June 11, 2008 15:41 WSPC/178-JTCC 00378

Journal of Theoretical and Computational Chemistry

Vol. 7, No. 3 (2008) 331–346

c World Scientific Publishing Company

MODELING THE GROUND STATE GEOMETRY AND

ESTIMATING THE CHARGE TRANSFER TRANSITION
ENERGY OF THE TOLUENE–ICl MOLECULAR
COMPLEX BY AB INITIO AND DFT METHODS

AMIT S. TIWARY
Department of Chemistry, Netaji Mahavidyalaya
Arambagh, Hooghly 712601, India

PARTHA SARATHI SENGUPTA

Department of Chemistry, Vivekananda Mahavidyalaya
Burdwan 713103, India

ASOK K. MUKHERJEE∗
Department of Chemistry, The University of Burdwan
Burdwan 713104, India

Received 25 August 2007

Accepted 12 December 2007

Out of several plausible isomeric structures of the toluene–ICl charge transfer (CT)
complex, the most feasible one was determined by a detailed ab initio and DFT study
at the HF, B3LYP, and mPW1PW91 levels using 6-31++G(d, p) basis set. Potential
energy surface scans were performed with six possible structures (I and Cl facing the
o-, m-, and p-carbon atoms of toluene separately); the structures at the local minima
of the surfaces were subjected to frequency calculation and the ones having no negative
frequency were accepted as the real structure in the ground state. These structures
were then subjected to full optimization. It was observed that the I–Cl bond, with
its I atom oriented toward the aromatic ring, stands vertically above a C-atom at the
ortho or para positions, being inclined at about 9◦ to the line perpendicular to the
aromatic ring. Complexation increases the I–Cl bond length. After correction for basis
set superposition error through a counterpoise calculation, we conclude from the binding
energy that the preferred structure is the one with ICl above the ortho C atom. The
calculated binding energy closely matches the experimental free energy of complexation.
The electronic CT transition energy (hνCT ) with this structure in the ground state was
calculated in vacuo by the restricted configuration interaction singlets method and in
carbontetrachloride medium by the time dependent density functional theory method
under the polarizable continuum model. The value of hνCT obtained from the ground-
to-excited state transition electric dipole moments of the complex, is close to (somewhat
underestimated) the reported experimental value.

Keywords: Toluene–ICl; charge transfer complex; potential energy surface; TDDFT.

∗ Corresponding author.

331
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332 A. S. Tiwary, P. S. Sengupta & A. K. Mukherjee

1. Introduction
Benzene and substituted benzenes are known to form weak molecular complexes
with small molecules such as HF, HCl, Cl2 , Br2 , I2 , and interhalogens (ICl, IBr).
Complexes of aromatic rings with proton donors such as HF, HCl, etc. are mainly
stabilized by hydrogen bonding interactions while complexes with halogens and
interhalogens are of electron donor–acceptor or charge transfer (CT) type, where
the aromatic ring donates π-electron to the σ ∗ orbital of the halogens/interhalogens.
Although simple in appearance, the structures of such complexes have been the sub-
ject of many experimental1−5 and theoretical6−10 investigations. The structure of
the benzene–ICl (Bz–ICl) complex is of special interest because there are many
orientational possibilities of the ICl moiety with respect to the aromatic ring. Such
possibilities have been investigated by Hegde and coworkers11 theoretically at the
Hatree–Fock (HF) and the second order Møller–Plesset perturbation theory (MP2)
levels and also by using the density functional theory (DFT) with hybrid functionals
within symmetry constraints (B3LYP). Their findings are in conformity with the
qualitative expectations: (i) since the periphery of the aromatic ring is richer in π-
electron density than the central region, the ICl moiety avoids the resting conforma-
tion (i.e. in which the I–Cl bond is parallel to the ring); (ii) the positively charged I
atom of ICl stands above a C=C rather than a C atom of the ring because of greater
π-electron density on such bonds, and (iii) the ICl bond is slightly tilted (with the
Cl atom away from the ring) with respect to the C6 -axis, the tilting being caused
by electrostatic repulsion between the π-electron cloud and the negatively charged
Cl atom. The CT transition energy (hνCT ) of the Bz–ICl complex has recently been
subjected to theoretical estimation12 in both gas phase and CCl4 medium at the
HF, B3LYP, and mPW1PW91 levels and slightly underestimated values have been
obtained. The ICl complex with toluene, a benzene homologue, is expected to have a
different picture regarding its ground state geometry. The methyl group of toluene,
owing to its inductive effect13 has a pronounced influence on the π-electron distri-
bution; instead of the C=C bonds, the ortho and para carbon atoms become richer
in π-electron density. This should make the ground state geometry of the toluene–
ICl (Tol–ICl) complex different from that of the Bz–ICl complex in several aspects.
The question also arises as to which position, ortho or para, is preferred by ICl while
forming the complex. Moreover, the hνCT value of the Tol–ICl complex is expected
to be lower than that of the Bz–ICl complex. The objective of the present work is to
carry out these investigations by ab initio and DFT methods. Such quantum chemi-
cal methods are recently being used14−16 for molecular structural and spectroscopic
analyses. In our earlier calculation12 the time dependent density functional theory
(TDDFT) was used along with the basis set 6-31G(d). However, use of additional
polarization function in the basis set has been shown to be useful in the study of
ICl–amine complexes by Wirth and coworkers.17 Although the DFT method has
been shown to be successful in predicting ground state geometries of molecular CT
complexes which involve long-range interactions, it is known that prediction of CT
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Modeling the Ground State Geometry and Estimating the CT Transition Energy 333

excitation energy by TDDFT method is difficult.18−20 This is because in standard

TDDFT, the exchange correlation functionals correspond to potentials which do
not exhibit the correct 1/r asymptotic behavior21 (where r is the electron–nucleus
distance) but fall off rapidly.22 Application of the straight-forward TDDFT method
always underestimates the CT transition energy, sometimes by an extent22 of 60%
of the exact hνCT .

2. Computational Details
All computations were performed on a Pentium computer with the Gaussian 03
Revision-D.01 suite of programs.23 DFT calculations were done by using the combi-
nation of the Becke’s three-parameter hybrid24 exchange potential with the correla-
tion functional of Lee, Yang and Parr25 (B3LYP). Another level of DFT introduced
by Adamo and Barone26 and abbreviated as mPW1PW91, which utilizes a modi-
fication of the gradient corrected Perdew–Wang exchange functional, PW91, com-
bined with the non-local Perdew–Wang correlation functional27,28 was also tried.
The basis set 6-31++G(d, p) was used for hydrogen, carbon, and chlorine29,30 and
LANL2DZ (which utilizes the effective core potentials suggested by Dunning and
Hay31 and Hay and Wadt32,33 ) was used for iodine. A thorough study of the ground
state geometry of the complex (as also of the individual components, Tol and ICl)
at the HF, B3LYP, and mPW1PW91 levels of theory was carried out in the gas
phase (i.e. in the absence of solvent) and also in CCl4 solution by the polarizable
continuum model (PCM).34,35 Using the ground state optimized geometry at the
respective levels of theory; CT transition energy of the complex in gas phase was
calculated at each of these levels by the restricted configuration interaction singlets
(RCIS) method. Similarly by using the time dependent Hartree–Fock and DFT
methods36,37 under the PCM formalism, the transition energy in CCl4 medium
was calculated at these levels. In the PCM, the solute is placed in the solvent
reaction field cavity created by a series of overlapping spheres initially devised by
Tomasi and coworkers.34,35 and implemented by Barone and coworkers38−41 also
by Tomasi and coworkers.42

3. Results and Discussion

3.1. Search for possible isomeric structures in the ground state of
the complex
From the results of study11 of the Bz–ICl complex, it was guessed that the toluene–
ICl complex might also have a structure with the ICl bond above a C atom or
a C–C bond and slightly tilted away from the ring with respect to the vertical
line perpendicular to the aromatic ring plane. Six possible isomeric structures as
shown in Fig. 1 were selected, three with I atom and three with Cl atom facing the
ring at the o-, m-, and p-positions. These were subjected to potential energy surface
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334 A. S. Tiwary, P. S. Sengupta & A. K. Mukherjee

I
cl O cl
o o

C o O
cl I
I

CH3 CH3 CH3

(i) (ii) (iii)

I cl I
O o O

o O o
cl I cl

CH3 CH3 CH3

(iv) (v) (vi)

Fig. 1. Different possible conformations of the Tol–ICl complex.

(PES) scans by the DFT/B3LYP method. One typical PES is shown in Fig. 2. Each
structure yielded a number of local minima. The geometries at these minima were
then used as initial guess for full optimization followed by frequency calculation to
ascertain whether the optimized geometries were real minima or saddle points. It
was found that structures (ii), (iv), and (vi) gave one imaginary frequency each,
indicating that they were first-order saddle points. Structure (iii) converged to
structure (v) on full optimization. So we are left with structures (i) and (v) only;
on full optimization each of them gave no imaginary frequency. These two structures
were subjected to counterpoise calculation in order to get the complexation energies
after correction for basis set superposition error (BSSE). Results are shown in
Table 1. The BSSE corrected geometrical parameters do not change significantly
from those obtained by full optimization. Both the structures (i) and (v) exhibit
weak binding and have no imaginary frequency. Hence both are potential candidates
for the geometry of the complex in the ground state. Experimental enthalpy of
formation of the Tol–ICl complex is not available. However, the free energy of
formation is available2 which, in magnitude, is close to the calculated complexation
energies (∼10−1 kcal/mol).
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Modeling the Ground State Geometry and Estimating the CT Transition Energy 335

Fig. 2. Potential energy surface for DFT/B3LYP-optimized geometry of the ortho isomer of the
Tol–ICl complex in the ground state in gas phase. SC1 means C7 -I distance in Å and SC2 means
C7 –I–Cl angle in degree.

Table 1. Complexation energies (∆Eb ), BSSE, counterpoise-

corrected interaction energy (∆EbCP ) in kcal/mol, and number
of imaginary frequencies (ni ) for the Tol–ICl complex.

Parameter
Structure Method ∆Eb BSSE ∆EbCP ni
(i) HF 1.778 0.406 2.184 0
B3LYP 0.650 0.739 1.389 0
mPW1PW91 3.138 0.762 3.945 0
(v) HF 1.765 0.367 2.135 0
B3LYP 0.590 0.680 1.270 0
mPW1PW91 2.943 0.690 3.633 0

3.2. Results of ground state optimization of structures (i) and (v)

in gas phase and in CCl4 medium
Using the optimized geometries of the structures (i) and (v) as the initial guess in
gas phase full optimizations of their structures in CCl4 medium were performed
by the PCM formalism at HF, B3LYP, and mPW1PW91 levels. Results are shown
in Tables 2 and 3. In a separate calculation the optimized bond lengths (in Å) of
free ICl in gas phase and in CCl4 medium were found to be, respectively, 2.378
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336 A. S. Tiwary, P. S. Sengupta & A. K. Mukherjee

Table 2. Some important parameters obtained from the optimization of the ortho isomer
of the Tol–ICl complex in its ground state.

HF B3LYP mPW1PW91
Parameters Gas CCl4 Gas CCl4 Gas CCl4
r(I–Cl)/Å 2.386 2.391 2.474 2.514 2.450 2.477
R(C7 –I)/Å 3.697 3.595 3.108 2.964 2.995 2.892
a(C7 –I–Cl)/deg 168.698 170.310 171.952 172.089 171.817 172.763
µx (Debye) 2.663 3.030 −4.364 −6.435 −4.531 −6.011
µy (Debye) 0.163 0.134 0.138 −0.075 0.160 0.084
µz (Debye) 0.295 0.415 −0.530 −0.834 −0.565 −0.797
QTol (a.u.) 0.010 0.014 0.089 0.131 0.094 0.135
QICl (a.u.) −0.010 −0.014 −0.090 −0.131 −0.094 −0.135
QI (a.u.) 0.297 0.311 0.203 0.203 0.208 0.210
QI (a.u.) 0.278 0.301 0.235 0.253 0.237 0.254

QTol = total electronic charge in the toluene moiety of the complex; QICl = total elec-
tronic charge in the ICl moiety; QI = electronic charge on the I atom in the complex;
QI = electronic charge on the I atom of free ICl. The charges have been calculated by
natural population analysis with the respective optimized geometries.

Table 3. Some important parameters obtained from the optimization of the para isomer
of the Tol–ICl complex in its ground state.

HF B3LYP mPW1PW91
Parameters Gas CCl4 Gas CCl4 Gas CCl4
r(I–Cl)/Å 2.399 2.391 2.486 2.503 2.450 2.477
R(C5 –I)/Å 3.537 3.609 3.056 2.995 3.004 2.903
a(C5 –I–Cl)/deg 172.491 173.795 173.290 174.444 173.827 174.612
µx (Debye) 3.208 3.151 5.250 6.222 4.856 6.327
µy (Debye) −0.498 −0.451 −0.866 −1.093 −0.720 −1.180
µz (Debye) 0.000 0.001 −0.016 −0.009 0.005 0.010
QTol (a.u.) 0.010 0.014 0.010 0.137 0.095 0.141
QICl (a.u.) −0.010 −0.014 −0.010 −0.137 −0.095 −0.141
QI (a.u.) 0.297 0.312 0.198 0.199 0.206 0.206
QI (a.u.) 0.278 0.301 0.235 0.253 0.237 0.254

QTol = total electronic charge in the Toluene moiety of the complex; QICl = total elec-
tronic charge in the ICl moiety; QI = electronic charge on the I atom in the complex;
QI = electronic charge on the I atom of free ICl. The charges have been calculated by
natural population analysis with the respective optimized geometries.

and 2.382 in HF, 2.430 and 2.433 in B3LYP, and 2.402 and 2.405 in mPW1PW91.
Electronic charge on the I atom of ICl in gas phase and in CCl4 medium were,
respectively, 0.274 and 0.301 a.u. in HF, 0.193 and 0.214 a.u. in B3LYP, and 0.197
and 0.217 a.u. in mPW1PW91. Tables 2 and 3 reveal that on complexation with
toluene (Tol) these parameters undergo appreciable change. The iodine end of the
ICl moiety in the complex is directed toward the aromatic ring of Tol in all the
levels of theory. This is expected since the I atom is the best co-ordination site for
an electron donor, as Cl is substantially more electronegative than iodine.3 Also, in
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Modeling the Ground State Geometry and Estimating the CT Transition Energy 337

all the levels of calculation, the I–Cl bond length increases on complexation, and is
situated above the ortho C atom in structure (i) and para carbon in structure (v) of
the aromatic ring; with respect to an axis perpendicular to the ring, the I–Cl bond
has a tilt of about 9◦ away from the ring (in both B3LYP and mPW1PW91 levels).
The tilting is less by about 2◦ in the case of para isomer. This may be attributed
to the fact that the classical inductive effect of the methyl group is more prominent
at the o-position than at the p-position. Moreover, data in Tables 2 and 3 also reveal
that the I–Cl bond length increases by about 0.03 Å on going from the gas phase
to solution, calculated at all the three levels of theory. The optimized geometries
of the structures (i) and (v) with axial orientation are shown in Fig. 3. The major
component of the dipole moment (µ) of the complex is along the x-axis, directed
from the aromatic ring to the ICl moiety (Fig. 3, Tables 2 and 3); according to
Gaussian convention,  µ is directed from the negative to the positive end of the
dipole. In all the levels of theory and in both gas phase and CCl4 medium, the
major component of the dipole moment of the complex is from the aromatic ring
toward the ICl moiety. Further, natural population analysis reveals that the charge
on the I atom (QI ) of the complex in its ground state is less positive than that
(QI ) in the isolated ICl molecule at B3LYP and mPW1PW91 levels. (However,
this trend is not observed at HF level, the reason for which may be the lack of
consideration of electron correlation effect in the HF method.) All these indicate
that even in the ground state some electronic charge has been transferred from
Tol to ICl. Also, the sum of the charges on the Tol moiety and that on the ICl
moiety of the complex (Tables 2 and 3) indicate that with respect to Tol the ICl
moiety is negatively charged, and about 1.0–1.4% of the charge of an electron has

(a) (b)

Fig. 3. B3LYP-optimized geometries of (a) the ortho isomer and (b) the para isomer of the Tol–ICl
complex in the ground state in gas phase.
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338 A. S. Tiwary, P. S. Sengupta & A. K. Mukherjee

been transferred from Tol to ICl in the ground state of the complex. The extent of
charge transfer is slightly greater in CCl4 medium than in gas phase and also for
the para isomer than for the ortho isomer.

3.3. Calculation of charge transfer transition energy

by RCIS in gas phase
For identification of CT transition energy, structures (i) and (v) of the Tol–ICl com-
plex and of the individual components (toluene and ICl) were separately subjected
to configuration interaction calculation (RCIS) at the three levels of theory (using
30 states in CI calculation). From the results in Table 4 it is found that the first
two transitions of ICl are components of a doubly degenerate transition polarized
along the x- and y-directions. This is expected from the C∞v symmetry of ICl. The
third and fourth transitions are similarly polarized and doubly degenerate. The
other calculated transitions of ICl are of higher energy (greater than 6 eV) and are
not relevant to the present work. Again, the RCIS-calculated transition energies
of free toluene in gas phase were all found to be greater than 6 eV, far from the
experimental CT transition energy of the complex; the first two transition energies
of toluene, which were close to (but still greater than) 6 eV were of poor oscillator
strength (≈ 10−3 ) and the others were above 8 eV. Hence the electronic transi-
tions of free toluene were disregarded in locating the CT transition of the complex.
The first six transition energies for each of the structures (i) and (v) of the Tol–
ICl complex along with oscillator strengths and ground-to-excited state transition
electric dipole moments, computed by RCIS method at the three levels of theory
(using thirty states in CI calculation) are shown in Tables 5 and 6. By comparing
the results in Tables 4 and 5, it is found that the first four transition energies of
the complex in structure (i) (at each level of calculation) correspond to transitions
among the perturbed MOs of ICl and the fifth one is a new transition (the sixth
one at the HF level). Evidently, the degeneracy of the ICl transitions is lifted by
complexation which reduces its symmetry from C∞v to C1 . The new transition
may be assigned to a charge transfer from toluene to ICl by inspecting the carte-
sian components of the ground-to-excited state transition electric dipole moment,
µGE . A similar comparison of Tables 4 and 6 and an inspection of the cartesian

components of the ground-to-excited state transition electric dipole moment also
reveals a transfer of charge from Tol to ICl at the para orientation (str.v). For
a comparison with the Bz–ICl complex, ground state optimization and RCIS cal-
culation were also performed on the latter using 6-31++G(d, p) basis set at HF,
B3LYP, and mPW1PW91 levels. The RCIS calculated CT transition energies are
summarized in Table 7. Toluene is expected to be a better π-donor than benzene
because of the inductive effect of methyl group. So the Tol–ICl complex is expected
to have a lower CT transition energy (hνCT ). The Tol–ICl complex with both the
possible orientations (structures (i) and (v)) are found to obey the expected trend
(Table 7); however the para isomer obeys the trend more prominently.
Table 4. Excitation energies of ICl: Results of configuration interaction calculation in gas phase and TDDFT calculation
in CCl4 by PCM.

Transition energy (eV) Oscillator strength 

µGE (axis of polarization) (a.u.)
June 11, 2008 15:41 WSPC/178-JTCC

RCIS gas TD gas TD RCIS gas TD gas TD RCIS in TD gas TD

Method phase phase CCl4 phase phase CCl4 gas phase phase CCl4
HF 2.973 2.897 2.868 0.0003 0.0001 0.0001 0.0600 (x) 0.0290 (x) 0.0337 (y)
2.973 2.897 2.868 0.0003 0.0001 0.0001 0.0600 (y) 0.0290 (y) 0.0337 (x)
00378

5.495 5.453 5.524 0.0023 0.0023 0.0027 0.1294 (y) 0.1311 (y) 0.1406 (y)
5.495 5.453 5.524 0.0023 0.0023 0.0027 0.1294 (x) 0.1311 (x) 0.1406 (x)
B3LYP 2.751 2.222 2.217 0.0002 0.0000 0.0000 0.0535 (x) −0.0124 (y) −0.009 (y)
2.751 2.222 2.217 0.0002 0.0000 0.0000 0.0535 (y) −0.0124 (x) −0.009 (x)
5.076 4.108 4.153 0.0018 0.0009 0.0012 0.1206 (y) 0.0971 (y) 0.1063 (y)
5.076 4.108 4.153 0.0018 0.0009 0.0012 0.1206 (x) 0.0971 (x) 0.1063 (x)
mPW1-PW91 2.870 2.377 2.372 0.0002 0.000 0.0000 0.0570 (x) −0.0032 (y) 0.0005 (x)
2.870 2.377 2.372 0.0002 0.000 0.0000 0.0570 (y) 0.0032 (x) 0.0005 (y)
5.301 4.407 4.453 0.0020 0.0011 0.0013 0.1252 (y) 0.0999 (x) 0.1088 (x)
5.301 4.407 4.453 0.0020 0.0011 0.0013 0.1252 (x) 0.0999 (y) 0.1088 (y)
Modeling the Ground State Geometry and Estimating the CT Transition Energy
339
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340 A. S. Tiwary, P. S. Sengupta & A. K. Mukherjee

Table 5. Results of configuration interaction calculation on ortho isomer

of the Tol–ICl complex in gas phase.

µ
 GE (a.u.)
Transition Oscillator
Method energy (eV) strength x y z
HF 3.059 0.0005 −0.0184 0.0802 0.0168
3.064 0.0006 −0.0435 −0.0131 0.0760
5.406 0.0191 −0.3767 −0.0320 0.0390
5.577 0.0602 −0.6470 0.0579 0.1359
5.630 0.0112 −0.2323 −0.1648 −0.0072
5.676∗ 0.1196 −0.9144 0.1399 −0.0654
B3LYP 2.943 0.0004 −0.0387 −0.0605 0.0034
2.970 0.0005 0.0412 0.0079 −0.0712
5.062 0.0404 0.5686 −0.0428 −0.0282
5.148 0.0165 −0.3365 −0.0484 0.1238
5.273∗ 0.3262 −1.5832 0.1367 −0.0059
5.400 0.3090 −1.4614 −0.4197 −0.1549
mPW1PW91 3.120 0.0005 0.0540 0.0561 0.0011
3.156 0.0008 −0.0692 −0.0185 0.0755
5.252 0.1011 −0.8768 0.1169 0.0538
5.394 0.1111 0.0965 0.1014 −0.0919
5.477∗ 0.3777 1.6755 −0.0345 0.0822
5.577 0.1454 0.9083 0.4517 0.1872

The assigned CT transition energies are marked with asterisks.

Table 6. Results of configuration interaction calculation on para isomer of

the Tol–ICl complex in gas phase.

µ
 GE (a.u.)
Transition Oscillator
Method energy (eV) strength x y z
HF 3.051 0.0005 0.0004 0.0014 0.0836
3.061 0.0006 0.0604 0.0698 −0.0012
5.443∗ 0.1921 1.1996 −0.0386 −0.0008
5.570 0.0022 −0.0029 0.0029 0.1282
5.618 0.0140 −0.2780 0.1565 −0.0015
5.754 0.0011 −0.0017 0.0023 0.0634
B3LYP 2.917 0.0003 −0.0031 0.0001 −0.0004
2.946 0.0011 −0.1102 −0.0596 0.0662
5.054 0.0012 −0.0726 0.0049 0.0053
5.071 0.1629 1.1451 −0.0023 0.0044
5.181∗ 0.6130 2.1769 −0.3020 0.2993
5.517 0.0121 −0.0163 −0.0066 −0.0619
mPW1PW91 3.081 0.0003 −0.0012 −0.0010 −0.0619
3.123 0.0017 0.1348 0.0617 −0.0001
5.261∗ 0.5699 −2.0971 0.1532 −0.0036
5.276 0.0001 −0.0099 −0.0022 −0.0245
5.377 0.2475 1.3434 −0.2716 0.0032
5.667 0.0142 0.0089 0.0078 −0.3198

The assigned CT transition energies are marked with asterisks.

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Modeling the Ground State Geometry and Estimating the CT Transition Energy 341

Table 7. Comparison of CT transition energies of Tol–ICl complex

in structures (i) and (v) with that of the Bz–ICl complex by RCIS
in gas phase.

CT transition energy/ev
Complex HF B3LYP mPW1PW91
Bz–ICl 5.574 5.741 5.567
Tol–ICl (structure (i)) 5.676 5.273 5.477
Tol–ICl (structure (v)) 5.443 5.181 5.380

3.4. Calculation of CT transition energy in gas phase and in CCl4

medium (under the PCM formalism) by TDDFT method
The Tol–ICl complex in the two isomeric forms (i) and (v), free ICl and free toluene
were subjected to TDDFT calculation for the excited states in gas phase and also in
CCl4 medium (dielectric constant 2.228) under the PCM formalism. The optimized
ground state geometries in the respective media were used for such calculation.
The transition energies of the complex thus found are shown in Tables 8 and 9
and those for free ICl in Table 4. A calculated UV–VIS spectrum (drawn by Gauss
View 4.1) is shown in Fig. 4, where the longest wavelength band is clearly the CT
absorption band. All transition energies of free toluene computed by the TDDFT
method were found in the deep UV region (greater than 6 eV) and so were dis-
carded for reasons discussed in the previous section. A comparison of Tables 4
and 8 reveals that the complex has an electronic transition different from those of
the individual components and the ground-to-excited state transition electric dipole
moment of the complex has a dominant component directed from Tol to ICl. The
state corresponding to this CT transition in the ortho complex (structure (i)) is

Fig. 4. UV–VIS spectra of the para isomer of Tol–ICl complex in CCl4 medium calculated by
TDDFT/B3LYP/6-31++G(d, p). The CT absorption band appears at 390 nm.
Table 8. Results of time dependent HF and DFT calculation on ortho isomer of the Tol–ICl complex in gas phase and in CCl4 medium. 342

Transition energy (eV) Oscillator strength µ

 GE (a.u.) in gas phase µ
 GE (a.u.) in CCl4
Method Gas CCl4 Gas CCl4 x y z x y z
HF 2.982 2.957 0.0003 0.0003 −0.019 0.055 0.010 −0.014 0.059 0.001
2.988 2.965 0.0003 0.0004 −0.035 −0.006 0.053 −0.047 0.005 0.058
5.377 5.200 0.0193 0.0602 −0.377 −0.057 0.040 −0.674 −0.108 0.044
June 11, 2008 15:41 WSPC/178-JTCC

5.356 5.384∗ 0.0503 0.2383 −0.594 0.049 0.125 −1.330 0.197 −0.002
5.588 5.615 0.0123 0.0083 −0.240 −0.181 −0.010 0.192 0.040 0.149
5.634∗ 5.624 0.1007 0.0072 −0.839 0.133 −0.092 0.044 −0.214 0.069
B3LYP 2.376 2.336 0.0008 0.0021 −0.107 0.047 0.007 −0.170 0.086 0.018
2.436 2.442 0.0005 0.0012 0.094 0.013 0.140 0.020
00378

−0.009 −0.011
2.912 2.848 0.0074 0.0137 0.273 −0.168 −0.021 −0.382 0.222 0.035.
3.501∗ 3.397∗ 0.3481 0.5397 −2.005 −0.169 −0.062 2.535 0.229 0.084
A. S. Tiwary, P. S. Sengupta & A. K. Mukherjee

4.130 4.096 0.0030 0.0036 −0.111 0.046 −0.122 −0.127 0.061 −0.127
4.144 4.110 0.0025 0.0031 0.003 −0.147 −0.050 −0.006 0.164 −0.063
mPW1PW91 2.565 2.541 0.0007 0.0018 −0.103 0.035 0.006 −0.154 0.074 0.017
2.630 2.645 0.0009 0.0019 0.112 0.016 −0.018 0.167 0.024 −0.021
3.339 3.256 0.0122 0.0222 0.329 −0.202 −0.032 −0.453 0.265 0.048
3.923∗ 3.783∗ 0.3990 0.6162 2.029 0.176 0.057 2.565 0.250 0.087
4.436 4.406 0.0057 0.0064 −0.185 0.041 −0.127 −0.196 0.054 −0.135
4.456 4.426 0.0032 0.0043 −0.008 −0.163 −0.054 −0.018 −0.186 −0.067

The assigned CT transition energies are marked with asterisks.

Table 9. Results of time dependent HF and DFT calculation on para isomer of the Tol–ICl complex in gas phase and in CCl4 medium.

Transition energy (eV) Oscillator strength µ

 GE (a.u.) in gas phase µ
 GE (a.u.) in CCl4
Method Gas CCl4 Gas CCl4 x y z x y z
HF 2.975 2.951 0.0003 0.0003 0.001 0.001 0.059 −0.001 −0.002 −0.063
2.985 2.964 0.0003 0.0005 0.049 0.047 −0.001 −0.063 −0.049 0.001
June 11, 2008 15:41 WSPC/178-JTCC

5.411∗ 5.180∗ 0.1808 0.3075 1.168 −0.021 −0.000 −1.552 0.124 0.000
5.529 5.461 0.0023 0.0001 −0.003 0.003 0.129 −0.008 −0.003 0.016
5.576 5.614 0.0146 0.0046 −0.289 0.153 −0.002 0.089 −0.160 0.002
5.710 5.648 0.0008 0.0049 −0.001 0.005 −0.074 −0.002 −0.000 −0.189
00378

B3LYP 2.355 2.335 0.0000 0.0001 −0.005 0.001 −0.014 0.005 −0.001 −0.189
2.413 2.420 0.0020 0.0035 0.185 −0.008 0.000 −0.241 0.012 0.041
3.203 3.056 0.0017 0.0029 0.047 −0.007 0.139 0.042 −0.006 0.000
3.362∗ 3.177∗ 0.3804 0.5495 2.137 −0.223 −0.004 2.640 −0.301 0.191
4.072 4.073 0.0029 0.0027 −0.100 0.138 0.001 −0.075 0.145 −0.003
4.092 4.093 0.0026 0.0031 0.000 0.001 −0.162 0.000 0.000 −0.000
mPW1PW91 2.535 2.527 0.0000 0.0001 0.004 0.000 −0.011 0.006 −0.002 −0.032
2.592 2.620 0.0016 0.0041 0.161 0.006 −0.000 −0.253 0.002 0.000
3.670 3.471 0.0027 0.0045 0.020 −0.003 −0.171 0.049 −0.070 −0.225
3.826∗ 3.539∗ 0.4767 0.6192 2.244 −0.223 0.004 2.655 −0.306 0.007
4.297 4.388 0.0072 0.0041 −0.212 0.153 −0.003 −0.119 0.155 −0.003
4.345 4.418 0.0041 0.0003 0.001 0.003 0.196 0.001 0.003 0.196

The assigned CT transition energies are marked with asterisks.

Modeling the Ground State Geometry and Estimating the CT Transition Energy
343
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344 A. S. Tiwary, P. S. Sengupta & A. K. Mukherjee

Table 10. Comparison of calculated CT transition energies of Tol–ICl com-

plex in structures (i) and (v) with that of the Bz–ICl complex by TDDFT
in CCl4 medium and also with the experimental value.

CT transition energy/ev
Experimental
Complex HF B3LYP mPW1PW91 hνCT in CCl4
Bz–ICl 5.434 3.328 3.706 4.400 eV
Tol–ICl (structure (i)) 5.384 3.397 3.783 4.309 eV
Tol–ICl (structure (v)) 5.180 3.177 3.539

the fourth excited state (Table 8) in all the levels of theory. The hνCT value of
the para complex (structure (v)) was found in a similar way by comparing Tables 4
and 9. The TDDFT results for hνCT of both the isomers in CCl4 medium are shown
in Table 10 for a comparison with the Bz–ICl complex and with the experimen-
tal value of hνCT (= 4.309 eV in CCl4 medium) collected from the literature.2 It
is found that the para isomer has a lower hνCT (calculated) than the ortho iso-
mer in all the levels and, as found in RCIS calculation, the para isomer follows the
expected trend (hνCT (Bz–ICl) > hνCT (Tol–ICl)) better than the ortho isomer. The
transition energy substantially decreases in going from the gas phase to solution.
From Table 10 it is observed that the HF method highly overestimates hνCT while
the B3LYP and mPW1PW91 values are somewhat close to the experimental one;
the former underestimates hνCT by 0.912 and 1.132 eV for the ortho isomer and
the para isomer, respectively while the latter underestimates it only by 0.526 eV for
the ortho and 0.770 eV for the para isomer. For reasons discussed in Refs. 18–22 and
mentioned in the Sec. 1, such underestimations cannot be got rid of by the present
day TDDFT.

4. Conclusion
So far there is no experimental evidence for the existence of different isomeric
species of the Tol–ICl complex. However, theoretically we arrive at two stable iso-
meric forms. The expected trend in calculated CT transition energy by RCIS or
TDDFT method is better followed by the para isomer, but owing to the known
uncertainties18−21 of these methods to predict hνCT values, we rely on the stabi-
lization energies of the two isomeric complexes. The DFT-calculated complexation
energy of the ortho isomer is higher in magnitude than that of the para isomer.
In order to substantiate this point further, we carried out single point energy cal-
culations by the MP2 method43 using the DFT-optimized geometries in the gas
phase. It was found that the o-isomer is stabilized to the extent of 0.816 kcal/mol,
whereas the p-isomer is destabilized by 0.0003 kcal/mol with respect to the sep-
arated toluene and ICl moieties. For this reason we conclude that the o-isomer
is the preferred structure of the Tol–ICl complex, and this is in compliance with
the fact that inductive effect of methyl group falls off with distance. Steric effect
of the methyl group could have directed ICl to the para position. But there are
June 11, 2008 15:41 WSPC/178-JTCC 00378

Modeling the Ground State Geometry and Estimating the CT Transition Energy 345

experimental evidences that the inductive effect dominates over the steric effect of
the methyl group in toluene. For example, chlorination of toluene yields isomeric
chlorotoluenes in an ortho:para ratio of 62:38, which shows that the ortho isomer
is favorable over the para isomer (p. 511 of Ref. 13). The order of calculated com-
plexation energies found in the present work is in accord with such experimental
evidences.

Acknowledgments
The authors thank the reviewers for their valuable suggestions. Financial assistance
by the UGC, New Delhi, extended through the DSA project in chemistry, Burdwan
University is also thankfully acknowledged.

References
1. Mulliken RS, J Am Chem Soc 72:600, 1950.
2. Keefer RM, Andrews LJ, J Am Chem Soc 74:4500, 1952.
3. Hassel O, Proc Chem Soc 250:957.
4. Ferguson EE, J Chem Phys 25:577, 1956; Spectrochim Acta 10:123, 1957; J Chem
Phys 26:1357, 1957.
5. Ananthavel SP, Hegde MS, J Chem Phys 105:4395, 1996.
6. Mulliken RS, J Am Chem Soc 74:811, 1952.
7. Mulliken RS, J Chem Phys 23:397, 1955.
8. Hanna MW, J Am Chem Soc 90:285, 1968.
9. Cook EG Jr, Schug JC, J Chem Phys 53:723, 1970.
10. Jano I, Theor Chim Acta 66:341, 1985.
11. Chettu Ammal SS, Ananthavel SP, Venuvanalingam P, Hegde MS, J Phys Chem A
102:532, 1998.
12. Tiwary AS, Sengupta PS, Mukherjee AK, Chem Phys Lett 433:427, 2007.
13. March J, Advanced Organic Chemistry, 4th ed., John Wiley & Sons, p. 17.
14. Chesnut DB, Chem Phys 305:237, 2004.
15. Chis V, Pirnau A, Jurca T, Vasilescu M, Simon S, Cozar O, David L, Chem Phys
316:153, 2005.
16. Wang Z, Liu D, Su K, Fan H, Li Y, Wen Z, Chem Phys 331:309, 2007.
17. Hass J, Bissmire S, Wirth T, J Eur Chem 11:5777, 2005.
18. Gritsenko O, Baerends EJ, J Chem Phys 121:655, 2004.
19. Tozer DJ, J Chem Phys 119:12697, 2003.
20. Dreuw A, Head-Gordon M, J Am Chem Soc 126:4007, 2004.
21. Casida ME, Jamorski C, Casida KC, Salahub DR, J Chem Phys 108:4439, 1998.
22. Tozer DJ, Handy NC, J Chem Phys 109:10180, 1998.
23. Frisch MJ et al., GAUSSIAN 03, Revision D. 01, Gaussian, Inc., Wallingford CT,
2004.
24. Becke AD, J Chem Phys 98:5648, 1993.
25. Lee C, Yang W, Parr RG, Phys Rev B 37:785, 1988.
26. Adamo C, Barone V, J Chem Phys 108:664, 1998.
27. Perdew JP, in Ziesche P, Eschrig H (eds.), Electronic Structure of Solids, Akademie
Verlag, Berlin, 1991, p. 11.
28. Perdew JP, Wang Y, Phys Rev B 45:13244, 1992.
29. Clark T, Chandrasekhar J, Spitznagel GW, Schleyer PvR, J Com Chem 4:294, 1983.
June 11, 2008 15:41 WSPC/178-JTCC 00378

346 A. S. Tiwary, P. S. Sengupta & A. K. Mukherjee

30. Frish MJ, Pople JA, Binkley JS, J Chem Phys 80:3265, 1984.
31. Dunning TH Jr., Hay PJ, in Schaefer HF III (ed.), Modern Theoretical Chemistry,
Vol. 3, Plenum Press, NewYork, pp. 1–28, 1976.
32. Hay PJ, Wadt WR, J Chem Phys 82:270, 1985; ibid 299.
33. Wadt WR, Hay PJ, J Chem Phys 82:284, 1985.
34. Cossi M, Barone V, Cammi R, Tomasi J, J Chem Phys Lett 255:327, 1996.
35. Cancès MT, Mennucci B, Tomasi J, J Chem Phys 107:3032, 1997.
36. Stratmann RE, Scuseria GE, Frisch MJ, J Chem Phys 109:8218, 1998.
37. Bauernschmitt R, Ahlrichs R, Chem Phys Lett 256:454, 1996.
38. Cossi M, Barone V, Robb MA, J Chem Phys 111:5295, 1999.
39. Cossi M, Barone V, J Chem Phys 112:2427, 2000.
40. Cossi M, Barone V, J Chem Phys 115:4708, 2001.
41. Cossi M, Scalmani G, Rega N, Barone V, J Chem Phys 117:43, 2002.
42. Cammi R, Mennucci B, Tomasi J, J Phys Chem A 104:5631, 2000.
43. Head-Gordon M, Pople JA, Frisch MJ, Chem Phys Lett 153:503, 1998.