Chemical Physics 52 (1980) 151-163

@ North-Holland Publishing Company

THEORETICAL

ANALYSIS

OF THE CYCLOADDITION

E. KASSAB, E.M. EVLETH,

J.J. DANNENBERG*

OF ETHYLENE

and J.C. RAYEZ**

Cenne de Micanique OndularoireAppliqu&, 75019 Paris, France,

and the Deparhnent of Chemistry, City Universityof New York, Hmrer College,
New York, N-Y. 10021, USA
Received 2 January 1980
Revised manuscript received 1 July 1980

The cycloaddition of ethylene is theoretically analyzed for portions of the excited singlet and triplet hypersurfaces
using a combination of semi-empirical and intermediate level ab initio techniques. The semi-empirical UHF calculations
on the addition of triplet ethylene and methyl radical to ethylene showed that these two reactions have comparable
theoretical parameters, including activation energies, spin transfer and spin polarization at the transition state. For the
?.S+ZS excitedsingletstate surfaces, the results of both the ab initio and semi-empirical calculations are qualitatively the
same and correspond to the classical ideas generated from orbital symmetry rules. At the ab initio level the results are
quantitatively poor, partially due to the use of an intermediate level configuration interaction treatment. In particular, it
was not possible to obtain other than a small fraction of the total estimated valence correlation energy in cyclobutane.
The configuration interaction problem for both ab initio and semi-empirical calculations is discussed in detail.

1. Introduction

The goals of this article are two-fold. First,

we will characterize the theoretical nature of the
photodimerization of ethylene for portions of
both the excited singlet and triplet hypersurfaces. Second, we will explore some of the
methodological problems encountered in using
semi-empirical and ab initio methods to elucidate photochemical reaction mechanisms. We
are especially interested in developing semiempirical methods in order to investigate larger
systems on which good quality ab initio calculations are presently financially impractical.
The dimerization of ethylene and other
related olefins to give substituted cyciobutanes
(or the retroaction) is well studied both
experimentally [l] and theoretically [2]. The
orbital symmetry rules for the concerted 2S+2S
process are a standard pedagogical exercise [3].

* City University of New York, Hunter College, USA.

* Present address: Univeaiti de Bordeaux I, Talence,
NATO Postodoctoral Fellow, 1975-76.

While existing theoretical work is in support of

these rules, there are several important nuances
with regard to the excited state surfaces. Firstly
the triplet surfaces have not been explored.
Secondly, recent work on the analogous Hq
surface [4] indicates that a conceivable route for
deactivation of the excited singlet state of the
ethylene dimer could occur by a crossed (Dzd)
approach of two ethylenes [4b]. Thirdly, the
theoretical nature of the so-called doubly
excited state at large ethylene-ethylene
separations is not anticipated by the orbital symmetry
rules [4]. In this article we will explore portions
of the triplet surface which yield the triplet
tetramethylene diradicd. For the singlet surface
we will only explore planar face-to-face
approaches having rectangular-trapezoidal
carbon atom configurations.
We will specifically treat the theoretical
nature of the doubly excited state at both small
and large ethyiene+thylene
separations. Finally,
we will discuss the problems encountered in
using an intermediate level configuration interaction treatment.

1JI

E. Kassab et al. / 77worelicnfnnnlysis of!hc cycloaddirion

of erhpkne

and ethylene. This was done u&g &

modification cf the Gaussian 70
m in
which the size of the individual I
d s-cl.
3G orbitals is related to the mrrelalion cw?gy

Tlncmajor portionsof the ab initio cal~~~~t~~n~

were performedusing the gaussian
dique of Whitten and co-workers [S].
an over contractedvalence basis set,
olg) for carbon and (5s/24 for hydromd with orbital exponents,

[SJ.Further studies using a

~~~~nt~r~d using the intermediate tevel CI
W&Mrnffnt dl~ubeed below and lack of financial
&a#b srrry oul a complete treatment.
@fesU%ZPcalculutionswere performed oh
dk# @l@#B#hell ground and open shell singlet
&nd @ipfftt ctlnflgurutians. The CI treatment [6]
8%t9~ ir,irrlly symmetricstates was expanded

two parents,one being the original

sh@llconflgmkm, the other being the
nntigtration resulting from two
promofcd from the HOMO to
Is trentmentyields au after CI
ground state, So, and the sonclted stnte, !P*. By symmetry

@QrMlUnn,the rlagtetand triplet states cal@&MrPj

her@,87 ltndTI, have B1,, symmetries
i&f the OJ~form of the dimsr, these being
r&&d to r&Hasgeneratedby cxcitoa interHi8dttbof the mr* (%J,,)stutes with the
$$t%unrd
618IQ, Thu Cl cxpansious for these open
sr&ll etztes WQ~Q performed around only one
%Liparent cznllgurutian. All CI calculations
WVrl@the result of the threshold terms [?i] of 5 x
n with tho number of configurations
1 4OfJin each af the three separate
i%lpcl salcululions were performed by EreezMI oh@~OWVM 1 MOs (essentially Is on C), the
rNiano9 searchbeing done over the next

8, Fhusthe highest 12 virtual orbitals

%@~i-
not ttxaminad. Since the Ci calculations
@@IF
perfarmr;donly ORa portion of the
&M arhitz\lswe decided to estimate the
a%1 4%lencle
currrelntiun
energies of tiylobutane

PI.
2.2. Semi-empirical
The method used is the previowfy
moderately reparameterized CM)0 te&niq~e
[2fl applied at the medium CI tevei @O-120~ CPI
at the UHF level. An identical paratneter&&on
was used which yielded, at the 60x60 level. an
approximate enthalpy of -20 k&/mole [Zfj*
(obs., -18) [lc] for the reaction of two ethylenes to give cyclobutane as well as reasoaabk
geometries for these two molecules (e.g. CC
distar.aes of 1.35 and 1.56 A, respe&vely). The
semi-empirical CI treatment is to be contrasted
with the ab initio one in that both the grauhd
and excited singlet aud triplet Cl states were
generated from the same set of CN00 SCF
closed s!~ell molecular basis orbit&. In add&n,
no z!ltomatic confguration selection procedure
was used in the semi-empirical CI treatment.
Important configurations were inch&d in the
treatment as a result of a number of trial c2&
culations in which the inadequzy of the Cl
basis set was evident by disco&n&ties of the
S** and Sf surfaces at the HOMN,UiMO
inversion geometry (ca. 2.1 A separation
between the two ethylenes). AIthougb the original calibration of the relative enthalpies of
ethylene and cyclobutanewas done at the 60 x
60 CI level, it was found that the excited states
were better treated at a larger CI level Thus,
the So and S** states shown here were treated
at the 102 CI level of which 88 were doubly
excited including 26 four open shel9 amfigurations whose importance will be d&cussed later.
The ST and T1 states were treated at the 75 md
84 CI level, respe-tively.
At the time this study was done we had no
available scheme for geometry optimization at
the after-C1 level. We performed a partial
point-by-point optimization for the S** state al
t A misprinl in ref. [2fl

quotesthis value at 4 kczllmk

2.0 A ethylene-ethylene separation. The same

was done for the ST state at 2.8 A. This afterCI optimization was done by varying only the
CC distances and the CHI ffap angles.
For the UHF triplet surface a more complete
optimization was performed [g] using the same
repatameterized CNDO method [2f]. However,
exploratory calculations were aiso done using
the unparameterized INDO as well as
MINbO/S methods. These latter methods were
rejected for reasons discussed below,

energies of different molecules [12] hes been

established [13] and largely corrected at the
MCSCF level [14]. Likewise, we have demonstrated that our reparameterized CNDQ CI
method yields adequate appearing ground and
excited state bond rupture surfaces [2f]. It
remains to be shown by comparative calculations, however, whether or not a CNDO CI
method can generally mimic the excited state
surface features generated by an ab initio calculation of similar basis size. Thus, part of what
.-Jill be explored here is a comparison of such
calculations and problems encountered.

3. Reaulls nnlddiscussion
3.2. The ethylene-ethylene triplet dimerizatiotl
3.1. Gerteral methodological onsideratiorrs
It is our general view that useful inexpensive
information on excited state behavior can be
obtained using semi-empirical methods [2f, 91.
The disrepute of such methods lies mainly with
their quantitative uncertainties and seemingly
ever changing parameterization schemes. It 1s
probably a general opinion that for small molecular systems with a large basis set, large CI
cnlculation can be trusted for a surface calculation involving some changes in relative correlstion energies along that surface [lo]. For
huge molecular systems, financial or technical
limitations impose smeller basis sets such ih:lt a
lorgc CI treatment may be difficult or presently
impossible and the resulting surfaces poor [IO].
Since both ab initio and semi-empirical calculntions using similar size basis sets will carry
the same symmetry information, semi-empi::ical
CI methods still have the potential of giving
useful information on large systems, In this case
the advantages of the small basis set semiempirical CI method over its ab initio counterpart lies in its variable parameterization. Th,us,
the CNDQ/S method [l 11, will still give be.ter
estimates of transition energies For a large
system tharl will a small basis set ab initio
method. Neither the CNDCI/S nor the original
CNDQ/INDO methods were originally
parameterized with the intention of doing s.uface calculations. The main reason for their
poor estimate of the relative ground state

Available thermodynamic, spectroscopic and

theoretical data indicate that the reaction of
twisted triplet ethylene (3E90-, CC = 1.48 a [IS])
with ground state ethyfene (l$) to give the
triplet tetra-methylene diradicai (TMDR) is
about 19 kcal/mole exothermic:
Eob+ 3Ego.= 3TMDR,

AH = - 19 kcal/mole,
(l!

I$,- -I-I& = cyclobutaae,

AH = - 18 kcal/moIe [ Ic],
cyclobutane

(:!;

= TMDR,

AH =53 kcal/mofe [ICI,

*Eoo+ hv = Euom, AH = 64 kcal;mole,

13)
(1)

This estimate (1) is obtained by combining

reactions (2), (3), and assuming that TMDR
and TMDR are nearly isoenergetic.
Only in reaction (2) do we have a true
experimental value. For reaction (3) we assume
that, the activation energy for the thermal
decomposition of cycfobutane is identical to the
enthalpy change generating TMDR even
though it has been theoretically indicated [Zc]
that there may be several TMDR intermediates
which are several kcal/mole lower in energy.
This would make the value shown for (1)
slightly more negative. Finaflv, the value shmvn
for reaction (4) is theoretical [15a. b]. Llowevcr.
theoretically Ego0and Ew are nearly isoenergetic and thus the energy of reaction (2)

E. Kassab et al. 1 theoretical analysis of the cycloadditiin of ethylene

154

will approach the known activation energy for

thermal cis-trans isomerization of ethylene [lc].
Even though triplet sensitized photodimerizations of small ring oIefins have been
commonly observed [le-j] reaction (1) has
never been fully demonstrated to occur with
ethylene .of simple acyclic olefins. This observation WI be conveniently rationalized [lg] by
examining the kinetic expression for the disappearance of triplet olefin (3A) by competitive
unimolecular intersystem crossing
3A%1A,,

(5)

and bimoIecular dimerization

3A c A,, 2

3DR_

(6)

The fates of the generated diradical, DR+

DR, would only be important if for some
reason the regeneration of starting material
from DR was highly favored only in the case of
acyclic olefins. if we assume that only reactions
(5) and (6) dominate in both types of olefins,
then:
d(3A)/dt = -!c~(~A) - kX3A)(A,J.

(7)

The trajectory calculations of Warshel and

Karplus 1161, indicate that ki, in ethylene is
strongly dependent on the 3AS(l,1A90- energy
gap, a result similar to the known experimental
and theoretical energy gap dependence for triplet-ground state intersystem crossing in
aromatics [17]. The near degeneracy of the tripIet and ground state surfaces in olefins occurs
onIy near the twisted 90 configuration of the
p-orbitals comprising the z-bond. While the
triplet states of small ring olefins will undergo
some relaxation, it is axiomatic that the T-S
energy gaps in relaxed cyclic olefin triplets will
be larger than for acyclic triplets. Thus, it can
be argued that it is the variation of kk with
olefin structure which controls the partitioning
of reactions (5) and (6).
There is an additional nuance to the
arguments posed above. If the values for kd are
less than diffusion controlled ones! this implies
enthalpyas well as entropy of activation effects

in reactions of the same type as (1). It is commonly assumed that triplet addition reactions
are radical-like in character. If so, one can
anticipate radical-like kinetic parameters. Our
goal will be to estimate activation energy and
enthalpy for reaction (1) as well as to attempt to
characterize the radical-like nature of the reaction pathway using geometry and spin transferspin polarization criteria_ We will also investigate
the possibie differences in triplet sensitized
photodimerization
cyclic and acyclic olefins.
We will only report in detail on the computed
optimized triplet reaction path for reaction (1)
generated using our reparameterized CNDOUHF method [2f]. It was initially determined
that an unreparameterized
INDO-UHF method
gave a hopelessly false enthalpy for reaction (1)
(ca. -100 kcal/moIe, versus -19 estimated) as
well as intuitively false geometries for 3TMDR
and intermediate structures. While the
MINDOi3 half-electron method gave a
reasonable estimate of this enthalpy
(-31 kcal/moIe), the optimized C-C geometry
for 3E90n(1.36 A) was very far from the best ab
initio value (1.48) [15]. Likewise, the
MIND0/3 optimized geometry for trans3TMDR gave 1.44 8, for the -CHz-CHz distance, somewhat far from what one would
expect from a C-C sp3-sp2 hybrid (1.52) [IS]+.
Our own CNDO-UHF reparameterization
yielded -27 kcal/mole for the enthalpy of reaction (l), and 1.49 and 1.52 for the C-C distances in 3Egc. and 3TMDR. Since the same
CNDO reparameterization
is used in our
CI calculations discussed in the next section
we decided to retain the same overall
parameterization for both the UHF triplet and
RHF-CI singlet surface in spite of the fact, as
will be shown, that the final computed activation energy for reaction (1) was not satisfactory.
It should be stressed, however, that from a
general methodological point of view the use of
a UHF single determinate method to compute a
surface of a bimolecular reaction between what
are, at a dissociation limit, a closed and open
shell species, will give rise to a relative corf See also ref. [k].

E. Kassab et al. /

Theoreticalanalysisof the cycloodditionof ethylene

relation energy error [19]. In any case, the

following energetic analysis is given using the
reparameterized CNDO-UHF approximation.
First, in order to determine the energetics of
the reaction of nearly rigid smali ring triplets we
computed the following UHF geometry optimized reactions using our modified CNDO
parameterization:
3Eoa(CC= 1.35) = 3Erp(CC = 1.54),
AH = -28 kcal/mole,
3Eoe(CC= 1.54) = 3E90.(CC= 1.49),
M = -16 kcal/mole.

(8)
(9)

Reactions (8) and (9) have previously been

estimated by Baird and co-workers 1201 at -32
and -16 kcal/mole, respectively, with virtually
the same optimized CC distance. As a model
calculation for the cyclopentene triplet, we performed geometry optimizations on ethylene in
which only two cis-hydrogens and the CC distance were allowed to vary and found an essentialIy planar structure with the same CC distance and energy as shown for reaction (8).
Thus, in a certain sense, small ring cyclic olefin
triplets contain about 16 kcal/mole excess
energy as compared to relaxed acyclic olefin
triplets.
The geometry optimized CNDO-UHF minimum energy pathway for the reaction of 3Eg0.
with the ethylene ground state is shown in fig.
1. For comparison purposes, the reaction of the
methyl radical with ethylene is shown in the
same figure. The critical coordinate is the CC
bond distance between reacting carbon centers,
this being sufficiently large at the transition state
(ca. 2.5 A) that little activation energy
difference was found for rotational variants
about the forming CC bond. The optimized
geometry of the tfansition state for reaction (l),
shown in fig. 2, shows little geometry change in
the reacting moieties as compared with their
isolated structures. The possibly more critical
measure of progress along the reaction coordinate is the spin density. In both reactions
there is virtually no spin transfer at the transition state. Both the geometry and spin density
transfer criteria are consistent with the inter-

155

pretation that the transition state is more reactant-like than product-like. On the other hand,

while little spin transfer has occurred, the

accepting carbon atom in both reactions exhibits
a large negative spin density, a polarization
which occurs well before the transition state.
Even though an unprojected UHF calculation
will overemphasize such spin polarization, what
is observed demonstrates the principle that a
negative spin density at the receiving carbon
atom in radical reactions is a required precondition for bond formation [22]. What we had
not anticipated is that such spin polarization
would occur at distances very much larger than
that occurring for the threshold for spin transfer. In any case, the theoretical profiles for both
radical and triplet addition to ethylene are
similar, giving theoretical support to the idea
[22] that some triplet state reactions are radicallike in character.
As discussed below, the main negative feature
of the CNDO-UHF calculations presented is
that they give unreasonably high activation
energies. However, we decided to use our
CNDO-UHF calcuiation of the methyl radicalethylene reaction to estimate the probable
activation energy of reaction (1). Reaction (1)
has a computed activation energy of
28 kcaljmole while that of a simulated cyclopentene triplet-cyclopentene
is 21 kcal/mole.
This latter value is comparable with our own
computed value, 19 kcal/mole, for the methyl
radical-ethylene reaction which is, in turn,
about a factor of two, too large (ohs., 8
kcal/mole) [23]. Thus, it can be argued that the
olefin tripiet-olefin reaction should have an
activation energy comparable to normal radical
addition reactions. Therefore, based on this
comparative method we predict that the reaction of cyclic olefin triplets with olefins should
have activation energies in a region of
8 kcal/mole. Acyclic olefin triplets may have
activation energies several kcaljmole higher
than this value. Thus, it is predicted that the
low quantum yields of acyclic triplet sensitized
photodimerizations are due to a combined high
value for kec and lower than diffusion controlled
rate for kd. However, in cyclic olefins ka should

CARBQN-CARBON

BOND

DISTANCE,

ANGSTROMS

Flfl. I. Rep~rnmcterizizd
[2f] CNDO4JHF
calculations of the addition of triplet ethylene to ethyk~
and m&,4
r&k%! BD
cthylct~c. Shown is the minimum geometry optimized pathway for an in-plane carbon amm co&go&o%
wi~-irhCfM &T%B~
kept constnnl al 1.08 A. Also shown are the spin transfer from the radical or triplet species to e~I~@oe and the mzgz~~ spz~
dcnuily n1 the occepling carbon atom along the reaction coordinate.

..
nlso be lower than diffusion controlled rate.
lhus, in a renl sense, ir is the variation in the
kilir values which differentiate the triplet sensitized phatodimerization kinetics of acycIic and
cyclic olcfins. Sin&r effects should occur in
cyclic and acyclic polyenes. It is known that the
qunntum yields for sensitized photodimerization
OFcyclohexadiene (ca. 1) are much higher than
for butadiene (O.Ol) [22]. On the other nand,
\ve have found virtually no reported experimcntul values for activation energies for triplet
nddition reaction aside from a recent value for
tht! reaction of triplet trimethylenemethane with
a substituted olefir~ (6 kcal/mole) [24].
3.3 LVe cthyltme-eth ylene excited singlet surfaces
3.3. I. Qttalitative aspects
The essential details of the calculations
presented here are shown in figs. 3 and 4 for
the semi-empirical and ab initio calculations,

respectively. The detailed energeti

of the
latter calculations are shown in tablie P. I%e
geometry choices for the ab in&o ~~~~~
at
the intermediate geometries (ca.!cuLat&~, B-5
table 1 and fig. 2) were bzsed cm S&ese1?3empirical results, oost amsi&rat&ms preventing
us from doing a surface sear& fcr the 9*
minimum. In both the semi-empfal
a& &
initio czlculatians the minimum d timeS 51ifface is in the 2.0-2.2 A regk~~
Qualitatively, the ab initio ay.xdse&e
calculations show the same be
portions af the H, surface wea
Michl and co-workers 13
possible photochemical
faces has already been
these workers. We will dli
ia detail s~mr:d
the complications invoived in treatig a very
much larger system, especially in wbzt mzmncr
OUTcalcul2tions are diEerentia@d &om mrE+
calculations on the same system.

E. Kmab

er al. f Th@orelfcal at&is

Fig 2. The geomeby of the uptiMid

transition state of the
calculation shown in fig. 1. A&J shown are the individual
atomic spin deMies as well I the total amount of spin
density tidefred
of retained on each ethylene udit.

Both the semi-empirical and ao initio ca!culatiors give essentially the same qualitative
infarmation, namely that there are two excited
states Sf and S** of the ethylene dimer which

oftlthz
cyclnaddirion

ofethylene

157

are involved in the photodimerizadon process.

Initially, ar large ethylene-ethylene separations,
tbe ST surface is lower or nearly isoenergetic to
the S** state, but dt the HOMQ-LUMP
avoided state crossing region near 2.0-i-2 8,
ethylene-ethylene separatian the S** state
becomes lower in energy. A5 seen in table 2, at
short ethjrkne-ethylene distances, the
configurational compasitinns of the SOand s
states are as expected from orbitel symmetry
rules. They both consist mainly of plus and
minus combinations of two major configurations, one the closed shell SCF solution
(HOMO doubly occupied) and the other the
doubly excited configuration (LUMO doubly
occupied). The relative weights of these two
configurations change radically for the SOand
S** states over a Iairly narrow geometry region
of

significence

singlet excited stare, S, and dauhty excited state, S**.

E. Kasab eta!. / ?heoreticaI analysis of the cycloaddition of ethylene

158
I

simple, it becomes largely monoconfigurational

at the cyclobutane or two ethylene limit.
The configurational behavior of the S** state
is much more complicated. It does not evolve
towards a S** state of monomeric ethylene as
might be indicated by a 2 ~2 CI [2b] or a state
correlation diagram. As in the case of I& the
S** state correlates with two ethylene triplets
[4,26]f. This is shown in table 2 where the S**
state is shown to be neither principally a closed
shell doubly excited state nor a two open shell
monoexcited state but a four open shell doubly
excited state at 3.5 A. The calculation shown in
table 2 is done under conditions where the
ethylene dimer is in a trapezoidal geometry
where the MOs are Iocalized on either one
ethylene or the other at large ethylene-ethylene
separations. If the dimer is calctdated under DZh
symmetry, a set of delocalized MOs is obtained
which have a correspondance with those anticipated from orbital symmetry rules. Unfortunately, the configurational composition of
the S* state at large ethylene-ethylene separations depends on whether one is working with
localized or delocalized MOs In the case of

Fig. 4. Ab initio CI calculation of the cycloaddition of

ethy!ene to give cylobutane. See table 1 for geometry
detaiIs. Caicularion used an after contraction 40 orbital basis
set for cyclobutane plus CI at about the 400x400 level
using a configuration selection threshold of 5x IOm1hartree.
Energies for the e:hylene (e) dimer limit (00) are twice the
energies shown in table 1.

than it is usually. Likewise, this surface instability will permit the formulation of diabatic
functions interconnecting the SOand S**.surfaces [257. More simply stated, this geometry
region is sutliciently theoretically special to
warrant the speculation that it is where the
internal conversion from S** and So occurs [4d].
A detailed discussion is necessary concerning
the correlation of the S** state at large ethylene-ethylene separations [26]. The configurational behavior (table 2) of the So state is

? Note that this point is overlooked in the correlation

diagrams proposed in related types of photocycloaddition
reactions: see for instance ref. [27].

Table 1
AS initio SCF-CI calculations on ethylene-ethylene
Cal.

.9

R,

RL

R,

State

SO

1
2
3
4
5
6
7

IS
1.41
13
1.40
11
1.39
9
1.38
3.8 134
ethylene
cyclobutaneb

1.415
1.425
I.435
1.440
1.500

1.90
2.00
2.10
2.20
335

S**

T*

SCF

CI

CI

SCF

-155.562
-155.640
-155.700
-155.747
-156.875
-17.952
-155.961

-155.955
-155.936
-155.931
-155.945
-155.078
-78.079
-156.029

-155.745
-155.809
-155.838
-155.825
-155.733
-77.477

-155.562
-155.767
-155.639
-155.789
-155.645
-155.792
-155.644
- 155.787
nonconvergent
-77.526
-77.672

CI

SCF

CI

-155.736
-155.757
-155.766
-155.771
-155.723
-77.808

-155.866
-155.886
-155.893
-155.889
-155.908
-77.852

a)Experimental geometry.
) Planar geometry as found in 6-31G* calcuiation of Cremer [32]. Other geometries were taken from semi-empirical calculations, geometrical parameters not shown were not changed, CH kept constant at 1.09, HCH bond angle at 112. See fig.
1 for definitions of S, R,. R2 and RO_

E. Kassab eta!. / Theoreticalanalysis of the cycloaddition of ethylene

Table 2
Leading configurational

terms in the ab initio calculations

Config.

Ri

coeKb

(HOMO)

1.9

So
s**
So
.S**
So
!Y*
SO
.S**
So
S**

=
=
=
=
=
=
=
=
=

0.215
0.900
0.379
0.846
0.662
0.539
0.842
0.397
0.929
-0.048

2.0
2.1
2.2
3.5

(LUMO)
+
-I+
c
-

0.919
0.200
0.860
0.359
0.665
0.639
0.420
0.807
0.151
0.213=j

AngtrBm units.
) Either double occupation of HOMO or LUMO.
For this distance the major configuration is a four open
shell having a value of 0.771. this configuration is related
IO two ethylene triplets, see text.
d For both the S* and T states at each distance, the major
configuration (0.9.5-0.96) has a single occupation for the
HOMO and LUMO.

between these five configurations and two triplet

ethylenes at large ethylene-ethylene
separations
is difficult to see. Our general conclusion is that
in this and similar types of calculations it is best
to impose a slight symmetry breaking on the
system is order to obtain localized orbitals at
large separations.
With respect to the ab initio calculations the
configurational behavior of the SF and T1 states
is simple, they are both largely purely HOMO+
LUMO open shell states (over 90% monoconfigurational). With regard to the semiempirical calculations the lowest energy S* state
(Bz in C,,) has Z-U* not Z-T* character at large
ethylene-ethylene
separations but undergoes
change in configurational character at small
separations and becomes JXT*. This is an artifact of the CNDO method even under our
parameterization.

3.3.2. Quantitative aspects-the

localized orbitals (table 2) the double triplet
character of the proper (S2 = 0) four open shell
configuration is hidden within the polydeterminatal structure shown below:

where the indices 1 and 2 refer to orbitals

largely localized on either ethylene 1 or 2. The
energy of this configuration at large ethyleneethylene distances tends to become bitriplet in
character because only the central two determinates contribute to the orbital-orbital
exchange term K. Likewise these central
determinates are triplet in character because
one has either both (Yor fl spins in the same
molecule. This behavior is also found in the
semi-empirical calculations performed using
localized orbitals. However, using del6calized
orbitals the S**state becomes polyconfigurational at large distances, i.e. HOlMO+
LUM02; HOMO+ (LUMO + 1); (HOMO l)+ LUM02; (HOMO - 1)2-+ (LUMO -I-1)
together with the four-bpen-shell determinate
shown above. The conceptual relationship

1.59

correlation

energy problem

With regard to the computed ground state

energetics of the cycloaddition of ethylene,
there are a number of previous calculations at
the ab initio SCF [2b, 2c] SCF-small CI [2b, 2~1
as well as ihe semi-empirical level [2a, 2d, 2f2i]. At the SCF level, the ground state thermodynamics are greatly in error using a small ST0
[2b] or STOJG [2c] basis set (talc. ca.
-80 kcal/mole, obs., -18) [lc]. Essentially
experimental values are obtained from 4-31G
and 6-31G* calculations [28]. With regard to
the STO-calculations [2b] a simple 2 ~2 CI
showed essentially no energy lowering for
cyclobutane but about 0.08 au (ca. 50
kcal/mole) for two ethylenes. Similarly a srpall
CI treatment [2b] at the STO-3G level
shows a much greater energy lowering for
ethylene than for cyclobutane [2c]. These
small C&mall basis set treatments essentially
improve the apparent agreement between
the calculated (after CI) and observed enthalpies
of the reaction by lowering the energy of
ethylene more than cyclobutane. This implies
that the total valence correlation energy of
two ethylenes is much different than

for cyclobutane which, as we wid show, is not

the case. Our own calculation at the SCF level
yielded a computed enthalpy for this ethylene
cyeloaddition reaction of -44 kcaf/mole (exptl.
-!,R) which while better than the STO-3G-ST0
cefculationa quoted above is worse than a 41 I G or 6-31G estimate. However, imposition
af Cf at about the 400x400 level makes this
value in even worse*(ca. +bO kcal/mole)
ngrcrmcnt with the experimental value than at
the SCF level! The possi,bfe sohnxon of imptovbrg rho SCF treatment using a larger basis set
will not improve the above agreement except at
the SCb Icvel. The problem resides in the CI
technique used. An analysis of this problem
requires some estimate of the correlation energies of both ethylene and cyclobutane in order
to find cut how much of this energy is not being
cnlculntcd.
Shown in tnble 3 are the estimated correkition cncrgies for each localized carbon 1s
?orc, rmd the CH and CC valence orbitals for
koth ethylene and cyclobutane as obtained from
a correlative equation [7] relating the SKI-3Ci
localized orbital size to the correlation energy.
In the RISCof ethylene, the computed total
corrclntion energy, OS4 au, is sufficiently close
10 the estimated vult~c (0.522) 17,291 that some

lilhk I
~~~~IcIIII~B~
energy
__Ix_

-.-_..

h~<Illxulo
. .._ _
0iiylrnc

cyclulullrrllc

Donrl or orbital
type lacnlircd
In
Cti
CT

Is

C.~~f
CC

__,_ .,...*., _-_

AimatCs

___

fat ethylene

and cyclobutane

((rllrl$))*
R,

Correlation
energya (au)

(1.316
0.1040
1.516
0.0560
1.6X
0.0546
correlation energy, core * 0.207
vnlctke
shell * 0.333
total * 0.540
0.317
0.1033
I.515
0.0560
1.544
0.0567
corrclntion cnurgy, core = 0.413
velencr shell = 0.671
total = 1.084

Iidculuted
from the equation, Emrr = -0.06593
IIIR,, Vh), see textnnd ref. [7].

confidence can be placed in ~dd~t~o~~ par&

tioning of this energy into core and valence
terms. Our computed valence correlation energies
of ethylene (0.333) and cyclobutane (8.671 j
are such that there is essentizify no great carrelation energy difference for the reactioraof
two ethylenes to give cyclobutane. Thus, if we
were onfy interested in the enthafpy of this
reaction, we would not wish to go beyond a
large basis set SCF estimate. With regard to a
very large basis set-nearly complete CI treatment of the ground state of etiyfene, the
valence correlation energy actmlly obtained has
evolved over the years from intermedir?e values
of about 0.2 au to the most recently co;.rputed
value of about 0.33 au (0.36 estimated] l30].
Our own middle level CZ treatment yielded only
0.13 au for ethylene and 0.068 for cyclabutane.
Especially in the case of cyclobutane the Cl
treatment has only obtained about 10% of the
total valence correlation energy.
We know from the above discussion that the
calculations shown in fig. 4 and table 1 .re
faultsd because of an imbalance in the estimated relative correlation energies of ~~ctobutane and two ethylenes. The reason for this
imbalance is that the CI ~afcufation estimates
between cyclobutane and ethylene are not size
consistent [31]. Since the CI space of ethy;;ne is
smaller than cyclobutane the same configurational selection criteria (5 X lO-4 au) will yield
more correlation energy in the case of ethyfene
thhn for cyclobutane. Thus, from a size consistent stand point, only calculations l-5.7 shown
in table I and fig. 4 are comparable. Does this
mean that we can regard that portion of fig. 4
(and table 1) as more believable if one rejects
the consideration of the two ethylene limit?
Two things argue against this ahernate pofie.
First, since only 10% of the valence correlation
energy is estimated in the case of the grouno
state of cyclobutane there remains a large
margin of error. As one proceeds afong the
surface some of the orbit& will fncrease in
energy and states witi approach one another. fi
is likely that the same configuration selection
threshold energy wit1 produce a much higher
percentage of the vafence correlation energy

.G. Karsnb

et al.

/ Theoreiicqt

analpis

along certain portions of the surface than along

others in addition to that obtained from a mere
HOMO-LUMO indwcd avoided crossing
behveen SOand S* (i,e. a 2x 2 CI). In the case
treated here, the computed barrier for the
concerted 2S+2S transition state for the ground
State surface decomposition of cyclobutane to
two ethylenes is less than 60 kcal/mole. This is
less than the observed activation energy (+63
kcal/mole) [lc] for a process which is probably
biradical-like in character [2c]. Our conclusion
is that an intermediate level CI treatment
cannot give adequate results on this surface
regardlessof the irrikd ab initib basis set.
With regard to the CNDO-CI calculations it
must be pointed out that a similar size consistency problem exists with regard to the CI This
can be demonstrated by examining fig. 3. Originally the overall thermodynamics of the
cyclobutane-two-ethylene reaction was calibrated at the 60x60 CI level by individual calculations on cyslobutane and a sblgle ethylene
to give the experiniental value of about
20 kcal/mole [2f]. In the surface actually
generated in fig. 3 the same configurational
composit,an was maintained along a soxface
which begins with cyclobutane and terminates at
4.5 A with an ethyb;e dimer. The So surface in
fig. 3 does not asympotitically approach the
20 kcal/mole calibrated value at large
separations. This results from the fact that as
with the ab initio CI calculation it is easier to
compute a greater percentage of the correlation
energy when the system is smaller (e.g. ethylene) than larger (ethylene dimet) using the same
number of configurations. However, unlike the
ab initio calculations, a semi-empirical technique can be recalibrated under size consistent
conditions (i.e. cyclobutane and ethylene dimer
at large separations). Likewise, since the semiempirical-after-Cl results are parameter
dependent, a completc CI is not necessary as
long as the major correlatively important
configurations are included. In the case of the
S** surface at large ethylene-ethylene sepatations the semi-empirical CI treatment must
include doubly excited four-open-shell
configurations. In principle, the inclusion of

of the cycloaddition

ofethykne

161

such configurations would involve a large CX

treatment requiring a Parge search ta obtain rhe
important ones* In fact, the important
configuratiuns can be detelm,ined by a few preliminary calculations at various points along ?he
reaction surface. Ir this mtmner, the semiempirical Cf treatment can be kept wlthin the
level 100 x 100. However, it must be pointed
out that the amount of semi-empirical carrel&ion energy will also depend on the size of
the Cl treatment. At the 60 x 60 level this
energy was found to be 0.045 au for the So stntc
of ethylene, increasing to 0,087 au ai the 1lllx
110 level, the latter containing all totally symmetric mono- and dr;uble+xcitations. The latter
energy obviously has no relationship to lhc
above discussed estimated valeilce correlation
energy (table 2) of 0.33 au. Likewise, a semiempirical potential eaergy curve calibrated with
one set of configurations Will be out of calibr;ltion under another set.
With regard to I~.:: problem treated here, $1

comparison of the semi-empirical and ab initio

stirfeces (figs. 3 and 4j shows that there is a
VISUJresemblance in the two computations ~II
the region of avoided crossing at 2.0-2.2 A ill:
well as along the surface between 2.0 to 4.5 h.
The semi-empirical calculation gives the same
correlative information as does the ab initio
one. Both sets of calculations, however, Jo Ilot
give us an accurate idea as to the height of the
So and S*kstates in the region of thy HOMOLUMQ crossing,

For the triplet diradical surface reparameter&ted CNbO-UHF calculations indicate

that the reaction of olefin triplets with olefins
should involve activation energies similar to
I-adical-olefin reactions. The theoretical profi!t.s

of both types of reaction are similar, as

measured by spin transfer and spin polarizotiotl
;rt the transition state as well as the general
:!ppearance of the reaction diagtan?.
A comparison of ab initio sod semi-empilicl!
I :I calculations for the 2S+ 2S cyctoaddition

162

E. Kamb et al. / Theoretical analysis of the cycloaddition

of ethylene

surfaces shows similar qualitative behavior. We

demonstrate that the configurational behavior of
the S** state at large ethylene+zthylene distaxes is unlike that prediCted by simple orbital
symmetry rules. This state correlates with two
triplets of ethylene. FinAlly, we show -that the
system cannot be treated using ab initio techniques at the intermediate CI level. A separate

estimate of the valence correlation energy of

cyclobutane shows that our calculations only
obtained about 10% of that energy using a
configuration

selection of 5 X low4 au.

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