Theoret. chim.

Acta (BerL) t, 83--85 (1962)

British Columbia Research Council, University of British Columbia, Vancouver 8, B.C., Canada

Self Consistent Field Molecular Orbital Calculations

for Mono and Disubstituted Benzenes*
By
J. E. BLoon and F. PERADEJORDI**

The semi-empirical modifications introduced into the self-consistent field

molecular orbital method (SCFMO) by POPLE [13] and P A ~ I s ~ and PA~R [10]
make it quite feasible to compute the excited state energies of monosnbstituted
benzenes using self-consistent field orbitals. The only published work on this topic
has been on aniline [12, 11]. I n one of these studies [12] the energy levels were not
reported and in the other [11] the agreement between experiment (Tab. i) and
theory (Tab. l) was not very good for the second transition. Since data on the
effect of polar substituents on the properties of benzene form a large part of the
experimental results available for testing theories of molecular structure, it is
important t h a t the theoretical calculation of such properties be carried out with
as much detail as is possible.
As part of a more general programme on the calculation of molecular properties
of disubstituted benzenes we have applied the SCFMO method to phenol, to aniline
and to benzaldehyde where the substituents are a weakly interacting electron
donating one, a strongly interacting electron donating one and a strongly inter-
acting electron attracting one, respectively.
The calculation of the SCF ground state orbitals was made b y the semi-
empirical MO method [13] using empirical values of the resonance integrals from
the literature.
i.e. flc--c (r ~ i.39 •) ~ - - 2 . 3 9 ev, flc--c (r ~-- 1.48 -~) ~ - - 1 . 6 8 ev,
flc--o = - - 2 . i 2 ev [9], fic--~v ---- - - 2 . 7 4 ev [12], and fic=o = - - 2 . 7 0 ev [1].
The core integrals with the exception of t h a t of nitrogen, were those also used by
previous workers,
i.e. We+ ~- - - f i . 2 8 ev [10], Wo+ -~ - - 1 8 . 2 9 ev [1], and Wo2+ -- - - 3 4 . 9 5 ev [9].
For nitrogen Wzr = - - 24.56 isless than t h a t usually used, i.e. Wiv2+ -----27Ai4 ev [2]
but similar to t h a t used b y M c E w ~ for nitroamide (W~ve+ ------24.83cv[5]).
The effect of varying the value of the core integral will be discussed elsewhere.
The molecular repulsion integrals were calculated using the approximation
suggested by MALAGA [all, rather than the more usual P A n x s ~ and P ~ R

* Given in part at the XVIIIth International Congress of Pure and Applied Chemistry,
Montreal, August 1961.
** Permanen~ address: Centre de M6canique Ondulatolre Appliqu~e, 155, l%uede S~vres,
Paris t5% France.
6*
84 J.E. BLooI~ and F. PERADEJORDI:

a p p r o x i m a t i o n [10]. T h e results are c o m p a r e d w i t h e x p e r i m e n t a l t r a n s i t i o n energies

(E) a n d oscillator s t r e n g t h s (f) in T a b . I. The a g r e e m e n t w i t h e x p e r i m e n t is quite
s a t i s f a c t o r y . Self consistent orbitals, o b t a i n e d as d e s c r i b e d above, m a y be u s e d
as a basis for t h e calculation o f e n e r g y s t a t e s o f c o n j u g a t e d molecules R - - S b y
treating t h e b o n d b e t w e e n t h e t w o f r a g m e n t s R a n d S as a p e r t u r b a t i o n on e x c i t e d

Table 7. SCF Calculations on Monosubstituted Benzenes

E (ev) f* E (ev) f E (ev)

C6HsNH~. Exp . . . . . . . . . . 4.30 .03 5.27 .t7 6.4

Prey. Calc. [11] . . . . . . . . . 4.30 4.30 6A
New Cale . . . . . . . . . . . . . . 4.24 .99 5.29 .44 6.57
6.61
C~I-I~OH. Exp . . . . . . . . . 4,60 .02 5.83 A0 6.54 1.00
Calc . . . . . . . . . 4.80 .01 5.96 .06 6.82 ~i.20
6.83 1.09
C~HsCH0. Exp . . . . . . . . . 4.50 .01 5.16--5.30 .25 6.36
Calc . . . . . . . . . 4.69 .03 5.39 .39 6.48 .83
6.88 .99

* A.~ defined in ref. [6].

configurations built, u p f r o m S C F w a v e functions of R - - H a n d S - - H [8, 7]. The

configurations are of t w o kinds, locally e x c i t e d (LE) ones i n v o l v i n g t h e orbitals
of R or o f S only, a n d electron t r a n s f e r (ET) configurations, i n v o l v i n g electron
t r a n s f e r b e t w e e n R a n d S.
P r e l i m i n a r y results using this m e t h o d for b e n z a l d e h y d e a n d t h e t h r e e h y d r o x y -
b e n z a l d c h y d e isomers are g i v e n in T a b . 2. The e x p e r i m e n t a l d a t a r e c o r d e d are

Table 2. IntramolecuIar Charge Trans/er Calculations

E (ev) E (ev)

C6HsCH0. Exp . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4.50 .01 5.20 .25

Calc . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4.80 .01 5.30 .15
para-OMeC~HdCH0. Exp . . . . . . . . . . . . . . . . . . . 4.4j .01 4,50 .42
Ca,lc. . . . . . . . . . . . . . . . . . . 4.5 .00 4.83 .20
meta-OMeOaHaCHO. Exp . . . . . . . . . . . . . . . . . . . 4.30 .05 5.00 A4
Calc . . . . . . . . . . . . . . . . . . . 4.47 .07 5.30 .16
ortho-OMeC6HdCHO. Exp . . . . . . . . . . . . . . . . . . . 4.00 .06 5.00 .22
Calc. . . . . . . . . . . . . . . . . . . 4.38 .08 5.28 A6

those for t h e m e t h o x y b e n z a l d e h y d e s , since this eliminates t h e necessity of t a k i n g

into consideration t h e effect of i n t r a m o l e c u l a r h y d r o g e n bonding, T h e p u r e l y
electronic effect of replacing h y d r o x y l b y m e t h o x y l is k n o w n to be small [3].
T h e S C F orbitals o f R a n d S were t a k e n as t h o s e of p h e n o l a n d o f f o r m a l d e h y d e ,
while t h e energies of t h e L E s t a t e s were t a k e n f r o m t h e o b s e r v e d s p e c t r a of these
molecules. F u r t h e r details t o g e t h e r w i t h f u r t h e r calculations on s u b s t i t u t e d nitro
c o m p o u n d s a n d anilines will be r e p o r t e d elsewhere.
 SCF Calculations for Mono and Disubstituted Benzenes 85

We wish to thank the National Research Council os Canada, for financial aid, and the
University of British Columbia compubing centre and Mine. BEN JEY[IA of the Centre de
M6canique Ondulatoire Appliqu~e for help with the computations. One of us (F.P.) also
wishes to record his thanks to NATO for a travelling Fellowship, and to Professor DAU1)EL
and the CNt~S (Paris, France) for leave of absence.

References
[1] BROWN, 1~. D., and M. L. I - I E F F E R N A N : Trans. Faraday Soc. 54, 757 (1958).
[2] BRow~, l~. D., and M. L. K~FFERNAN:Austral. J. Chem. 12, 557 (1959).
[3] Bvu_awoY,A.: Hydrogen Bonding, Ed. D. Had~i Pergamon Press, London (19.~91 p. 259.
[4] MATAGA,N., and K. NmniMowo: Z. physik. Chem. [Frankfurt a.M.] 13, 140 (1957).
[5] McEwEN, K. I,.: J. chem. Physics $4, 547 (t961).
[6] !V~uLLIKEN,~:~.~., and C. A. ~:~IEKE;Rep. Prog. Phys 8, 231 (194i).
[7] MVUUELL,J. N. : Proc. physic. Soc. A, 68, 969 (t955).
[8] M u u R ~ . , J. N , and H. C. LONGVET-HIGGINS:Proc. phys. Soc. A 68, 661 (1955).
[9] NIsamowo, K., and 1~. FvJisn~mo: But]. chem. Soc. Japan ~1, ~1036 (1958).
[10] P~Is~.~, I~., and 1~. G. PA~u: J. chem. Physics 21, 466, 767 {1953).
[11] PEACOCK,T. E. : Mo]. Phys. 3, 453 (t960).
[12] P~D~JORDI, F.: Calcul des Fonctions d'Onde Moleculaire, CN]~S, Paris (t958) p. 247.
[13] POPLE, J. A. : Trans. Faraday Soc. 49, 1375 (1953).

(Received March 3, 1962)