, its planarity, The vibrational canonical partition function is determined by
which allow p–p stacking of its oxidized derivatives, its high sym- multiplying the contribution from each of the normal modes.
metry, which promotes charge delocalization, thereby minimizing Assuming harmonic modes and choosing the zero of energy as
coulomb repulsion, and its ability to undergo oxidization at mid the ground vibrational level for each mode, i.e., neglecting the zero
potential to give a stable cation radical. Wudl et al. first demon- point energy for each mode, the vibrational canonical partition
strated that [TTF+]Cl was a semiconductor [2]. Subsequently, Ferr- function is defined as [17,18]:
aris et al. showed that the charge transfer salt [TTF]TCNQ is a
Y 1
narrow band gap semiconductor [3]. X-ray diffraction studies of Z vib ¼ ð1Þ
[TTF]TCNQ revealed stacks of partially oxidized TTF molecules i
1  expðhcm
i =kTÞ
adjacent to anionic stacks of TCNQ molecules. This segregated
where i is the index representing the normal modes. The vibrational
stack motif was unexpected and responsible for the distinctive
contribution to the specific heat, entropy, free energy and enthalpy
electrical properties, i.e., high and anisotropic electrical
are given by
conductivity.
Recently, Jaiswal et al. [4] have presented optimized geometry i =kTÞ2 expðhcm
X ðhcm i =kTÞ
and vibrational frequencies of 1,3-dithiole-2-thione (DTT) and re- C v;vib ¼ R ð2Þ
i
i =kTÞ2
½1  expðhcm
lated compounds which are important precursors in the synthesis
of TTF and its derivatives (organic p-donors). The IR and Raman
X hcm
i =kT

spectra of TTF and TTF-d4 were reported earlier in which an assign- Svib ¼ R  logf1  expðhcm
i =kTÞg ð3Þ
ment of the fundamental vibrational modes were presented only i
fexpðhcm
i =kTÞ  1g
for planar modes [5]. However, vibrational spectroscopic studies X
of TTF and its several derivatives have been reported so far [6–13]. F v ;vib ¼ RT log f1  expðhcm
i =kTÞg ð4Þ
Our articles surveys reveal that the normal coordinates analysis i
(NCA) of TTF molecule has not been carried so far which is an
important tool for mode assignment. In all the previous works X hcm
i =kT
hvib ¼ RT ð5Þ
vibrational frequencies of TTF were assigned to the corresponding i
expðhcm
i =kTÞ  1
normal modes using band positions, intensities and animations
available in Gaussian program which may not be reliable hence,
we are interested to present DFT and NCA calculations for TTF. Results and discussions
Since TTF is a fulvalene derivative, therefore, we have included
PFV in our study. In addition, TTF salts show more conducting nat- Molecular structure
ure rather TTF, therefore, we have also included TTF+ in our study.
Therefore, our aim is to investigate optimum geometry and vibra- The optimized bond lengths and bond angles of the title mole-
tional frequencies of PFV, TTF and TTF+ molecules. Moreover, we cules at the B3LYP/6–31++G(d,p) level along with the experimental
have also aimed to calculate vibrational canonical partition func- values for TTF [19] are collected in Table 2. The optimized
 V. Mukherjee, N.P. Singh / Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 117 (2014) 315–322 317

Table 1
Local symmetry coordinates and scale factors.

S. no. Parameters Symmetry coordinatesa Scale factorsb

Stretching
1 rCC1(exo-cyclic) R1 0.87473
2–3 rCC2 (ring) p1ffiffi ðR2 þ R3 Þ; p1ffiffi ðR2  R3 Þ 0.87473
2 2
4–11 rCS 1 1
2 ðR4 þ R5 þ R6 þ R7 Þ; 2 ðR4 þ R5  R6  R7 Þ;
1 1
2 ðR4 þ R 6  R5  R7 2 ðR4 þ R7  R6  R5 Þ;
Þ;
1 1
2 ðR8 þ R9 þ R10 þ R11 Þ; 2 ðR8 þ R9  R10  R11 Þ;
1
2 ðR8 þ R 10  R 9  R Þ; 1
11 2 ðR8 þ R11  R10  R9 Þ 0.99672
1 1 1
12–15 rCH 2 ðR12 þ R13 þ R14 þ R15 Þ; 2 ðR12 þ R13  R14  R15 Þ; 2 ðR12 þ R14  R13  R15 Þ; 12 ðR12 þ R15  R13  R14 Þ 0.89976

Bending
16–19 bCCS, bCSC, bSCS p1ffiffi ðR16 þ R17 Þ; p1ffiffi ðR16  R17 Þ;
2 2
1 1
2 ðR18 þ R19  R20  R21 Þ; 2 ðR22 þ R23  R24  R25 Þ 1.02281
20 bCC1 R26 1.12674
21 bCC2 R27 1.12674
22–25 bCCH 1 1 1 1 0.94093
2 ðR28 þ R29 þ R23 þ R31 Þ; 2 ðR28 þ R29  R30  R31 Þ; 2 ðR28 þ R29  R30  R31 Þ; 2 ðR28 þ R29  R30  R31 Þ

Wagging
26–29 xCH 1 1 1 1
2 ðR32 þ R33 þ R34 þ R35 Þ; 2 ðR32 þ R33  R34  R35 Þ; 2 ðR32 þ R33  R34  R35 Þ; 2 ðR32 þ R33  R34  R35 Þ
0.94093
30 xCC1 R36 1.12674
31 xCC2 R37 1.12674
Twisting
32–33 sCC p1ffiffi ðR38 þ R39 Þ; p1ffiffi ðR38  R39 Þ 1.00473
2 2
34–35 sCS 1 1
2 ðR40 þ R41  R42  R43 Þ; 2 ðR44 þ R45  R46  R47 Þ 1.00473
36 sCC1 (exo-cyclic) R48 1.00473
a
symmetry coordinates are written in terms of internal coordinates and their definitions are given in Supplementary table S1.
b
incorporated only seven different scale factor values.

molecular structures of PFV, TTF and TTF+ with atomic labeling are
shown in Fig. 1. The theoretical bond lengths of TTF are found
slightly higher than the corresponding experimental values except
for C1@C6 [19]. The optimized bond length of C1@C6 is in good
agreement with the experimental one. There is also a good agree-
ment between theoretical and experimental values of most of the
bond angles for TTF.
PFV forms planar structure with D2h point group of symmetry
while substitution(s) of four S atoms perturb the planarity of TTF
in such a way that symmetry of TTF drops to C2v point group.
The torsional angles C4AC2AS14AC1 and S14AC1AS13AC4 in
TTF are nearly 6° and 10° respectively. In addition, optimization
of TTF+ radical shows that TTF+ forms a planar structure similar
to PFV, i.e., having D2h point group of symmetry, therefore, it is
concluded that torsional perturbation produced by four S atoms
is balanced by a positive charge (+e) transfer by p-bond of exocy-
clic C@C. This C@C bond length is 1.366Å, 1.352 Å and 1.399 Å for
PFV, TTF and TTF+ respectively, i.e., the substitutions of S atoms in
TTF bring closer the two rings slightly as compare to PFV while in
TTF+, this bond length shows single bond character which is the
consequence of charge transfer. Each dithiolylidene ring in TTF
has 7p electrons: 2 for each sulfur atom, 1 for each sp2 carbon
atom. Thus, ionization converts each ring to an aromatic 6p-elec-
tron configuration, consequently leaving the central double bond
essentially a single bond, as all p-electrons occupy ring orbitals.
The cyclic C@C bond lengths is changed significantly in TTF and
shortened by 0.14 Å as compared to PFV while this bond length
is nearly same for TTF and TTF+.
The CAS bond lengths show a significant change in TTF+ as com-
pared to TTF and interestingly, all the eight CAS bond lengths are

Table 2
Optimized bond lengths (Å) and bond angles (°).

S. no. Parameters PFV TTF TTF+

a
Theo. Exp.
1 C1AC2/C1AS14 1.473 1.787 1.748 1.748
2 C1AC6/C1AS13 1.473 1.787 1.748 1.744
3 C1AC10/C1AC6 1.366 1.352 1.358 1.399
4 C2AC4/C2AS14 1.357 1.763 1.729 1.741
5 C4AC8/C2AC4 1.477 1.339 1.314 1.348
6 C6AC8/C4AS13 1.357 1.763 1.729 1.741
7 C2AH3 1.081 – – –
8 C4AH5/C2AH3 1.084 1.083 – 1.084
9 C6AH7 1.081 – – –
10 C8AH9/C4AH5 1.084 1.083 – 1.084
11 C2AC1AC6/S14AC1AS13 106.410 113.740 114.2 114.540
12 C1AC2AC4/C1AS14AC2 107.840 94.640 94.50 95.520
13 C2AC4AC8/S14AC2AC4 108.950 117.960 118.0 117.210
14 C4AC8AC6/C2AC4AS13 108.950 117.960 – 117.210
15 C8AC6AC1/C4AS13AC1 107.840 94.640 94.50 95.520
16 C2AC1AC10/S14AC1AC6 126.800 123.130 – 122.730
17 C4AC2AS14AC1 – 6.120 – 0.000
18 S14AC1AS13AC4 – 9.920 – 0.000
19 Potential energy (a.u.) 385.830 1823.760 1823.520
a
Ref. [19].
318 V. Mukherjee, N.P. Singh / Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 117 (2014) 315–322
Fig. 1. Optimized molecular structures: (a) PFV, (b) TTF (transverse view), (c) TTF (longitudinal view) and (d) TTF+ (longitudinal view).
nearly same in TTF+ which is not in TTF. In TTF, the theoretical bond
length of those CAS bonds which are near to conjugation point is
1.787 Å while it is 1.763 Å for those CAS bonds which are relatively
far from conjugation point whereas all the CAS bonds are nearly
1.74 Å in TTF+. The CAS bonds lengths in TTF are also found slightly
larger than that in DTT [4].
The electrostatic potential energies of all three molecules are
also calculated at same level of theory and these are listed at the
last row of Table 2. The inspection of potential energy directly re-
veals that TTF is much more stable than PFV. Since the potential
energy is calculated for isolated molecule, therefore, it is evident
that PFV substance must have higher energy when lattice forma-
tion will take place, i.e., increase in entropy (disorder) and hence,
result is less stability. However, TTF+ is slightly excited due to
charge transfer and its excess energy is 150 kcal/mol than TTF.
Vibrational dynamics
The harmonic vibrational frequencies calculated for the PFV,
TTF and TTF+ molecules at the B3LYP level using the triple split va-
lence basis set along with diffuse and polarization functions, 6-
31++G(d,p) are collected in Tables 3–5 respectively. The observed
IR and Raman frequencies [6] for various modes of vibrations of
TTF are also presented in same table for comparison reason. Com-
parison of the calculated frequencies with experimental values re-
veals the overestimation of the calculated vibrational modes due to
neglect of anharmonicity in real system. However, inclusion of
electron correlation in density functional theory to a certain extent
makes the frequency values smaller. Reduction in the computed
harmonic vibrations, though basis set sensitive are only marginal
as observed in the DFT values using 6-31++G(d,p). Any way not-
withstanding the level of calculations, it is customary to scale
down the calculated harmonic frequencies in order to improve
the agreement with the experiment and therefore, the calculated
frequencies are scaled using NCA method implemented in MOLVIB
7.0 program [15,16]. The potential energy distributions (PEDs) are
also calculated for conspicuous normal mode assignment. A brief
discussion regarding the vibrational absorption and scattering pro-
files and normal modes analysis of the considered molecules are as
follows-
Vibrational absorption profile
The calculated IR (absorption) spectra of PFV, TTF and TTF+ are
depicted in Fig. 2. Absorption profile of PFV is much better than
other two. TTF and TTF+ have nearly same profiles below
1800 cm1 while in higher wavenumber region, all the bands in
TTF are very much weak and only one band (3254 cm1) is strong
enough in IR spectrum of TTF+. The bands at 1533 cm1, 648 cm1
and 701 cm1 in PFV, TTF and TTF+ respectively, are the strongest
in the IR spectra. The PEDs reveal that the strongest band in PFV
is due to the ring stretching mode while in both the TTF and
TTF+, it is due to the CH wagging mode. However, the band at
780 cm1 due to the CH wagging in PFV is also showing strong IR
intensity.
Vibrational scattering profile
The calculated Raman spectra of PFV, TTF and TTF+ are depicted
in Fig. 3. The Gaussian (DFT) calculation provides Raman activity
instead of Raman intensity which can be further converted into
corresponding Raman intensity using empirical formula [20]. PFV
has only one strong band at 1685 cm1 and others are relatively
weak in its Raman spectrum. The PEDs of the mode of this fre-
quency shows maximum contribution of the C@C (exocyclic)
stretching vibration. Raman spectra of TTF and TTF+ show few
strong bands along with the most strong band at 1583 cm1 and
1563 cm1 respectively. The scattering of these frequencies are
contributed by C@C (exocyclic) stretching vibration in TTF and by
C@C (ring) stretching vibration in TTF+. An interesting result is
found for TTF and TTF+ that their IR spectra are somewhat same
with a slight frequency shift but their Raman spectra show great
discrepancy. In TTF, lower frequencies are relatively strong than
the higher frequencies up to 1500 cm1 while in TTF+, frequencies
below 150 cm1 are completely disappeared and only one band at
265 cm1 is strong enough in the far-IR region.
Normal modes
Our present calculations reveal that PFV, TTF and TTF+ belong to
D2h, C2v and D2h point groups of symmetry respectively and hence,
all the normal modes are distributed in corresponding species
and the distributions are 9Ag + 3B1g + 4B2g + 8B3g + 4Au + 8B1u +
8B2u + 4B3u, 10A1 + 9A2 + 8B1 + 9B2 and 7Ag + 2B1g + 3B2g +
6B3g + 3Au + 6B1u + 6B2u + 3B3u respectively. These distributions
are also shown in corresponding tables.
There are three frequencies for TTF and two frequencies for TTF+
below 100 cm1. The normal mode having frequency 38 cm1 and
84 cm1 for TTF and TTF+ respectively, is the CAS twisting which
looks like very similar to butterfly mode. The animation available
in Gaussian 03 program [14] shows that when TTF vibrates in this
mode, it gains its planarity at either extrema which is possible only
when TTF is ionized (TTF+), therefore it may be concluded that in
this mode TTF periodically losses and gains charge of one unit,
i.e., a periodic motion of a charge of one unit is set up in lattice
of TTF. Therefore, this mode has a good significance and may be
responsible for conductivity in TTF. This mode mostly shows a blue
 V. Mukherjee, N.P. Singh / Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 117 (2014) 315–322 319

Table 3
Normal mode assignment for PFV (D2h point group).

ma IRb Ramanc Species d

PEDs
3264 0.0 363.64 Ag 99rCH
3261 10.66 0.0 B2u 99rCH
3258 13.33 0.0 B1u 99rCH
3255 0.0 25.73 B3g 99rCH
3233 0.0 391.85 Ag 99rCH
3232 16.73 0.0 B1u 99rCH
3222 10.22 0.0 B2u 99rCH
3221 0.0 211.39 B3g 99rCH
1685 0.0 1438.42 Ag 70rCC1 + 16rCC2 + 6bCCH
1614 0.0 26.96 B3g 65rCC2 + 27bCCH
1610 0.18 0.0 B2u 67rCC2 + 27bCCH
1536 0.0 296.63 Ag 81rCC2 + 13bCCH
1533 169.65 0.0 B1u 74rCC2 + 19bCCH
1401 78.25 0.0 B1u 68bCCH + 28rCC2
1387 0.0 46.70 Ag 72bCCH + 19rCC2
1329 2.56 0.0 B2u 81bCCH + 15rCC2
1328 0.0 26.45 B3g 55bCCH + 32rCC2
1244 0.0 21.13 B3g 42bCCH + 30rCC2 + 11bCC1 + 11bCC2
1146 0.04 0.0 B2u 52bCCH + 41rCC2
1145 0.08 0.0 B1u 71bCCH + 26rCC2
1116 0.0 163.0 Ag 89bCCH + 8rCC2
1112 35.75 0.0 B2u 49bCCH + 38rCC2 + 5bCCC1 + 5bCCC2
1105 0.0 4.72 B3g 84bCCH + 14rCC2
1030 70.58 0.0 B1u 68rCC2 + 29bCCH
1007 0.0 59.34 Ag 80rCC2 + 15bCCH
954 1.14 0.0 B1u 58rCC2 + 32bCCH
943 0.0 2.35 B1g 66xCH + 17sCC2 + 16sCC1
938 0.0 0.0 Au 66xCH + 17sCC2 + 17sCC1
932 0.13 0.0 B3u 586xCH + 25sCC2 + 18sCC1
925 0.0 10.62 B2g 59xCH + 24sCC2 + 17sCC1
903 0.0 57.22 Ag 42rCC2 + 26bCCH + 15bCCC2 + 15bCCC1
835 38.97 0.0 B1u 30bCCC1 + 30bCCC2 + 25bCCH + 6rCC2
806 0.0 2.70 B2g 49xCH + 25xCC1 + 11sCC2 + 10xCC1 + 6sCC1
803 1.73 0.0 B2u 26bCCC1 + 26bCCC2 + 25rCC2 + 23bCCH
791 0.0 0.50 B3g 26bCCC1 + 26bCCC2 + 24bCCH + 19rCC2
776 171.78 0.0 B3u 86xCH
730 0.0 0.31 B1g 65xCH + 20sCC2 + 15sCC1
729 0.0 0.0 Au 64xCH + 22sCC2 + 13sCC1
659 0.0 9.33 B2g 51xCH + 25xCC1 + 10sCC2 + 10xCC2
608 34.65 0.0 B3u 34sCC2 + 30xCH + 18xCC1 + 11sCC1 + 7xCC2
572 0.0 0.0 Au 59sCC2 + 20sCC1 + 15xCH + 5sCC
522 0.0 0.03 B1g 54sCC2 + 26xCH + 20sCC1
444 0.0 1.80 B3g 35bCC1 + 35bCC2 + 22rCC2
399 0.0 23.28 Ag 30rCC1 + 27rCC2 + 15bCCC1 + 15bCCC2
249 0.0 1.21 B2g 51sCC2 + 18sCC1 + 17xCC1 + 7xCH + 7xCC2
159 0.0 0.0 B2u 47bCC1 + 47bCC2
121 0.0 0.0 Au 79sCC + 11xCH + 7sCC2
102 1.54 0.0 B3u 41sCC2 + 27xCC1 + 15sC11 + 11xCC2

The abbreviations are: r–stretching, b–bending, x–wagging, s–twisting.

a
Gaussian calculated frequencies.
b
IR intensity in KM/mol.
c
Raman scattering activity in Å4/amu.
d
Main% contributions to the P.E.D. in sym. Coordinates (contributions below 5% are not considered).

shift in TTF derivatives [6]. Similarly, the normal modes having fre-
quencies 82 cm1 and 48 cm1 for TTF and TTF+ respectively in-
volve C@C bond (exocyclic) twisting, i.e., the relative twisting of
two thiole rings. PFV absorbs at 121 cm1 due to this mode, i.e.
substitutions of S atoms in TTF decreases the frequency of C@C
twisting mode and further decrement is attributed by charge
transfer in TTF+. TTF also shows degeneracy at 82 cm1 however,
this normal mode is contributed by CAS twisting which looks like
relative wagging of two thiole rings.
The important and common mode in all three molecules is C@C
(exocyclic) stretching mode. The frequency for this normal mode is
1685 cm1, 1583 cm1 and 1444 cm1 for PFV, TTF and TTF+
respectively. For PFV and TTF+, this normal mode shows pure
C@C (exocyclic) stretching but for TTF, it is equally coupled by
C@C (exocyclic) and C@C (ring) stretching vibrations. The red shift
found in this normal mode from PFV to TTF+ is due to electron-
molecular vibration (EMV) coupling which increases with the cou-
pling constant [21,22]. More recently, a normal mode assignment
has also been presented for TTF without PEDs and the bands at
1616 cm1, 1592 cm1 and 1573 cm1 were assigned for three
CAC stretching modes in which former was assigned for exocyclic
C@C [6]. However, in present calculation the corresponding fre-
quencies are 1626 cm1, 1602 cm1 and 1583 cm1 and PEDs re-
veal that the normal modes having frequencies 1626 cm1 and
1583 cm1 are strongly coupled by both the ring and exocyclic
C@C stretching vibrations and the normal mode of the latter fre-
quency shows comparatively maximum contribution of exocyclic
C@C stretching vibration. The bands at 1666 cm1, 1651 cm1,
1588 cm1, 1581 cm1 and 1537 cm1 were assigned to have
C@C stretching vibrations for C60-TTF dyad, bismethoxycarbonyl-
TTF and bisbromomethyl-TTF [23]. All the bands except at
1537 cm1 show blue shift upon substitutions in TTF.
There are eight CAS bonds in TTF and TTF+ but appreciable con-
tributions of the CAS stretching vibrations can be found in more
320 V. Mukherjee, N.P. Singh / Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 117 (2014) 315–322

Table 4
Normal mode assignment for TTF (C2v point group).

ma IRb Ramanc Scaled Exp.e Species f

PEDs
3248 0.02 561.09 3081 A1 99rCH
3248 0.11 69.48 3081 3082 B2 99rCH
3229 5.35 4.25 3063 3064 B1 100rCH
3229 0.0 233.33 3063 A2 100rCH
1626 0.39 40.27 1541 A1 40rCC1 + 39rCC2 + 7bCCH + 7rCS
1602 38.01 1.60 1521 1528 B2 78rCC2 + 13bCCH + 6rCS
1583 0.50 396.22 1501 1496 A1 55rCC1 + 29rCC2 + 8rCS
1288 0.0 7.16 1254 A2 87bCCH + 10rCS
1286 0.01 0.01 1250 1254 B1 89bCCH + 9rCS
1124 0.32 24.69 1088 A1 94bCCH + 6rCC2
1124 2.56 0.11 1088 1076 B2 93bCCH + 6rCC2
976 0.0 4.14 1003 A2 48rCS + 22bCC2 + 22bCC1
864 0.30 1.18 854 B1 54sCC + 44xCH
864 0.0 0.06 854 A2 54sCC + 44xCH
836 2.67 0.21 835 B1 78rCS + 6bSCC + 5bCSC
806 0.0 22.03 803 A2 50rCS + 33bSCC + 15bCCH
799 53.37 0.14 796 796 B1 58rCS + 26bSCC + 14bCCH
774 24.76 0.19 782 780 B2 64rCS + 19bSCS + 8bCSC
735 0.0 19.62 734 A1 92rCS
732 10.27 0.20 732 734 B2 92rCS
648 133.54 3.57 629 646 A1 100xCH
647 1.92 2.13 629 636 B2 97xCH
624 1.58 0.06 625 B1 57rCS + 18bSCC + 18bCSC + 6bCCH
615 0.0 0.11 615 A2 57rCS + 19bSCC + 16bCSC + 6bCCH
506 2.27 0.08 534 B2 45xCC1 + 45xCC2
474 0.02 14.42 474 A1 68rCS + 17bCSC + 6bSCC
433 14.32 0.02 437 439 B2 32rCS + 29bCSC + 13bSCS + 7bSCC
419 0.0 3.86 413 B1 40sCS + 35xCH + 25sCC
415 0.0 0.26 409 A2 39sCS + 36xCH + 25sCC
308 0.0 8.88 317 A2 51rCS + 21bCC1 + 21bCC2
267 0.66 4.51 276 A1 31xCC1 + 31xCC2 + 15sCS + 10rCS + 6bCSC
237 0.20 10.98 244 A1 19xCC1 + 19xCC1 + 18bSCS + 11sCS + 8rCC1 + 8rCS
111 0.59 0.05 117 B1 49bCC1 + 49bCC1
82 2.86 0.19 84 B2 85sCS + 5xCH
82 0.0 0.03 82 A2 95sCC1
38 3.83 0.57 38 A1 80sCS+7xCH

The abbreviations are: r–stretching, b–bending, x–wagging, s–twisting.

a
Gaussian calculated frequencies.
b
IR intensity in KM/mol.
c
Raman scattering activity in Å4/amu.
d
Scaled frequencies using MOLVIB-7.0.
e
Taken from [6].
f
Main% contributions to the P.E.D. in sym. Coordinates (contributions below 5% are not considered).

than eight normal modes having frequencies below 1000 cm1.
However, the bands at 735 cm1 and 732 cm1 for TTF and at
836 cm1, 752 cm1 and 741 cm1 for TTF+ are contributed by pure
CAS stretching vibrations. Rani and Yadav have also presented nor-
mal modes assignment for TTF but they assigned all the stretching
modes of ring as ring stretching modes instead of the CAS and C@C
stretching modes [6]. Some TTF derivatives show slight blue shift
in one CAS stretching mode, however, most of the CAS normal
modes have frequencies in agreement with the present assignment
[21]. For C60-TTF dyad, one CAS stretching mode was assigned at
1188 cm1 and other below 700 cm1 [23]. Therefore, most of the
CAS stretching modes shift towards lower wavenumber region and
one mode shows blue shift upon substitution(s) in TTF.
Thermodynamics
The vibrational canonical partition function and some impor-
tant thermodynamical parameters are calculated (at T = 300 K)
for PFV, TTF and TTF+ using Eqs. (1)–(5)[17,18] and these are col-
lected in Table 6. The thermodynamics of several TTF salts have
been studied earlier [24,25]. The variation of vibrational partition
function (Z) and specific heat (Cv) with temperature taking same
vibrational frequencies at each time are also studied and the vari-
ations are shown in Fig. 4 and Figs. 5 and 6 (supplementary)
respectively. Since partition function plays the role of a normaliz-
ing constant and it encodes how the probabilities are portioned
among the different microstates based on their individual ener-
gies [26], it can be concluded from Table 6 that there are much
larger possibilities of distributions of TTF molecules in different
vibrational energy levels than PFV and TTF+ at a given tempera-
ture. Since Z counts also the occupied energy states, at 300 K
(room temperature) TTF have relatively much more occupied
states than PFV and TTF+ and lesser vibrational states are accessi-
ble for PFV.
The variation of Z with respect to temperature (Fig. 4) for all
three molecules shows that the variation is linear up to 250 K,
75 K and 100 K and then there is an exponential growth for PFV,
TTF and TTF+ respectively. From Eq. (1), it is clear that Z = 1 at
T = 0 K, which is known as condensation. Clearly, Z = 1 represents
that all the molecules are condensed to the ground state which oc-
curs at absolute zero. However, some real systems show condensa-
tion (Z = 1) above absolute zero which is known as Bose–Einstein
condensation. Normally, B–E condensation occurs at extreme low
temperature which is also true for TTF and TTF+ (Z = 1 at 3 K and
4 K respectively) but interestingly, for PFV, condensation starts at
108 K as above this temperature Z P 2. As temperature decreases,
Z decreases and it is 1.101, 1.043, 1.011, 1.001 and 1 at 50 K, 40 K,
30 K, 20 K and 10 K respectively. Therefore, all the molecules are
 V. Mukherjee, N.P. Singh / Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 117 (2014) 315–322 321

Table 5
Normal mode assignment for TTF+ (D2h point group).

ma IRb Ramanc Species f

PEDs
3254 0.0 667.07 Ag 99rCH
3254 65.44 0.0 B1u 99rCH
3238 35.41 0.0 B2u 100rCH
3238 0.0 205.86 B3g 100rCH
1563 0.0 521.90 Ag 77rCC2 + 14bCCH + 5rCS
1544 106.67 0.0 B1u 77rCC2 + 15bCCH + 5rCS
1444 0.0 280.42 Ag 81rCC1 + 10rCS
1298 0.0 11.53 Ag 87bCCH + 10rCS
1294 6.34 0.0 B1u 90bCCH + 8rCS
1131 0.0 17.81 B3g 92bCCH + 7rCC2
1131 0.09 0.0 B2u 93 bCCH + 7rCC2
1034 0.0 0.04 B3g 54rCS + 19bCC1 + 19bCC2
886 6.56 0.0 B2u 91rCS
882 0.0 0.13 B1g 51sCC + 46xCH
879 0.0 0.0 Au 51sCC + 46xCH
834 0.0 12.35 B3g 55rCS + 30bSCC + 14bCCH
833 24.42 0.0 B2u 55rCS + 30bSCC + 14bCCH
821 38.72 0.0 B1u 66rCS + 18bSCS + 8bCSC
752 0.0 8.64 Ag 93rCS
741 7.42 0.0 B1u 93rCS
701 136.95 0.0 B3u 100xCH
699 0.0 0.46 B2g 99xCH
639 0.86 0.0 B2u 43rCS + 26bSCC + 22bCSC + 8bCCH
630 0.0 12.20 B3g 45rCS + 27bSCC + 19bCSC + 8bCCH
512 0.0 0.25 B2g 42xCC1 + 42xCC2 + 15sCS
507 0.0 91.99 Ag 70rCS + 16bSCS + 6bSCC
471 15.01 0.0 B1u 34bCSC + 33rCS + 15bSCS + 7bSCC
431 0.0 2.38 B1g 60sCS + 22xCH + 19sCC
418 0.0 0.0 Au 60sCS + 21xCH + 19sCC
324 2.18 0.0 B3u 53sCS + 23xCC1 + 23xCC2
302 0.0 3.78 B3g 38rCS + 29bCC1 + 29bCC2
265 0.0 29.25 Ag 26bSCS + 27rCS + 20rCC1 + 20bCSC + 5bCC1 + 5bCC2
145 0.0 0.45 B2g 92sCS + 7xCH
119 0.29 0.0 B2u 49bCC1 + 49bCC2
84 4.48 0.0 B3u 56sCS + 19xCC1 + 19xCC2 + 6xCH
48 0.0 0.0 Au 80sCC1 + 12sCS

The abbreviations are: r–stretching, b–bending, x–wagging, s–twisting.

d
Scaled frequencies using MOLVIB-7.0
e
taken from
a
Gaussian calculated frequencies.
b
IR intensity in KM/mol.
c
Raman intensity in Å4/amu.
f
Main% contributions to the PED. in sym. Coordinates (contributions below 5% are not considered).

Fig. 2. Theoretical IR spectra. Fig. 3. Theoretical Raman spectra.

322 V. Mukherjee, N.P. Singh / Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 117 (2014) 315–322
Table 6
Statistical thermodynamics (at T = 300 K).
S. no. Thermodynamics PFV TTF
1 Partition function (Z) 35.692 999.757
2 Entropy (S) (Cal/Mol-Kelvin) 17.416 28.709
3 Specific heat (Cv) (Cal/Mol-Kelvin) 25.077 30.277
4 Enthalpy (h) (kcal/Mol) 3.114 4.514
5 Helmholtz free energy (Fv) (kcal/mol) 2.134 4.106
6 Gibbs potential (G) 1.720 3.512
7 Thermal energy (kcal/Mol) 93.403 55.779
Fig. 4. Vibrational canonical partition function (Zvib) with temperature.
completely condensed at 10 K. This result may be significant as PFV
exists at low temperature [1].
Fig. 5 (supplementary) shows the variation of specific heat (Cv)
with temperature up to 50 K and Fig. 6 (supplementary) shows
same in the temperature range 50–500 K of all three molecules.
Variation of Cv with temperature is almost linear for all three mol-
ecules and at any temperature the inequality is given by, (Cv)TTF >
(Cv)TTF+ > (Cv)PFV. Below 50 K, Cv profile is appreciably different for
TTF and PFV and it is zero at 0 K and 15 K for TTF and PFV respec-
tively. For TTF+, variation is quite similar to TTF with slightly lesser
value at each point. Above 50 K, Cv profile of PFV approaches to-
wards that of TTF and intersects nearly at 450 K. Then after the var-
iation reverses and inequality is given by, (Cv)PFV > (Cv)TTF > (Cv)TTF+.
The variation of Cv with temperature for PFV is also interesting as
Cv approaches zero at 15 K which is an abnormal phenomena.
Conclusions
A theoretical study of molecular structure, vibrational frequen-
cies and thermodynamics of PFV, TTF and its cation based upon
DFT calculation are reported. PFV has higher symmetry (D2h) but
substitutions of S atoms lowered the symmetry (C2v) of TTF but
however, removal of one p electron from exocyclic C@C bond
brings the symmetry of TTF+(D2h) identical to that of PFV. Despite
of having large numbers of normal modes and higher symmetry,
the absorption profile of both the TTF and TTF+ are very poor com-
pared to that of PFV. Most of the normal modes are IR inactive for
TTF and TTF+. Below 400 cm1, all the modes are Raman inactive
for PFV while only on band at 265 cm1 is strongly appeared in Ra-
man spectrum of TTF+ and few bands are appeared in Raman spec-
trum of TTF.
Thermodynamics of selected molecules show very interesting
result, especially, partition function and specific heat at low tem-
TTF+ perature of PFV show significant result. At low temperature very
384.236 few vibrational states are accessible for PFV while TTF have much
25.838 more accessible states at any temperature than TTF+ and PFV. Con-
29.233 densation of PFV in ground states is commenced at 108 K and com-
4.223 plete condensation occurs at 10 K and Cv approaches to zero at
3.535
2.941
15 K.
56.151
Acknowledgement
The UGC (India) is gratefully acknowledged for the financial
assistance through a research project. Prof. T. Sundius is also grate-
fully acknowledged to provide us his own program MOLVIB.
Appendix A. Supplementary material
Supplementary data associated with this article can be found, in
the online version, at http://dx.doi.org/10.1016/j.saa.2013.07.105.
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