Journal of i%folecularStructure.

50 (1978) 155-160
OElsevier Scientific Publishing Company, Amsterdam - Printed in The Netherlands

LOCALIZED MOLECULAR ORBITALS FOR POLYATOMIC MOLECULES

Part VII. The tetracyanoquinodimethan molecule and its anions

D. A. DIXON*, H. SIMMONS and W. N. LIPSCOMB

Gibbs Chemical Laboratory, Haruard University, Cambridge, Mass. 02138 (U.S.A.)
(Received 21 April 1978)

ABSTRACT

Wavefunctions for TCNQ, TCNQ-’ and TCNQmZ have been obtained in the approxi-
mation of partial retention of diatomic differential overlap (PRDDO). For TCNQ and
TCNQ- the geometries were partially optimized. Localized molecular orbit& (LMO’s)
have been obtained for TCNQ and TCNQ-’ using the Boys’ criterion. For TCNQ these
I&IO’s give the usual description of the bonding in the molecule. However, for TCNQ-*
the LMO’s show an unexpected bonding pattern of a benzenoid ring and lone pairs on
C7 and C8. The rotation barrier about the Cl-C7 bond in TCNQ-’ is calculated to be
12 kcal mole-‘, the maximum value for the conjugative effect in this bond.

INTRODUCTION

The electronic structure of tetracyanoquinodimethan (TCNQ) is of

significant interest due to its participation in charge transfer salts which
may exist in the metallic state [ 11. One of the best examples of such organic
metals is in the complex of TCNQ with tetrathiofulvene (TTF) where TTF
is the electron donor and TCNQ is the electron acceptor. A number of SCF
calculations at various levels of approximation have been carried out for
TCNQ and its mono-anion and dianion. These calculations include PPP 121,
CNDO [ 31, MIND0 [ 41, X-alpha [ 51 and ab initio results in which various
basis sets were used [6,7]. Cavallone and Clementi [8] have obtained the
wave function of the TTF-TCNQ complex using a minimum basis set.
While the ab initio calculations which employ a double zeta basis set are
the highest quality results so far, the computing times that are involved are
enormous [6] (3.5 h for the integrals alone on an IBM 370/165). Thus other
methods must be employed in order to obtain some properties, for example,
some degree of geometry optimization. The approximate method most like
ab initio methods is PRDDO [9], which has been used to study a wide range
of large molecules [lo, 111. In order to examine the relationship between
bonding in molecules and their chemical properties, it is often useful to
obtain localized molecular orbitals [lo, 111 (LMO’s) as well as the usual

*Junior Fellow, Society of Fellows, Harvard University.

156

canonical molecular orbital (CMO’s). The LMO’s are determined rigorously

by applying a unitary transformation to the CMO’s [ 121; the resulting
orbitals usually correspond to simple concepts of the chemical bond.
We have obtained wavef~ctions for the neutral moleclrle of TCNQ, its
monoanion and its dianion using the PRDDO method. Partial geometry optimi-
zation was done for the closed shell neutral and dianion species, and LMO’s
have been obtained for these two species using the Boys’ criterion [ 12, 131.

CALCULATIONS AND GEOMETRIES

The calculations were done using the PRDDO method [9] which employs
a minimum basis set of Slater orbitals. Standard Slater exponents for C
(5.7 for Is, 1.65 for 2s and 2~) and N (6.7 for Is, 1.95 for 2s and 2~) were
used while an exponent of 1.2 was used for H 1s. The initial geometry for
TCNQ was taken from a crystal structure 1141 and averaged to the L)2h
symmetry of the molecule. All C-H distances were set at 1.08 A, which is
appropriate for these molecules [lo]. Although the ---C(CN)* and C-H
groups were not optimized, the three unique C-C distances, l-3,1-7 and
34 were. These optimized neutral bond lengths (Table 1) compare well
with the average values found in the crystal structure [ 14 J .
The initial geometry of the dianion was chosen on the basis of a localization
of the dianion species starting from the initial geometry of the neutral
molecule (see below). The geometry was assumed to be that of a benzene
ring and an sp*- sp2 Cl-C, single bond (Table 1). The --C(CN), moieties
were assumed to be unchanged from their geometries in the neutral molecule.
~p~izat~on of the symmetry unique 1-3, l-7 and 3-4 bonds then gave
the results in Table 2. The major change upon optimization was a lengthening
of the 1-3 bond from 1.39 to 1.43 A. Except for the l-7 bond in TCNQm2
the bond lengths obtained here (PRDDO) are somewhat shorter than those
obtained here by the MIND0 approximation/3 (Table 1).

TABLE 1

Geometry comparison

Bonda R(TCNQ)b R(TCNQ)= R(TCNQ)d R(TCNQ-‘)e R(TCNQ-‘)b R(TCNQ-Z)C

PRDDO MIND0 EXP EXP PRDDO MIND0

Cl-C3 1.487 1.492 1.448 1.425 1.421 1.434

Cl-C? 1.374 1.383 1.374 1.408 1.487 1.478
C3-C4 1.346 1.354 1.346 1.362 1.390 1.403
C-3-H 1.08 1.107 - - 1.08 1.112
c7--c9 1.44 1.460 1.44 1.415 1.44 1.425
CS-N 1.14 1.161 1.14 1.154 1.14 1.176

=A11distancesin A. bGeometryoptimization,thiswork.The C3-H,C7-C9 andC9-N

values were not geometry optimized. CGeometry optimization, ref. 4. dExperimentaI
geometry, ref. 14. eAverageof experimentalvalues in ref. 15 as given by ref. 4.
 157

TABLE 2

Atomic charges and inner shell eigenvalues

Atom TCNQ TCNQ-’ TCNQ-’

Eigenvalue= Chargeb Eigenvalue= Chargeb Eigenvalue= Chargeb

N -15.651 -0.10 -15.493 -0.10 -15.257 -0.31

Cl -11.432 0.10 -11.227 0.07 -11.04 1 0.04
c3= -11.376 -0.12 (0.05) -11.175 -0.15 (-0.01) -11.010 -0.18 (--0.08)
c7 -11.448 0.03 -11.200 -0.13 -10.963 -0.18
c9 -11.367 0.00 -11.1.13 -0.11 -11.022 -0.04

=Eigenvalue of the 1s orbital in atomic units. bAtomic charge in units of electrons. =The
value in parentheses is the group charge for the C-H group obtained by adding the atomic
charges on C and H.

The geometry of the radical anion TCNQ-’ was taken as an average of the
reported crystal structure data as given in ref. 4 [ 151 (Table 1). Because the
cost of one calculation was quite high due, in part, to slow convergence of
the wavefunction, geometry optimization was not performed.
The canonical molecular orbitals obtained by the PRDDO method give
an eigenvalue spectrum which compares well with the large basis set cal-
culation [6]. For example, the ionization potential given by Koopmans’
theorem is 9.1 eV from the PRDDO calculation, 9.5 eV from the large
basis set [6] and 8.4 eV [16] from experiment for neutral TCNQ. Also the
PRDDO method gives as good a description of the n-eigenvalue spectrum
as it does for a number of fused ring aromatic hydrocarbons [ 111. As
expected, the minimum basis set fails to give negative eigenvalues for the
highest filled molecular orbitals of TCNQ-*. As in previous studies [ 10,111,
we rely on inner shell eigenvalues and group (Mulliken) charges for inter-
pretation of reactivities when dominated by the ground state. These values
are summarized in Table 2 for TCNQ, TCNQ-’ and TCNQ-*.
The localized molecular orbitals (LMO’s) are shown in Fig. 1 for TCNQ
and TCNQ-*. These LMO’s show the expected topology of single, double
and triple bonds. In the following discussion we shall examine only the
symmetry unique bonds. All of the bonds in TCNQ are quite highly localized.
The double and triple bonds do not show a CJT separation but, rather, bent
equivalent 7 bonds formed from the appropriate combination of c and 71
orbit&. These 7 bonds are a normal consequence of the localization of
structures containing 0 and rrbonds [ 111. The set of r bonds found between
3 and 4 have a delocalization index of only 11.5% [ 17]_ The C-C c bond
between 1 and 3 is essentially colinear with the C-C axis and is slightly
polarized towards 1 with a hybridization of sp’-‘. The T bonds between
1 and 7 ,are more delocalized than are their counterparts 3 and 4, and are
significantly polarized towards 7. The 7-O single u bond is polarized towards
9 and the centroid of charge lies slightly away from the C-C axis. The bonding
158

Fig. 1. Localized molecular orbitals for TCNQ and TCNQW2 together with the numbering
scheme. Two dots (:) correspond to a lone pair. Bent bonds are T bonds which for double
bonds are found above and below the molecular plane and for triple bonds are spaced at
120°C about the C-N axis. See text for details. (a) TCNQ. (b) One of the two equivalent
structures for TCNQe2, The second structure would correspond to the other KekulQ
structure for the ring and is not shown.

of C9 to N consists of three equivalent non-polar T bonds distributed about

the C-N axis. Since the basic convergence procedure used in obtaining the
LMO’s involves mixing two orbitals rather than the three orbitals found in
each CN group, convergence of the LMO’s is quite slow in TCNQ. These 7
bonds are approximately sp6 in hybridization at both C and N and have a
delocahzation index of only 6%. As a consequence of these hyb~diz~t~ons,
the bonding in the ‘7-9 bonds is sp at C9 and sp* at C7 as expected from
simple theories. The lone pair on N has substantial 2s character, 69%, based
upon population analysis.
The LMO’s for the dianion are quite different from those in the TCNQ
and were useful in pres~~~mg the inikiialgeometry for the dianion. The
initial TCNQ geometry was used to obtain a wavefunction for the ground
state of the dianion. Localization of the wavefunction yielded LMO’s in
the ring resembling the LMO of benzene, a Cl-C7 Q bond and a lone pair
on C7. Even though the initial geometry was far from correct, the LMO’s
predicted the correct direction for geometry opt~ization. The LMO’s for
TCNQ-* based on the fiial TCNQ-* geometry are shown in Fig. l(b). The
simple description as we have noted is a benzene ring and lone pairs on
C7 and C8. Two symmetry equivalent locahzations were obtained corre-
 159

sponding to the two Kekulk structures of benzene. Due to the asymmetry of

the ring geometry, the LMO’s are not equivalent as found in benzene. The
set of 7 bonds between 5 and 6 is non-polar as required by symmetry but
the set of 7 bonds between 1 and 3 is quite polar. The C--C u bonds are
slightly polar, have about spla8 hybridization and the centroid of charge
lies slightly away from the C--C axis. The C--C (Tbond between 1 and 7 is
essentially non-polar with a hybridization of sp”’ on 1 and sp ‘*’ on 7. The
lone pair on C7 has a population of 1.57 e on this carbon and has pure
p character. The delocalization of the remaining density is not solely in
the direction of Cl which has only 0.10 e delocalization density but rather
has density of 0.12 e on both C9 and C12. The excess density is evenly
divided among the p orbitals on three adjacent carbons. Thus, there is only
a very small amount of double bond character in the Cl-C7 bond. Notably,
this 0-n separation is observed using the criterion of Boys [lla] . The
bonding of C9 to N is again due to three T bonds which are not equivalent
because of delocalization of the lone pair. Two of the three 7 bonds are
approximately equivalent, and are slightly polarized towards N (1.03 e on
N and 0.97 e on C). The remaining 7 bond is more polar towards N (1.15 e
on N and 0.85 e on C) and is somewhat more delocalized than are the
other two C-N T bonds (7.3% for the unique orbital as compared to 6%
for the equivalent orbit&). The lone pair on the N is very similar to the
lone pair found in TCNQ having 68% 2s character in the population analysis.
The LMO’s suggest that the l-7 bond is very similar to a C-C single
bond. In order to test this result, we have examined the barrier to rotation
about the l-7 bond. Using the optimized TCNQ-* geometry, calculations
were done for rotation angles of 45 and 90” from the planar form. Upon
this rotation the energy of the molecule increases by 6 kcal mole-’ at 45”
and by 12 kcal mole-’ at 90”. The conjugative effect stabilizing the planar
form is estimated as -12 kcal mole-‘, provided we recognize that geometry
optimization of the perpendicular form would lower its energy. This value
of 12 kcal mole-’ for the conjugative effect is surprisingly similar to the
value of 8 kcal mole-’ found for nitrobenzene [18] defined by the 90”
twist about the C-N bond.

o- /O
“\, -
8 kml mole-

(o)-
NfO
‘X0

For neutral TCNQ, the energy for rotation about the l-7 bond is expected
to be between 45-65 kcal mole-’ depending on the energy gain in the
perpendicular form due to the five centered radical in the ring. Addition
of two electrons to TCNQ to form TCNQ-* provides a lower energy pathway
for isomerizing about the l-7 bond. Moreover, the molecule is predicted
to be much less rigid in the dianion form. The LMO’s and low value for
the conjugative effect suggest that TCNQm2may not, by itself, be a good
electron transfer agent. However, we cannot, as yet, determine how the
behavior of the free ion affects its characteristics in an infinite chain as found
in the solid state.

ACKNOWLEDGEMENT

We wish to thank the National Science Foundation Grant CHE 76 84183

for support of this research.

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normalizing.
18 D. A. Dixon, unpublished work.