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THEORETICAL
ANALYSIS
OF THE CYCLOADDITION
J.J. DANNENBERG*
OF ETHYLENE
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
1JI
of erhpkne
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
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
AH = - 19 kcal/mole,
(l!
(:!;
= TMDR,
13)
(1)
154
(5)
3DR_
(6)
(7)
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. /
(8)
(9)
155
pretation that the transition state is more reactant-like than product-like. On the other hand,
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,
E. Kmab
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
significence
158
I
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
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_
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.
1.59
correlation
energy problem
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].
.G. Karsnb
et al.
/ Theoreiicqt
analpis
of the cycloaddition
ofethykne
161
162
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163