3 October 1997

:5'~ ! ~, .'

CHEMICAL
PHYSICS
LETTERS

ELSEVIER

Chemical Physics Letters 277 (1997) 257-263

A theoretical study on the isomerization of cyclopropane to

propene with ab initio and DFT methods
Kang-Nian Fan

a,

Zhen-Hua Li a, Wen-Ning Wang a, Hsing-Hua Huang

Wei Huang b

b
9

a Department of Chemistry, Fudan University, Shanghai 200433, China

b Department of Chemistry., National University of Singapore, Singapore 119260
Received 4 April 1997; in final form 31 July 1997

Abstract

The isomerization of cyclopropane to propene had been studied by ab initio post-HF and DFT methods. Single-point
energy calculations at UMP4, UCCSD(T), UQCISD(T) and UBecke3LYP levels were carded out on the UMP2/6-31G * *
fully optimized structures. The reaction heat and activation energies for the whole isomerization reaction and the structural
isomerization of the C2-symmetry trimethylene intermediate were evaluated. The correlation methods employed release an
accuracy order of UBecke3LYP > UQCISD(T)--(UCCSD(T)> UMP4 > UMP2. UBecke3LYP is found to be the best
method to reproduce the experimental results. The spin contamination problem can be solved by using projected MP
energies. 1997 Elsevier Science B.V.
1. Introduction

Isomerization of cyclopropane to propene was

first studied by Chambers and Kistiakowsky in 1934
[1]. Since then the stereomutation and the whole
structural isomerization of cyclopropane (Scheme 1)
has become the subjects of dozens of experimental
and theoretical studies. Many experimental [2-4] and
theoretical [5-7] studies concentrated mainly on the
thermal stereomutations of non- or isotopically labeled cyclopropane, and singlet trimethylenes as the
intermediates of the stereomutation were well established. Other experiments mainly focused on the
isomerization of cyclopropane to propene and the
kinetic behaviors of the whole isomerization reaction
had been well studied by various methods [1,8-10].
Unfortunately the theoretical studies on the whole
structural isomerization of cyclopropane to propene

were far less satisfactory. In 1976, Jug Karl performed an INDO(SINDO) study on the whole isomerization reaction [11]. The activation energy obtained from their studies was about 25% less than the
experimental value. In 1988 Valko, Simon and Van
Cuong studied the structural isomerization of
trimethylenes with an extended bond-energy and
bond-order method (EBEBO) [12]. The activation
energy they obtained was 38.9 k J / m o l . Recently,
Doubleday studied the life time of the trimehtylenes
with RRKM theory [13]. The activation energy of the
structural isomerization of trimethylene to propene
he obtained was 28.9 k J / m o l and was believed to be
a little larger than the value predicted by Waage and
Rabinovitch in 1973 [14].
Although the geometrical isomerization of cyclopropane were well studied by aforementioned theoretical methods, and the structural isomerization of

0009-2614/97/$17.00 1997 Elsevier Science B.V. All rights reserved.

PII S 0 0 0 9 - 2 6 1 4 ( 9 7 ) 0 0 9 0 5 - 6

258

K.-N. Fan et al. / Chemical Physics Letters 277 (1997) 257-263

R~
//C~

opemuing.

Stmctm-al

C C ~
- CH2CH2CHz
eyelopropane(R0) trimethylene

~ CI-I~CHCH3
propene(P)

Scheme 1.
trimethylene biradical to propene was also well studied by Doubleday [13], the whole structural isomerizarion of cylopropane to propene has not been studied by any ab initio methods. Singlet biradicals are
important intermediates involved in most thermal
decomposition reactions, where electron correlation
energy plays a very important role. Since most correlation methods are very time consuming, we have to
balance between accuracy and time to find an appropriate tool in dealing with biradicals. Additionally
H-shifting reaction is also a very common reaction in
organic chemistry. Problems encountered here are
prototypical and they provide an interesting and challenging test ground for quantum chemical researches.

2. Calculation methodology
All calculations were carried out by using the
Gaussian 9 2 / D F T package of ab initio programs
[15] with the 6-31G * * basis set. Geometry optimizadons were performed at the UMP2 level with all
force constants calculated by using analytical method.
Although it is well known that MP2 is superior to
I-IF, here UI-IF method was also engaged for optimization to be compared with the UMP2 results. All
transition state structures were further confirmed by
intrinsic reaction coordinate aRC) calculations. Four
types of correlation methods, UMP4, UCCSD(T),
UQCISD(T) and UBecke3LYP were used for single
point energy calculation on the UMP2 optimized
structures.
Analytically evaluated frequencies at the UMP2
level were scaled by a factor of 0.93 [16]. In order to
obtain the activation energy, thermal energies of
species were calculated adopting ideal gas approximarion of statistical thermodynamics. Careful analyses were performed on the calculated frequencies of
those species and the lower frequencies related to
intramolecular rotations were treated as free rotations
in the calculation of the thermal energies above room
temperature.

3. Results and discussion

3.1. G e o m e t r i e s

Four transition structures and two intermediates

were located on the potential energy surface (PES).
The complete diagram of the whole reaction is illustrated in Scheme 2. IRC calculations show that R1 is
the intermediate that undergoes structural isomerization to propene (P). The stereomutation of R1 and
R2 demonstrated here is identical with that in Refs.
[6,13]. But the transition structure of the 1,3 H-shift
of trimethylene to form ethylcarbene optimized by
Doubleday was not obtained by us. As will be shown
later, TS2, R2 and TS3 make no contribution to the
reaction rate constant of the whole reaction or the
structural isomerization of R1 and will not be discussed here. Geometries of cyclopropane, TS1, R1,
TS4 and propene optimized at the UMP2 and UHF
levels are shown in Fig. 1.
UHF, UMP2 and CASSCF optimized structures
are very similar [13]. It is seen from Fig. 1 that CH
bonds optimized at the UHF level are always shorter
than those optimized at the UMP2 level. But this
simple relationship does not always hold for CC
bonds. As shown in Fig. 1, CC bonds in cyclopropane, C2C 3 bond in TS4 and CiC 2 bond in
propene optimized at the UHF level are all shorter
than those at the UMP2 level. But other CC bonds
optimized at the UI-IF level are longer. Pulay et al.
[17] had proposed a set of empirical correction parameters for the theoretical HF bond lengths. Correcting UHF optimized CH or CC bond length with
these parameters, we immediately get the bond
lengths which is very close to our UMP2 results.
Therefore, despite the lack of experimental geometry
data of the short-living species, the UMP2 optimized
structures should be very close to the real situation.
This is the reason why we use UMP2 as the optimization method.

R0.

RI(CD

TS4(CL)

TS2(Cs~ /TS3(C,)
~lt2(Cs)
Scheme 2.

- P(Cs)

259

K.-N. Fan et al. / Chemical Physics Letters 277 (1997) 257-263

1"076T

1.075

~ 1 . 0 9 0Z C C C 112"40
112.60

1. 511w

r.5o

1.078 ~

1.494

1.497 UHF/6-31G**
/I-[O3C 50.89
1.502 U M P 2 / 6 - 3 1 G * *
45.55

Cyclopropane(R0)(I~h)

/HbCCC -132.69
-140.43

TS 1(C2)

1 . 0 9 2 ~ L C C C 112.84
~ . 0 91 183 .~1 1 . 0 9 8 .. 113.I6

H4C2 1 . 2 3 9 _ _
_
1.186~

I "-0 7l ~ B
' ~ al ~ ~a[ ~m' 4 5a 0 l3 ' ~

"

H4
1.435
~1.497

/ ~ C U C 35.89 /Hb(ZI2-160.89
36.90

-15~85

1.079
C1C 2 1.413
1.430

RI(C2)
1.076

I-~

1AS1 " ~ 1.076

/ C C C 125.74
126.36

TS4(CI)

1.087
I-I3C2 1.080
1.085

1.078'~C 1
1.082 -CIC2 1.318
1.337

I - ~ . U 2 ~ / H5C 3 1.084
1.498 ~i5 -1.089
L C C C 125.30
124.45

Propene(Cs)
Fig. 1. Geometriesand importantgeometryparametersfor the reactant (R0), product(P), one intermediate(R) and two transition structures
(TS1 and TS4 respectively).
3.2. Energy profiles

The calculated total energies, zero-point vibrational energies and relative energies to R0 for all
species with six different methods are listed in Table
1. The PES of the tfimethylene is very flat [6,13]. It
is seen from Table 1 that TS1 and R1 are very close
in energy and the relative energy of TS1 or R1 to R0
evaluated at the I-IF level is much less than that
calculated by other correlation methods. This can be
explained by the following facts. Since two electrons
between two bonding carbon atoms in R0 are divided and located on two remote carbon atoms in

TS1 or R1, that part of correlation energy involving

these two electrons in R0 and TS1 or R1 may belong
to two different types. In R0 it is dynamic correlation, while in TS1 and R1 it is mainly static. Noticing that the SCF wavefunctions of R0 are RHF and
correct no dynamic correlation while those of TS1
and R1 are real UHF and correct static correlation to
some extent, so compared with correlation methods
which consider both dynamic in R0 and static correlation in TS1 or R1, HF method gives lower relative
energy difference for TS1 or R1 to R0. Since TS1
and R1 are very close in energy, electronic correlation and ZPE corrections must have a substantial

K.-N. Fan et al. / Chemical Physics Letters 277 (1997) 257-263

260

Table 1
T o t a l e n e r g i e s (in hartree), z e r o - p o i n t vibrational e n e r g i e s ( Z P E ) (in hartree a n d s c a l e d b y a f a c t o r o f 0.93), r e l a t i v e e n e r g i e s (in k J / m o l )
a n d ( S 2 ) for all s p e c i e s
Species cyciopropane (R0)

TSI

RI

TS4

p r o p e n e (P)

Methods

(D3h)

(C 2 )

(C 2 )

(C I )

(Cs)

UHF

- 117.068942
0.0

- 117.008680
136.6(158.2) a

- 117.008999
137.0(157.4)

- 116.958174
266.8(290.8)

- 117.081027
- 37.5( - 31.7)

UMP2

ZPE
(S 2) b

- 117.497142
0.0
- 117.545945
0.0
- 117.547102
0.0
- I 17.547275
0.0
- 117.904208
0.0
0.078379
0.0

- 117.388326
264.1(285.7)
- 117.442470
250.1(271.7)
- 117.445680
244.7(266.3)
- 117.445889
244.6(266.2)
- 117.807711
231.7(253.4)
0.070150
1.013(0.172) d

- 117.388419
265.1(285.4)
- 117.442480
251.3(271.6)
- 117.445575
246.2(266.6)
- 117.445774
246.1 ( 2 6 6 . 5 )
- 117.807230
234.2(254.6)
0.070624
1.018(0.172)

- 117.355115
348.9(372.9)
- 117.409322
334.7(358.7)
- 117.422982
301.9(325.9)
- 117.423012
302.2(326.2)
- 117.792120
270.3(294.3)
0.069232
0.858(0.208)

- 117.503914
- 23.5( - 17.8)
- 117.556484
- 33.4( - 27.7)
- 117.558460
- 35.6( - 29.8)
- 117.558710
- 35.8( - 30.0)
- 117.916427
- 37.8( - 32.1 )
0.076188
0.0

(S 2) c

0.0

0.960(0.046)

0.987(0.049)

0.153(0.001)

0.0

UMP4
UCCSD(T)
UQCISD(T)
UBecke3LYP

a
b
c
o

V a l u e s in p a r e n t h e s e s are not c o r r e c t e d b y Z P E .
U H F , U M P 2 , U M P 4 , U C C S D ( T ) a n d U Q C I S D ( T ) all h a v e the s a m e S C F r e f e r e n c e w a v e f u n c t i o n s and so h a v e the s a m e ( S 2 )
UBecke3LYP.
V a l u e s in p a r e n t h e s e s are t h o s e after h i g h spin c o n t a m i n a t i o n is annihilated.

influence on their relative positions. Table 1 shows

that at higher correlation levels such as UCCSD(T),
UQCISD(T) and UBecke3LYP, TS1 even lies
slightly below RI. After ZPE correction TS1 is
slightly lower than R1 at all six levels.

3.2.1. Reaction heat

The whole reaction is an isogyric process so even
the simplest model (SCF) which considers no correlation can reproduce the experimental value correctly
[18]. The reaction heat predicted at the UHF level is
- 3 6 . 8 k J / m o l and falls in the average error range
of experiments. Among those correlation methods
the best one is UBecke3LYP, and the worst is MP2.
UBecke3LYP predicts a value of - 3 7 . 2 k J / m o l .
The accuracy order of these six methods is
UBecke3LYP = UHF > UQCISD(T) > UCCSD(T)
> UMP4 > UMP2 (from the best to the worst).
However all methods underestimate the energy outcome of this reaction.
3.2.2. Activation energy for the structural isomerization of trimethylene R1 to propene (E,,(s))
According to the conventional transition state theory the activation energy of a elementary reaction is

equal to the energy barrier of the reaction plus RT

[19]. Activation energies in Table 2 are calculated at
800 K, since most experiments were performed near
this temperature. In contrast to the calculation of the
reaction heat, the activation energy predicted at UHF
level is 130.7 k J / m o l and is too high. UMP2 and
UMP4 have the same accuracy (-- 84.5 k J / m o l ) and
this also holds for UCCSD(T) and UQCISD(T) ( =
56.8 kJ/mol), but both pairs overestimate the activation energy needed. UBecke3LYP method predicts
an activation energy of 36.9 k J / m o l , excellently
reproducing the value of 39.7 k J / m o l that Benson
estimated in 1961 [20]. But this value is much higher
than that of Waage and Rabinovitch [14]. Waage and
Rabinovitch deduced a value of 3.7 kcal/mol for the
critical energy difference A E0* of the kg to kp (see
Ref. [14] for definition). If we take A E0* as
A E(TS4-TS1) (In fact, these two items are not
equal, since in order to get AE(TS4-TS1) from an
experiment we must employ some assumptions regarding kinetic isotope effects and a reasonable
mechanism about the isomerization reaction [6].) and
take the energy difference between TS 1 and R 1 to be
1 kcal/mol [6,7,13] and we will deduce a value of
about 4.7 k c a l / m o l (19.6 k J / m o l ) + R T for the

K.-N. Fan et al. / Chemical Physics Letters 277 (1997) 257-263

261

Table 2
Activation energies of structural isomerization (Ea(s)) and the whole H-shifting reaction (Ea(w)) and the enthalpy change of the whole
reaction at 298.15 K (kJ/mol)
Energies

UHF

UMP2

UMP4

UCCSD(T)

UQCISD(T)

UBeeke3LYP

exp.

AHr a
Ea(S) b
Ea(w)

-36.8
130.7
273.1

-22.8
84.7
355.2

-32.7
84.3
341.0

-33.9
56.6
308.2

-35.1
57.0
308.5

-37.2
36.9
276.6

-40.5 d
26.3 e
267.5 4- 3.6 [1(3]
276.0 4- 2.1 [9]
272-276 [ 1]

a A E ( P - R 0 ) at 298.15 K. b A E ( T S 4 - R 1 ) + RT at 800 K. c A E ( T S 4 - R 0 ) + R T at 800 K. d Calculated from the heats of combustion of

cyclopropane and propene from CRC Handbook of Chemistry and Physics (69th edition, 1988-1989). This value is deduced from ref. [14]
(A E0* + 1.0 kcal/mol + RT).

activation energy of R1 to propene. Nevertheless we

would call Waage and Rabinovitch value "experimental value" for comparison.

higher than those for the stereomutation of the

trimethylene intermediates [13] as well as those for
the ring close reaction and k_ 1, k_ 2, k3, k_ 3 are all
of the same magnitude order [6,13], we have

3.2.3. Activation energy for the whole reaction

(E~(w))

k-2+k 3
- k4<<k_2+k3"
k_l

For the whole isomerization process (Scheme 3),

engaging steady state approximation we get

d[P]
dt

Then from Eqs. (1) and (2) we get

kl

k4

kl

k_ 1 X

kwhle ~ k4 E

/_~ + k3 + (k2//q)/q
k_ 2 + k 3 + ( k_2/k_l)k_3 + (k_ 2 + k _ 3 / k _ l ) k 4
X [R0].

kBT

(AG*)
h exp
~-~

(2)

where k n is Boltzmann constant and AG* = G(TS)

- G(Reactant) [19]. So we have
k 2
k a = ~--~,"k_3,
I

--I

since A G ( k 2 ) * - A G ( k l ) * +AG(k3)* is equal to

AG(k_2)* - A G ( k _ i)* + AG(k-3)* Noticing that
energy harrier for the structure isomerization is much

kl

RO~.~/1""-~

k4

AG*(TS4-R1))
-

( knT/h ) exp{ - [ AG * (TS l - R 0 ) / R r ]

( knT/h ) exp{ - [ AG* (TS 1 - R I ) / R T ]

}
}

kaT

(1)

According to conventional transition state theory, the

rate constant of a unimolecular reaction is given by
k=

k Texp(
l =

(AG*(TS4-R0))
h exp ~-~

(3)

Eq. (3) has a similar form as Eq. (2) and can be

written in Arrhenius form. So the activation energy
for the whole reaction is equal to A E ( T S 4 - R 0 ) +
RT. The activation energies calculated with different
methods are listed in Table 2. At 800 K,
UBecke3LYP method yields a value of 276.6 k J / m o l
which agrees very well with the experimental value
of = 276 kJ/mol. The UHF method predicts a value
of 273.1 kJ/mol. UQCISD(T) and UCCSD(T) again
have the same accuracy but their value, --308
kJ/mol, is still too high as that for structural isomerization. Again we have an accuracy order of
UBecke3LYP ~ UHF > UQCISD(T) -- UCCSD(T)
> UMP4 > UMP2 (from the best to the worst).

3.3. Comparison of different methods

Scheme 3.

Factors affecting the accuracy of an ab initio

method generally include the completeness of the

262

K.-N. Fan et al. / Chemical Physics Letters 277 (1997) 257-263

basis set and the level of the correlation. Since our

study involves singlet biradicals and employs spin
unrestricted methods, there is a third factor which is
the spin contamination in the reference wavefunctions of the open shell species. It seems that 6-31G * *
basis set is adequate here since Refs. [7,21] have
shown that basis sets larger than 6-31G** do not
greatly change the relative energy of R1 or R2 to R0.
So only two factors, i.e. the correlation level and the
spin contamination are working here. As that previously mentioned, since the whole reaction is an
isogyric one, the HF reaction heat is very close to the
experimental value. The accuracy order of the other
four methods on the reaction heat calculations refleets their correlation level. It is clear that MP2 is
not adequate. MP4, CCSD(T) and UQCISD(T) are
better than MP2 but it seems that their consideration
of correlation is still not adequate. Thus Becke3LYP
is the most accurate method here.
The comparison of the calculation of the two
activation energies is somewhat complicated since it
is mixed with the effects of both correlation and spin
contamination. Computed values of ( S 2) are also
given in Table 1. From Table 1 we can see that ( S 2 )
of the three open shell species is large and the spin
contamination here is severe. The contamination in
the UBecke3LYP wavefunctions of the three species
is not as severe as other methods, especially for TS4.
Lower spin contamination and high correlation level
are the two factors that make the UBecke3LYP
method more accurate than the other correlation
methods. It would not be surprising had the UHF
method given the worst results, because it considers
correlation to some extent in its real UHF wavefunctions of the TS1, R1 and TS4 species but considers
none in its RHF wavefunctions of the R0. But it is
surprising that the activation energy for the whole
calculated reaction is so close to the experimental
value. Table 3 presents the results calculated from
HF, MP2 and MP4 energies with spin projection.
PUI-IF, PMP2 and PMP4 all lower the two activation
energies, E~(s) and Ea(w) remarkably. As for the
results of the PUHF, E~(s) is closer to the experimental value than Ea(W), but Ea(W) is far from the
experimental value. Ea(S) calculated from the PMP2
and PMP4 energies are much closer to the "experimental value" than that calculated from unprojected
MP energies. Ea(w) calculated from PMP2 energies

Table 3
Activation energies for the structural and whole isomerization
reaction obtained from PUHF, PMP2 and PMP4 energies a (in
kJ/mol)
Activation energy
PUHF
PMP2
PMP4
ea(s)
83.5
39.7
42.5
Ea(w)
210.7
294.4
283.2
a Spin contaminationis annihilated from s + 1 to s +4.

is greatly improved but is still not accurate enough.

This also shows that MP2 may not be sufficient for
correlation correction. The accuracy of the PMP4 is
very high. So we conclude that the spin contamination problem in the MP wavefunctions can be solved
by spin projection method. This is in agreement with
the results of ref. [22] and [23]. Since UCCSD(T)
and UQCISIXT) calculations are still performed on
the spin contaminated HF wavefunctions, it is expected that if we use projected UCCSD(T) and UQCISD(T) energies or MR-QCISD(T) and MRCCSD(T), the discrepancy between their calculations
and the experimental results should be healed. This
is true for Ea(S) since Doubleday's CAS-CISD
method got a better value for it than us. However,
this function has not yet been incorporated into
Gaussian and we are not able to perform these types
of calculations at present.
Although projected MP4 energies provide very
good results with regard to Ea(s) and E~(w), and so
will the projected CCSD(T) and QCISD(T) energies,
these three methods are more time consuming than
the UBecke3LYP method. So we recommend
UBecke3LYP as the first choice where singlet biradicals are involved.

4. Conclusions
UBecke3LYP is the best method which reproduces experimental reaction heat and activation energies, both for the structural isomerization and the
whole isomerization reaction, accurately. It can well
describe the behaviors of those open shell species
because its wavefunctions contain less spin contamination. It is also the least source requiring correlation
method employed in this study. Activation energies
calculated at UMP2, UMP4, UCCSD(T) and UQ-

K.-N. Fan et al. / Chemical Physics Letters 277 (1997) 257-263

CISD(T) levels are higher than the corresponding

experimental values. This is mainly because of the
spin contamination in their HF reference wavefunctions. For UMP2, this problem can be partly overcome by annihilating the high spin contamination in
its reference wavefunctions. Values derived from
projected MP4 energies agree with the experimental
results very well.

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