Geometry, Reactivity, and Spectrum of Cyclopropane 1299

in the case of adsorbed oxygen. Thus we conclude that step is in our opinion suitably characterized by means
different types of oxygen are involved even if, as in the
first case, we cannot postulate any reasonable model.
Our conclusions introduce into the chemistry of
catalytic oxidation of CO on semiconductor oxides (we
recall the analysis contained in the review of Stone3)
the concept of “precursors.” They are most likely CO
molecules reversibly linked to surface metal ions, and
play a determinant role in the formation of oxygenated
complexes. The process COgas —»COaas which is
considered, in the usual mechanism, as the preliminary
Downloaded via UNIV NACIONAL AUTONOMA MEXICO on January 24, 2024 at 00:34:31 (UTC).
See https://pubs.acs.org/sharingguidelines for options on how to legitimately share published articles.
of ir spectroscopy. The generic definition of COaaa
can thus be identified with the CO reversibly linked to
metal ions through a weak bond. Finally, we think
that the oxygenated complexes might be identified
with carboxylate structures, even if the complexity of
our spectra do not exclude the possibility of the presence
of other species on the surface.
Acknowledgment. This research was supported by
the Italian Consiglio Nazionale delle Ricerche,

Theoretical Study of the Geometry, Reactivity, and Spectrum of Cyclopropane

by Robert J. Buenker
Department of Chemistry, University of Nebraska, Lincoln, Nebraska 68508

and Sigrid D. Peyerimhoff

Instituí fur Theoretische Physik, Justus Liebig-Universitdt, 63 Giessen, Lahn, West Germany

Ab initio SCF-MO and Cl calculations have been carried out for the cyclopropane molecule CsH6 for a series
of CCC internuclear angles in order to study the geometry of this molecule in its ground and excited states;
from this treatment an equilibrium CCC angle of 65° is indicated. A basic similarity between cyclopropane
and the series of symmetric AB2 molecules (and others) is pointed out; all possess C2v symmetry throughout
their respective bending processes and their angular correlation diagrams show a general agreement between
shapes of corresponding orbital energy curves. The great disparity in the geometries of cyclopropane and
its isoelectronic AB2 and HAB2 counterparts ozone and formate ion is thereupon related to the fact that these
systems possess different ground-state electronic configurations; in turn it is shown that this distinction is
caused by the ability of hydrogen AO’s to selectively alter the stability of the orbitals of a parent AB2 molecule.
Development of this concept also allows a consistent explanation for the unusual reactivity of cyclopropane.
Cl calculations are employed to study the electronic spectrum of CgHg and they indicate that the majority
of the known ultraviolet absorptions of this system cannot reasonably be assigned to vertical transitions;
instead 0-0 excitations involving upper states with wide-angle equilibrium geometries are suggested.

I. Introduction for the unusual properties and reactivity of cyclo-

The cyclopropane molecule CsH6 is well known to
exhibit anomalous behavior among organic systems with
regard to binding and reactivity. According to the
simplest valence bond description the molecule possesses
pure CC single bonds (experimental bond length1·2
1.51 Á) and yet its CCC angles are all approximately
60°, much smaller than the tetrahedral angle character-
istic of other saturated organic molecules. Further-
more, cyclopropane undergoes certain addition re-
actions such as hydrogenation in the presence of a
catalyst and bromination in carbon tetrachloride, also
in definite contrast to the behavior generally observed
for singly bonded hydrocarbons.
Several explanations have previously been offered
propane,3 perhaps the most celebrated of which are due
to Walsh4 and Coulson and Moffitt.5 It is the purpose
of the present paper to discuss these matters in con-
siderably more quantitative detail, by means of ab
initio LCAO-MO SCF calculations, than has been
possible previously; a simple qualitative theory is
sought to explain the anomalous characteristics of
cyclopropane in a manner which is still clearly con-
(1) O. Bastiansen, F. N. Fritsch, and K. Hedberg, Acta Crysi.,
17, 538 (1963).
(2) L. C. Snyder and S. Meiboom, J. Chem. Phys., 47, 1480 (1967).
(3) W. A. Benett, J. Chem. Educ., 44, 17 (1967), and references
therein.
(4) A. D. Walsh, Trans. Faraday Soc., 45, 179 (1949).
(5) C. A. Coulson and W. E. MofBtt, Phil, Mag., 40, 1 (1949).

Volume 78, Number 6 May 1969

 1300
sistent with previous results concerning related sys-
tems. In particular, it is interesting to consider
cyclopropane in light of a former study dealing with
systems isoelectronic with it, namely ozone O3 and
formate ion6 HCOO-; from this it has been concluded
that at least the geometrical behavior of H„AB2
molecules in ground and excited states can be under-
stood in the same terms as that of simple triatomic
systems. In order to conduct such a study, SCF
wave functions are determined for cyclopropane as a
function of its internuclear CCC angle; configuration
interaction calculations based on the initial SCF
treatment are also helpful in this connection, in addition
to enabling detailed consideration of the molecular
spectrum of this compound.
II. Calculations
In order to be consistent with previous wrork dealing
with6·7 03 and HCOO~ a basis set of fixed group gauss-
ian lobe functions8 has been employed throughout this
investigation. The AO basis set consists of 25 gaussian
AO’s on each of the three carbons, ten of s and 15 of p
type (with the twro lobes representing a p function
being counted as one AO) and five additional s-type
gaussians on each of the six hydrogen atoms. These
functions are grouped in fixed linear combinations so
that only 24 linear coefficients are left free to be de-
termined by the SCF procedure, for three s and three
p group functions on each carbon and for one s group on
each hydrogen. Exact values for the exponents, lobe
separations, and fixed coefficients within the various
group functions have been given elsewhere8·9 (hydrogen
scale factor of 1.414).
The coordinate system employed for the 60° <£. CCC
calculation (equilateral triangle) is given in Figure 1;
the CC bond length was taken to be 2.88 bohrs, the CH
distance 2.022 bohrs, and the angle HCH equal to
120°. Each of these assignments10 differs slightly
from the present best experimental values1·2 for these
quantities, which were determined under the assump-
tion of an angle CCC of 60° (D3h symmetry). In
addition to this calculation, four others were carried
Figure 1. Molecular geometry oí cyclopropane C:¡He.
The Journal of Physical Chemistry
Robert J. Buenker and Sigrid D. Peyerimhoff
out at CCC angles of 45, 80, 100, and 120° for which
all other parameters such as CH distances, CC dis-
tances between the central and each terminal carbon
atom, and -£HOH remained the same (the HCH
plane is ahvays taken to bisect the respective -£CCC).
Two larger CCC angles were also considered, 140 and
160°, but for these cases <£HCH was also increased to
140 and 160°, respectively, in order to compensate for
an expected dependence of this parameter upon <£CCC.
The results of this series of SCF calculations show a
minimum in total energy at 63.5° for the closed-shell
ground state. The difference between this theo-
retical value and that generally assumed for equilib-
rium cyclopropane is larger than the difference found
for similar comparisons between calculated and ex-
perimental internuclear angles for other systems6·7
such as HC()0~ and O3, although it should be pointed
out that the existence of a number of additional free
geometrical parameters in the case of C3H6 not ex-
plicitly varied in the present treatment might be
responsible for much of the former discrepancy. Total,
kinetic, and orbital energies for the D3h calculation are
given in Table I along with corresponding data from a
previous gaussian calculation by Preuss and Diercksen.11
These authors employed a much smaller basis set of
42 AO’s and their resulting total energy is 0.90 hartree
(24.5 eV) higher than the present SCF value. The
orbital energy order is the same for both calculations
with the present set being everywhere lower than the
other. Using Koopmans’ theorem to calculate the
minimum ionization potential, one finds a value of
10.46 eV for the smaller basis set calculation11 and
11.97 eV for the present treatment (experimental
value 10.2 eV11). Semiemprical calculations on cyclo-
propane by Clark and Ragle12 give ionization potentials
of 15.4 and 11.6 eV by using the CNDO/2 and CNDO/1
methods, respectively.
At most CCC angles an SCF solution was also ob-
tained for an excited state of C3H6; this additional work
seemed necessary because of the following two points:
( ) the other state in question, in winch the 4b2~la2'
MO is doubly occupied at the expense of the le-fiax
MO relative to the configuration given in Table I,
becomes the lowest closed shell state at angles larger
() S. D, Peyerimhoff, J. Chem, Phys., 47, 349 (1967).
(7) S. D. Peyerimhoff and R. J. Buenker, ibid., 47, 1953 (1967).
(8) J. L. Whitten, ibid., 44, 359 (1966).
(9) The hydrogen function also due to Whitten is given by R. J.
Buenker, S. D. Peyerimhoff, and L. C. Alien, ibid., 45, 734 (1966),
Appendix I.
(10) “Tables of Interatomic Distances and Configuration in Mol-
ecules and Ions," Supplement, Special Publication No. 18, The
Chemical Society, London, 1965.
(11) H. Preuss and G. Diercksen, Intern. J. Quantum Chem., 1,
361 (1967), and “Arbeitsbericht der Gruppe Quantenchemie, Max-
Planck Instituí für Physik und Astrophysik,” No. 2, 1966. There
is a small discrepancy between the ionization potential given in the
article as 10.33 eV and the highest orbital energy of -0.3845
hartrees = 10.46 eV also given therein.
(12) P. A. Clark and J. L. Ragle, J. Chem. Phys., 46, 4235 (1967).
Geometry, Reactivity, and Spectrum of Cyclopropane 1301

Table I: Total Energy Et, kinetic energy f?k, and Orbital

but not in a given state of such systems, is placed in

Energies for the Ground-State Configuration of Cyclopropane

braces. The cyclopropane SCF ground state (Table
C3H« (<£CCC 60°) (All Values Are Given in hartrees.)
=
I) is thereby denoted as {4b22}. Classification of the
present AO basis set according to the irreducible
Present Preuss and
calcn“ Dlercksen6
representations of both the C2v and D3h point group is
given in Table II.
la' (lai) -11.2941 -11.1952 Previous work dealing with ozone and formate ion6
le' (2ai, lb2) -11.2933 -11.1946’
has indicated that the effects of this symmetry equiva-
-11.1934
2a/ (3ai) -1.1510 -1.1367' lence go far beyond the realm of mere notational con-
2e' (4ai, 2b2) -0.8344 -0.8034 venience; it has shown, for example, that definite
la2" (lb,) -0.7024 -0.6458 similarities exist between corresponding angular orbital
3a/ (5ai) -0.6257 -0.5868
energy curves of such systems. If one examines
le" (2b,, la2) -0.5460 -0.4826’
angular correlation diagrams given in Figures 2a-c
-0.4824,
3e' (6ai, 3b2) -0.4398 -0.3845' pertaining to the same state ({4b22}) of the three
la/ (4b2) 0.3734 molecules C3H6, 03, and HCOO- and fixes his attention
4e' (7ai, 5b2) 0.5643 solely upon the shapes of corresponding curves and not
2aj" (3b,) 0.7179
upon their absolute position on the energy scale, it is
-116.9164 -116.0153
clear that a definite similarity does indeed exist among
—~ / 0.99660
the three diagrams. The basic postulate suggested in
“
At fleo
2.88 bohr,
=
flCH = 2.022 bohr, <HCH = 120°, connection with the ozone-formate ion comparison,6
£CCC =
The
60°.corresponding orbital notation for C2v symmetry
is given in parentheses. 6 At flee = 2,85 bohr, Ach = 2.08 bohr; namely that the shapes of corresponding orbital energy
curves are relatively unaffected by redistribution of
<£HCH = 117.3°, <£CCC = 60°; ref 9.
protons within a family of molecules, is certainly not
invalidated by this rather drastic example, that is by
than 120° and (b) related excited states for 03 and the schematic transfer of six protons from the oxygen
HCOO- have already been reported and are thus avail- nuclei of ozone to give three carbon and six hydrogen
able for comparison. atoms. Clearly then one cannot point to distinctions
In addition to the SCF treatment a rather large scale
configuration interaction calculation has been carried
out for each of the CCC angles considered in order to
Table II: Symmetry Classification of the Atomic Basis
check the effect of such improvements upon the SCF Set Used for the Cyclopropane Molecule in
potential curve, particularly as it relates to the theo- C2v and DSh Symmetry ( is the Irreducible Representation)
retical determination of the equilibrium angle and to
provide an unambiguous description of the electronic --Djh-- r
11 .....
.......“Civ ^

AO’s AO’s
spectrum, not only near equilibrium but for the com-
plete range of CCC angles considered. si + s2 + s s, y
\/3%i —
-\/3x2 + yi + ai' Si + Sz, X\ + xz, yi + yz ai
III. Discussion of SCF Results V2
—
2 y

hi + h¡ + hs + h, + h¡ + he hi hz + hz + hi, hi + hi
A. Electronic Configurations of CsH<¡, The three
systems ozone, formate ion, and cyclopropane are re- Si —
s2 Si Sz
lated not only by the fact that they are all mutually si + s2
—
2s yi —

2/2, X hz
isoelectronic, but also by the possibility of each of ¡Vi, Vi, V, xi, Xi, x]a e' hi + hz hz hi
—

them retaining a minimum of C2v symmetry throughout hi hz —

k% hi
—·

the entire range of variations in their respective major hi h% hi hi —

2h$ —
2 hi
internuclear angles. Perhaps the most important
consequence of this symmetry relationship is the one- xi + xi -
2x -

y/Syl + a2'
to-one correspondence it fosters between sets of \ZWi
molecular orbitals for a large class of systems, including
not only the three isoelectronic molecules under dis- Z\ + Z2 'j- Z Z, Z\ + 22

cussion, but also the whole family of symmetric tri- hi —

hz + A3 —
hi + ag" hi —
hz + hs —

hi, hi —
hi bi
atomics. This symmetry property can be used ef- hi —
hi

fectively in the labeling of electronic configurations for —

Z2
such molecules; in particular, one can employ a con- Zi ~~
2z
Z2 Sl —

Zz
venient shorthand notation to distinguish the electronic hi —
hz h¡ ~h hi e" hi —

hz —
hz + hi as
configurations of 24-electron systems whereby each hi “
hz hs —
hi
MO { occupied in the ground state of F20 2 h¡}
—
2 hi
0
Linear combination of these AO’s.
[la12lb222ai23a122b224ai25ai2lbi23b224b226av2la222bi2] (1)

Volume 78, Number 5 May 1969

1302
Figure 2. Orbital energies e< (in hartrees) as a function of internuclear angle for the {4b22} state of (a) ozone,
(b) formate ion HCOO-, and (c) cyclopropane.
in the shapes of corresponding orbital energy
between cyclopropane and the ozone-formate ion pair
to explain their greatly dissimilar geometries.
A simple explanation for these differences can be
found, however, in the fact that the three molecules
possess different ground-state electronic configurations,
{4ba2} for cyclopropane (Table I) but {2bi2} for ozone
and formate ion.4 Consequently, the orbital energy
terms contained in the respective ground-state total
energy expressions of cyclopropane and the ozone-
formate ion pair are different; the fact that the 4b2
and 2bi orbital energy curves differ so greatly in shape
can thus be pointed to as the most important single
cause for the large difference in equilibrium geometry
observed between these molecules. Put another way,
one can say that what is the ground-state electronic
configuration of ozone and formate ion is really a doubly
excited state for cyclopropane and vice versa.
This difference in electronic configuration can be
explained in a straightforward manner on the basis of
obvious structural differences between the molecules.
Comparison of the charge density contours of the
le" (which correlates with 2bi and la2 in C2v) in
Figure 3a with those of the la2' (4b2 in C2v) in Figure
3b shows conclusively that hydrogen participation in
these orbitals is quite selective; the hydrogen atoms
The Journal of Physical Chemistry
Robert J. Buenker and Sigrid D. Peyerimhoff
curves are in excellent position for bonding with the pir
carbon AO’s of the le" perpendicular to the molecular
plane18,14 whereas the la2' is forbidden by symmetry
(Table II) to undergo any such mixing. As a result
the la2 and 2bi MO’s are relatively much more stable
in cyclopropane than for either of the other two
molecules, a fact which is borne out quite clearly in the
three correlation diagrams in Figures 2a-c. In sum-
mary, the presence of the hydrogen atoms systematic-
ally placed above and below the molecular plane in
cyclopropane alters its ground-state electronic con-
figuration relative to ozone and formate ion by making
it energetically favorable to occupy the out-of-plane
2bi MO instead of the in-plane 4b2.18 The combined
effect of these various factors can be seen from the
total charge density contours evaluated for the Dsh
geometry. (See Figure 4.)
The results of the above comparison can be gen-
eralized in terms of two well-defined principles to
(13) The le" MO is quite similar to the lbsg (see Figure 7 of ref 14).
(14) R. J. Buenker, 8. D. Peyerimhoff, and J. L. Whitten, J. Chem.
Phys46, 2029 (1967).
(15) The hydrogens can also mix with the le' MO, but since its
charge density maxima are in the molecular plane, the position of
the hydrogens is not particularly well suited to improving the con-
stitution of this orbital, although it is obviously more beneficial to
the le' than to the laa' (Table II).
Geometry, Reactivity, and Spectrum of Cyclopropane
Figure 3. (a) Charge density contours for the le" MO of
cyclopropane (at <£CCC = 60°). (b) Charge density contours
for the las' MO of cyclopropane (at ^CCC = 60°).
describe the effects upon correlation diagrams of
schematically redistributing protons for a family of
molecules; first, the shapes of corresponding curves are
relatively unaffected and secondly, the relative sta-
bility of the individual MO’s may be radically re-
adjusted.16 The generality of these trends can be
seen again by the analogous comparison of the cor-
relation diagrams of cyclopropane, ozone, and formate
ion for the {6ax2} SCF state of each molecule, pre-
sented in Figure 5a-c. The same general shapes are
observed for corresponding curves, but again in C3He
the la2 and 2bx MO’s are seen to be considerably more
stable on a relative scale than are the 3b¡>, 6ax, and
4b2 MO’s, particularly the latter.
It is also instructive to consider the schematic
transition from ozone in its equilibrium nuclear ar-
rangement (-£000 =
116.8°) to cyclopropane. With
the removal of protons from the oxygen nuclei comes a
definite reordering in the correlation diagram. By the
time the hydrogen atoms are extended to a sufficiently
large distance from the now carbon nuclei to obtain a
cyclopropane nuclear conformation (for <£CCC
116,8°) it is no longer energetically unfavorable to
1303
Figure 4. Charge density contours for the cyclopropane molecule
(a) in the molecular plane and (b) perpendicular to this plane.
occupy the 2bx in preference to the 4b2 or 6ax MO’s
occupied in ozone. At this relatively large angle which
one of the latter two orbitals is depopulated in lieu of
the 2bx is immaterial; the fact that the 2bx favors
smaller angles leads unambiguously to the choice of the
4b2, however, since it becomes rapidly less stable with
decreasing angle while the opposite is true for the 6ax.
The result quite consistently is the {4b22} electronic
configuration and with it the well-known cycle
(small angle) structure of cyclopropane.
Before closing this discussion of the calculated MO’s
of cyclopropane it is also worthwhile to comment upon
their relation to the Walsh model4 for this molecule.
A generally accepted aspect of this model is the ex-
istence of six sp2 CH bonds and one CC bonding orbital
of ax' symmetry composed almost exclusively of carbon
2p functions directed radially into the cyclopropane
ring; historically discussion of this model instead has
centered upon the composition of the highest occupied
MO, the le', of cyclopropane, Walsh having stated that
it is composed solely of tangential 2p carbon AO’s
(i.e., no contribution from radial 2p AO’s). The
= (16) This effect is most easily observed in the comparison of acetylene,
ethylene, and ethane with the corresponding isoelectronic homo-
nuclear diatomic molecules, i*
Volume 78, Number May 1969
1304
Figure 5. Orbital energies << (in hartrees) as a function of internuclear angle for the [6ai2j state of (a) ozone,
(b) formate ion HCOO-, and (c) cyclopropane.
present ab initio calculations find, however, that the
resultant 2p vector of the le' MO points 31.7° away
from the tangential direction toward the radial. Put
another way, this means that the p functions in the
le' meet each other at an angle of 28.3° above a given
CC axis, far less than the 60° figure given by Walsh
(in this notation a pure bond corresponds to 0°, a
pure bond to 90°). Walsh then went on to theorize
that his postulated wide angle p overlap ivas respon-
sible for certain well-known conjugative effects of
cyclopropane; the failure to detect such wide angle
overlap both in the present calculations and in the
results of others17·18 would thus seem to contradict
Walsh’s explanation for the occurrence of such phe-
nomena. The present angle of 28.3° is in much better
agreement with the angle of 22° given by Coulson and
Moffitt6 for the same parameter. In section V of the
present paper an alternative explanation for the con-
jugative effects exhibited by cyclopropane will be given
which does not require any degree of lateral overlap
between carbon 2p functions.
B. Single Determinantal Potential Curves. Potential
curves for three closed shell states of cyclopropane are
given in Figure 6a. Of these the {4b22} ground and the
{6ai2} excited state correspond to SCF wave functions;
The Journal of Physical Chemistry
Robert J. Buenker and Sigrid D. Peyerimhoff
the {2bj2j curve, on the other hand, has been calculated
by evaluating the total energy of an appropriate single
determinant constructed from the molecular orbitals
resulting from the {4b22} SCF solution for cyclopro-
pane. The general shape of the ground state total
energy curve agrees qualitatively with the correspond-
ing results obtained by Hoffmann19 via semiempirical
techniques. The analogous closed-shell potential
curves for 03 and HCOO- are given in Figures 6b and
6c, respectively; comparison among the various data
can be made more quantitative by calculating a poly-
nomial fit for each of the curves with subsequent de-
termination of equilibrium angles and bending force
constants (Table III).
In the present context the {4b22} potential curves are
the most interesting; of these the C3He ground state
shows the largest force constant and the smallest
equilibrium angle. All three curves bear a striking
resemblance to one another, and it is particularly
interesting that this electronic configuration is very
nearly also the ground state of 03, as well as of cyclo-
(17) R. Hoffmann, J, Chem. Phys., 40, 2480 (1964).
(18) J. E. Todd, M. A. Whitehead, and K. E. Weber, ibid., 39, 404
(1963).
(19) R. Hoffmann, J. Amer. Chem. Soc., 90, 1475 (1968).
Geometry, Reactivity, and Spectrum of Cyclopropane 1305

Figure 6. Angular potential curves for different *Ai states of (a) cyclopropane C3He, (b) ozone, and (c) formate ion HCOO-. (Energy
values are given in hartrees; all curves, with the exception of the {2bi2} state of cyclopropane, are obtained from an SCF procedure.)

propane, possessing a minimum in its total energy IV. Configuration Interaction

only 1 eV higher than the absolute minimum shown by
the {2bj2} state at 118.5°. In other words, but for the
slightly greater stability of the {2br2} state of Os,
this molecule also would possess a cyclic equilibrium
nuclear arrangement, quite similar to the familiar
cyclopropane geometry.
The similarity between the other sets of curves in
Figure 6a-c is not as great as it is for the {4b22} states,
with most of the dissimilarity occurring for angles
greater than 130°. Clearly this behavior is reasonable
in light of the greatly different environments en-
countered by the three systems at such angles, par-
ticularly at 180°; the effects of such differences are
most obvious for those states which have relatively
large equilibrium angles. Nevertheless, the overall
resemblance between the shapes of corresponding
potential curves would seem to demonstrate a basic
similarity between the molecules, which, in turn, is a
reflection of their nearly equivalent nuclear symmetries
and their mutually isoelectronic relationship.
The presence of the low lying {6ai2} doubly excited
state, with the minimum in its potential curve occur-
ring at a much larger angle than 60°, in the spectrum of
cyclopropane is interesting because it indicates the
possibility that significant changes in the calculated
ground-state potential curve might result through the
process of configuration interaction; this aspect of the
treatment is now considered.
A. Calculations. All determinants to be considered
in the following Cl calculations are constructed from
the same set of SCF MO’s (usually the ground state).
The first calculation to be discussed mixes the two low-
lying closed-shell states of cyclopropane {4b22} and
{6a!2};20 the resulting angular potential curve, denoted

Table III: Calculated Equilibrium Angles 0„ and

Bending Force Constants for Different States of 03,
HCOO-, and Cyclopropane C3H6

-O,--. .-HCOO"--. .-C,H.--.

State 0e V ,
I4W*} 71.5° 48 73° 57 63.5° 98
16a!2! 180° 0.75 160° 8.5 129° 19
!2b,8} 118.5° 13.8 128° 20.5 123° 42i
“
In 10-12 erg/radian2. 6 The values calculated for the ¡2bi8) state
of C3H3 are calculated by evaluating the energy expression using the Figure 7. Ground-state angular potential curves for cyclopropane
MO’s of the ground-state wave function. obtained from the SCF procedure and from three different levels
of a Cl treatment. (Energy values are given in hartrees.)

Volume 73, Number 5 May 1969

 1306
Table IV: Calculated Equilibrium Angles 9e and Bending Force Constants
Several States of Cyclopropane Obtained from Different Treatment
State ------
|4b22¡, SCF 63.5
Cl (2) CI(2 Exc) Cl(4 Exc)
2Ai 64.9 65.7
3, 88
3B2 116
'Bj 112
2 3B2
8a2 103
2»Ai
given in degrees, force constants in 10-12 erg/radian2.
“
Angles are
Cl (2), is given in Figure 7 along with those of several
other treatments of the ground state. In general,
mixing between the two closed-shell states is fairly sub-
stantial at all angles because of the existence of a large
exchange integral connecting the 4b2 and 6ai MO’s;
it is especially strong at larger angles where the di-
agonal energies of the two determinants are more nearly
equal, thereby leading to a definite change in shape
of the ground-state potential surface relative to its
{4b22} SCF representation. The calculated equilib-
rium angles and bending force constants bear these
observations out quantitatively (Table IV); the
equilibrium angle increases still further away from the
equilateral triangle value while the potential curve as a
whole becomes less steeped toward larger angles. Of
course this trend could have been predicted qualita-
tively from the angular correlation diagrams of Figures
2a and 5a; the Cl treatment is introducing consider-
able 4b2 character into the molecular wave function
and with it a definite tendency toward a skeletal linear
geometry.
In the remaining Cl calculations the valence set is
increased to include the highest four occupied and the
lowest three virtual orbitals at any given angle.21
Such a definition introduces a total of (V) 3003 =
determinants into each N electron basis set, 1225 of which
have Me 0. In a preliminary treatment only those
=
configurations within this set are included which cor-
respond to at most a double electronic excitation from
the SCF ground state. Table Va gives the number of
states of each symmetry classification considered in this
treatment [denoted Cl(2 Exc)]; the numbers differ
from angle to angle because of changes in the valence
set of MO’s which are caused, in turn, by the reordering
of orbital energies in the bending process. Potential
curves for the lowest-lying states of cyclopropane
resulting from this calculation are contained in Figure
8 while the 1Ai 1A1' ground-state curve is also in-
=
cluded in Figure 7 for comparison with related data.
Equilibrium CCC angles and bending force constants
for these potential curves are also included in Table
The Journal of Physical Chemistry
Robert J. Buenker and Sigrxd D. Peyerimhoff
K for
---lie"---
98
CI(2) CI (2 Exc) 01(4 Exc)
65.9 83 74 73
82 15 30
111 28 28
111 33 57
115 15
103 20 17
125 26
IV. The ground-state equilibrium angle is again
observed to increase relative to its corresponding value
in the previous two-configuration calculation but the
change is much smaller than is found in going from the
SCF to the Cl (2) treatment.
Of the excited states calculated at this level the
lowest lying at most angles is the 8B2-2E' (in fact, it
becomes the ground state in the neighborhood of
<CCC = 120°); its minimum in energy is found to
occur at 116° with a relatively large curvature at
that point (Table IV). The main contribution to this
state comes from the single excitation determinant
which singly occupies both the 6ai and 4b2 with un-
paired spins; the increase of 4b2 character relative to
the ground state again qualitatively explains its larger
equilibrium angle. Its corresponding singlet ^ is the
next excited state at most angles; the triplet-singlet
splitting is quite large, being approximately equal to
twice the aforementioned exchange integral connecting
the 6ai and 4b2 MO’s. As in the case of the ground-
state curve the general shape of the 31B2 curves is in
qualitative agreement with the analogous semiempirical
data obtained by Hoffmann.19
Both B2 species merge with Ai states of corresponding
multiplicity at 60° to form, respectively, the degenerate
8’1E/ states. The Ai states, also shown in Figure 8,
originate from single excitations from the 3b2 to the
4b2 MO; they lie much higher at larger angles than the
corresponding B2 species because the 3b2 is more stable
than the 6ai at such angles (see Figure 2a). Finally,
it should be noted that states of A2 or Bi symmetry lie
well above the Ai and B2 states, especially at smaller
angles, a fact which underscores the relatively greater
stability of the la2 and 2bi MO’s in cyclopropane
effected by their pronounced interaction with the
hydrogen AO’s (Figure 3a).
(20) The total energy of the |6ai!) determinant considered in this
calculation is nowhere more than 0.02 hartree higher than its cor-
responding SCF value.
(21) At a given angle all determinants thus considered have a common
core of eight doubly occupied MO's with their remaining columns
selected from the spin orbitals associated with the valence set.
Geometry, Reactivity, and Spectrum of Cyclopropane
Figure 8. Angular potential curves for a selected group of
low-lying states of cyclopropane calculated from the (2 Exc) Cl
treatment (solid lines). For comparison some of the corresponding
curves obtained from the (4 Exc) Cl treatment are also given
(dashed lines). (Energy values are given in hartrees.)
In the final Cl treatment [denoted Cl (4 Exc) ] the
restriction of including only single and double excita-
tion determinants is removed, although not all triple
and quadruple excitation determinants (selection
based on diagonal energy) and none in higher excitation
classes are considered. The size of the various secular
equations was kept down to a maximum order of about
80; the number of symmetrized states in each category
for this Cl treatment is given in Table Vb.
Examination of the eigenvectors resulting from this
calculation leaves little room for doubt that inclusion
of still more states of a given symmetry (within the
framework of the method discussed in this paper)
would not have affected the present results signifi-
cantly. Virtually no change is observed in either the
multideterminantal expansion of the cyclopropane
ground state or in its energy eigenvalue (Figure 7)
as a consequence of the addition of higher excitation
configurations; of course this result is certainly not
surprising in view of the orthogonality of the MO basis
set employed. On the other hand, mixing with the
more stable triple excitations does produce significant
energy lowerings for certain excited states, as can be
seen from Figure 8. Angular potential curves of the
final Cl calculation for the relatively low energy
states in the cyclopropane spectrum are shown in
Figure 9; corresponding values for equilibrium CCC
angles and bending force constants are found in Table
IV and a more complete tabulation of the various
energy levels is contained in the Appendix.
The present calculations thus indicate a CCC
1307
Figure 9. Angular potential curves for several low-lying states of
cyclopropane calculated from the (4 Exc) Cl treatment.
(Energy values are given in hartrees.)
equilibrium angle of roughly 65°, significantly greater
than the equilateral triangle value. While one may
point to the lack of optimization of all other inter-
nuclear parameters as the major cause for this dis-
crepancy it still seems appropriate to suggest (espe-
cially since previous work has indicated little inter-
dependence between calculated bond angles and bond
distances) on the basis of the present calculations
that the equilibrium CCC angles of cyclopropane are
not all equal. The best experimental indication for the
equilateral triangle arrangement of the molecule comes
from observation of how well it obeys the appropriate
selection rules in its ir and Raman spectra;22 it would
seem that such evidence is proof only of approximate
D3h symmetry, with the maximum possible structural
deviation in lieu of observation of these effects open to
question. Therefore closer examination of this matter
by means of both experimental and theoretical tech-
niques appears to be desirable.23
Before evaluating these Cl results as they relate to
the electronic spectrum of cyclopropane their de-
pendence upon the choice of MO basis sets should be
discussed. Energy levels obtained from the two
possible Cl calculations [Cl (4 exc) level, one using the
{4b22} set of SCF MO’s and denoted B, the other using
(22) G. Herzberg, “Infrared and Raman Spectra of Polyatomic
Molecules,” D. van Nostrand Co., Inc., Princeton, N. J., 1964, p 352.
(23) One expects comparatively negligible changes to occur in the
ground-state potential curves of ozone and formate ion as a result
of Cl since the pertinent exchange integrals connecting [{2bi2)J
ground and nearby excited states are much smaller than in the case
of cyclopropane (see Figure 6a, b).
Volume 73, Number May 1969
1308 Robebt J. Buenkeb and Sigbid D. Peyebimhoff

Table V: Number of Symmetrized States Included in the Two Configuration Interaction Treatments of
Cyclopropane at Different CCC Angles (The Numbers for the (2 Exc) Calculation Are Given
in Part A, Those for the (4 Exc) Treatment in Part B.)

< CCC: 45° eo° 80° 100° mm0 120°A° 140°B° 140° Aa 160°

Part A.

•A,' 12
, 28 28 34 34 34 34 34 37
iE' 16

3Ai' 5
•A, 21 19 26 26 26 26 26 27
3E' 14

6Ai' 2
•A, 6 4 6 5 5 5 5 3
»E' 2

," 7

’As 21 21 15 15 15 15 15 18
iE" 14

8Ai" 9
"As 25 27 20 20 19 20 19 24
3E" 18

3Ai" 2
‘As 4 6 5 5 4 5 4 6
«" 4

’As" 7

’B, 21 21 15 15 15 15 15 12
iE" 14

»As" 9
3Bi 25 27 19 19 20 19 20 15
8E" 18

6As" 2
‘B, 4 6 4 4 5 4 5 3
»E" 4

’As' 6
’» 21 21 27 27 27 27 27 24
iE' 16

3As' 9
aBs 25 23 31 31 31 31 31 30
3E' 14

•As' 0
‘B, 4 2 4 4 4 4 4 6
5E' 2

The Journal of Physical Chemistry

Geometry, Reactivity, and Spectrum of Cyclopropane 1309

Table V (Continued)

< CCC: 45° 60° 80° 100° 120°B° 120°A° 140°B° 140°A“ 160°

Part B.

'Ax' 33
‘A, 70 74 80 80 80 80 80 82
>E' 50

8Ai' 24
8A, 75 76 77 77 77 77 77 80
2E' 54

« ,' 7
‘A, 21 20 16 16 16 16 16 17
»E' 12

" 23
*a2 63 63 55 57 57 55 55 54
" 43

8A," 29
8a2 80 83 77 80 80 78 78 79
»E" 56

sAi" 6
«, 18 21 24 25 25 27 25 29
«" 14

2Aj" 23
‘Bi 63 62 56 57 56 55 55 54
iE" 43

8A2" 29
8B, 80 82 79 80 79 78 78 77
2E" 56

•Aj" 6
«, 18 21 25 25 25 27 25 23
»E" 14

Aj' 20
lB2 61 63 70 68 67 69 69 66
iE' 50

8AZ' 31
8b2 78 80 83 81 79 82 82 79
>E' 54

6A2' 4
6b2 18 19 14 14 13 15 14 13
SE' 12
“ B indicates that the MO’s of the {4b22) state are used in the 01 determinants; A means that those of the (6ai2| state are used.

Volume 73, Number 5 May 1969

1310 Robert J. Buenker and Sigrid D. Peyerimhoff

Table VI: Comparison of Energy Levels for Several States of Figure 9 lends itself to a more acceptable correlation
Cyclopropane at Angle CCC of 120 and 140° Obtained when it is noted that each of the low-lying excited states
from the (4 Exc) Cl Treatment Using the MO’s of the possesses a relatively large equilibrium angle and a
{4b22 ] SCF State (Denoted by B) and Those of the [6aizj potential curve which descends sharply toward this
SCF State (A) (All Values Are Given in hartrees.)
energy minimum.25 The 0-0 transition to the 4B2
120°B 120°A 140°B 140°A equilibrium nuclear configuration calculated at 6.9 eV
could thus be identified with the longest wavelength
3B2 -116.8784 -116.8795 -116.8213 -116.8208
‘A, -116.8706 -116.8700 -116.8162 -116.8174
absorption reported,24 especially since it is fully allowed
‘B2 -116.6914 -116.6930 -116.6642 -116.6630 by the dipole selection rules. The corresponding
2 zAt -116.6613 -116.6652 -116.6325 -116.6354 0-0 excitation to the 2 4Ai state, which is also fully
8Ai -116.5668 -116.5719 -116.5447 -116.5513 allowed, is then assigned to either of the next two
2 3B2 -116.5558 -116.5627 -116.5251 -116.5288 lowest experimental energies (Table VII); the fact
=a2 -116.5280 -116.5309 -116.4495 -116.4479 that the observed band systems overlap to a con-
4a2 -116.5167 -116.5170 -116.4388 -116.4337
siderable extent also lends credence to an assignment
3‘Ai -116.5139 -116.5126 -116.4722 -116.4689
based on nonvertical electronic transitions and suggests
further that the absorptions between 6.79 and 8.55 eV
the {6ai2 set and denoted A] for CCC angles of 120
}
may well correspond to only two distinct 0-0 excita-
and 140°, respectively, are given in Table VI. Com- tions rather than the three assigned experimentally.
parison of these data indicates strongly that the The first calculated fully allowed vertical transition
process of Cl is capable of arriving at a description of ( ' *— 'AV) can then be identified with the 10.32 eV
the electronic spectrum independently of which of the absorption; previous experience has indicated that
two sets of SCF MO’s is employed in the construction Cl calculations employing fixed group basis sets will
of the multideterminantal basis set. This relative overestimate this transition energy by at least 1 to 2
invariance represents a distinct advantage of the Cl eV. All the singlet-triplet species calculated at lower
treatment over the SCF calculations discussed earlier. energies should be ruled out on the basis of their
B. Electronic Spectrum. Experimental and calcu- expected weak oscillator strengths. The present
lated [Cl (4Exc) ] transition energies to the low-lying analysis suggests, however, that cyclopropane may show
excited states of cyclopropane are given in Table VII. some very weak absorption in the long wavelength
The experimental data24 are observed in the vacuum visible to infrared region of the spectrum corresponding
ultraviolet and are characterized by complex over- to the lowest 0-0 singlet-triplet transition calculated.
lapping band systems. None of the calculated vertical The semiempirical results of Hoffmann19 are also
transitions appears to be reasonably correlated with interesting in this connection; these calculations ex-
the observed species of lowest energy; its extinction plicitly consider the effect of rotating the terminal
coefficient seems inordinately large to be associated methylene groups of bent CsHe upon the stability of
with a singlet-triplet transition and at the same time the system in ground and excited states. They find
its term value of 6.79 eV is much too low to be ascribed a relatively stable closed-shell intermediate for angle

to any of the calculated vertical singlet-singlet species. CCC of 120° with terminal CH2 groups in the major
plane of the molecule; excitations to such an inter-
mediate could also be expected to further complicate
Table VII: Theoretical and Experimental Transition Energies the cyclopropane electronic spectrum. It also seems
for the Electronic Spectrum of Cyclopropane
[Cl (4 Exc) Treatment] (Vertical Excitation Energies Are possible that the excited states of this system might
Calculated for Angle CCC = 65°; the Equilibrium show a similar dependence upon hydrogen rotation,
Angle of the Upper States in the 0-0 Transition although Hoffman’s results indicate practically free
Is Given in Table IV.) rotation of the CH2 groups in the first excited state of
cyclopropane.
Type of ---Energy, eV---
An alternative assignment for the cyclopropane
Upper state transition Caled Bxpti
0 0
spectrum has been given by Clark26 on the basis of
‘A2
3B2 0-0 1.8 semiempirical calculations. This analysis ascribes the
4ß2 0-0 6.9 6.79 experimental absorptions exclusively to fully allowed
2 zAi 0-0 7.8 7.78' vertical singlet-singlet electronic transitions; it finds
8.55, no lessthan seven singlet-singlet species (degeneracies
3B2(3E') Vertical 9.1 counted only once) with excitation energies below
3A, 0-0 9.3
10.0 eV, in radical disagreement with the present
3Ai(3E') Vertical 10.3
2 3B2 0-0 10.5
3A2 0-0 11.2 (24) P. Wagner and A. B. F. Duncan, J. Chem. Phys., 21, 516 (1953).
iB2(iE') Vertical 13.1 10.32 (25) This behavior can be traced directly to a pronounced increase
in 4b8 character relative to the ground state.
2 ') Vertical 13.3
(26) D. T. Clark, Theor. Chim. Acta, 10, 111 (1968),

The Journal of Physical Chemistry

Geometry, Reactivity, and Spectrum of Cyclopropane
ab initio SCF-CI data. On the other hand, since the
parameterization employed to obtain these semi-
empirical results was chosen so as to give a good overall
fit to the observed electronic spectra of cyclopropane
and related molecules exclusively on the basis of ver-
tical transitions, it seems quite plausible that an
equally acceptable choice of parameters could well have
led to calculated excitation energies in much better
agreement with the present ab initio results. In short,
the paucity of low energy singlet-singlet vertical
transitions indicated in Figure 9 leads one to interpret
the electronic spectrum of cyclopropane largely on the
basis of 0-0 excitations.
V. Reactivity and Conjugative Effects
in Cyclopropane
It has been shown that qualitative MO theory can
explain the comparatively small equilibrium angle of
cyclopropane relative to that of the isoelectronic
molecules 03 and HCOO- quite simply in terms of a
change in electric configuration. In this section the
relevance of the present calculations to another interest-
ing characteristic of the cyclopropane molecule, namely
its unusual chemical reactivity, will be discussed.
Cyclopropane is known to undergo certain addition
reactions which are characteristic of molecules possess-
ing a carbon-carbon double bond. Walsh4 has sug-
gested that this behavior can be attributed to a large
amount of lateral overlap between carbon 2p functions
in the molecule, but it has already been pointed out in
section IIIA that such circumstances are not in fact
borne out by quantitative calculations. At the same
time a previous theoretical treatment14 of the addition
process for ethylene, a molecule which does contain a
classical carbon-carbon double bond, has indicated
quite strongly that even in this case the relative orienta-
tion of carbon 2p functions in itself is not directly
responsible for the unsaturation properties of this
system.
Instead, the following set of circumstances seems to
be necessary for addition reactions to take place.
Under hydrogenation the ir* MO (lb2g) of ethylene is
not only occupied but also considerably stabilized;
hydrogen bonding (now allowed for this MO by the
change in nuclear symmetry from C2H4 to C2H6)
considerably alters the composition of this orbital.
In contrast, almost no relationship is found between the
addition process and the bonding MO (lb3u, already
occupied in C2H4), except for the fact that it also gains
considerable stability by bonding with hydrogens in
D3d symmetry. The point to be emphasized is that in
ethylene (and other doubly bonded systems) addition is
made probable by the availability of a relatively stable
orbital (unoccupied in the ground state) to house the
extra electrons. The existence of similar circum-
stances for systems not containing double bonds would
1311
therefore also seem to be sufficient to allow such
molecules to undergo addition reactions.
It is certainly not mere coincidence, for example, that
ethylene and the large class of related molecules gen-
erally characterized as unsaturated toward addition
also are observed to possess relatively low-lying excited
electronic states with pertinent (vertical) transitions
corresponding to the visible or near-ultraviolet region
of the spectrum. The great abundance of multiple-
bonded systems in nature has led to a more or less
exclusive association between unsaturation and the
double bond (and with it lateral overlap of carbon
2p functions); the above arguments indicate, however,
that it is the circumstances accompanying the common
functional group in these molecules (namely, a - *
pair of MO’s with a relatively small orbital energy dif-
ference) which is critical in producing such reactivity.
The Cl calculations discussed herein have shown
that although cyclopropane does not possess any low-
lying excited states in its equilibrium nuclear arrange-
ment, it does have them at large CCC angles. Such
states occupy the 4b2-la2' MO, which, despite its
relative lack of stability around the equilibrium angle,
is the most likely candidate for occupation by the
electrons introduced by the attacking species in the
addition reactions of cyclopropane. Consequently,
under sufficiently rigorous experimental conditions
(i.e., moderately high temperatures or concentration of
reactants), a given complex of cyclopropane plus
adduct can take advantage of the strong linear tend-
ency of the 4b2 MO by increasing its CCC angle
relative to its preferred value in isolated C3H6. The
analogy in inorganic chemistry would clearly be a
schematic transition from the {4b22} state of ozone
(£000 approximately 70°) to the ground state of
F20, whose two differentiating electrons also occupy the
4b2 orbital (£FOF =
103°). The change in equilib-
rium angle in going from cyclopropane to propane
(£CCC 111°) is somewhat greater than the in-
=
crease observed in the aforementioned case, but it seems
clear that both instances are related to the same general
phenomenon, namely occupation of the 4b2 MO.
Put another way, it is clear that while cyclopropane
and propane are alike in many ways, particularly with
regard to their CC bond lengths, they differ quite
significantly in the fact that the lowest-lying unoc-
cupied MO of C3He is much more relatively stable
(especially at certain CCC angles) than the correspond-
ing entity in C3Hs; in this respect it can be asserted that
cyclopropane is more like a doubly bonded system.
The interesting point, however, is that in this case the
unsaturation is caused by a -type orbital (4b2-la2'),
not by one belonging to the family of MO’s.
The change in geometry induced by addition re-
actions in the two cases of cyclopropane and ordinary
alkenes is a distinguishing feature, but this is only a
matter of degree; the other C3H6 isomer propene, for
Volume 75, Number 6 May 1969
1312 Robert J. Buenker and Sigrid D. Peyerimhoff

Table AI

—45°--. --60°- *-i 50°--

‘A, -116.7329 ‘A/ (‘Ai) -116.9456 ‘Ai -116.9252

3A, -116.349 3E' (=A0 -116.542 3B2 -116.772
3BZ -116.296 (8B2) 3A2 -116.605
‘Ba -116.227 iE' (‘B2) -116.413 ‘B2 -116.574
2‘Ai -116.185 (2‘AO 2‘Ai -116.556
23B» -116.182 3A2' (2 3B2) -116.404 2 8B2 -116.523
8Bt -116.175 3E" (=B0 -116.383 3Ai -116.503
‘B, -116.156 (8A2) ‘Ai -116.502
8 -116.135 iE" (‘BO -116.366 3‘Ai -116.482
‘A, -116.119 (‘AO 2‘Bi -116.471
2 3Ai -116.118 3E' (2=A0 -116.356 3 3B2 -116.460
2 *Ai -116.097 (3 3B2) 8Bi -116.442
2 8Bi -116.090 ‘A2' (2‘BO -116.349 2 ®Ai -116.433
2’Ai -116.087 sAi' (3 0 -116.341 ‘Bi -116.405
2‘Bi -116.083 ‘Ai' (3‘AO -116.296 3 ‘B2 -116.372
3A2" (2 =B0 -116.256
iE' (3‘BO -116.247
(4‘AO
____
1Ü0 i*o 1*40

‘Ai -116.8922 3B2 -116.8790 =BS -116.8211

=b2 -116.873 ‘Ai -116.870 ‘A, -116.817
‘B2 -116.682 ‘, -116.692 ‘Ba -116.663
2‘Ai -116.641 2‘Ai -116.663 2‘Ai -116.634
sAi -116.592 8Ai -116.569 8Ai -116.548
2 3B2 -116.549 2 3B2 -116.560 2 3B2 -116.527
sa2 -116.541 8a2 -116.529 3 3B2 -116.479
3‘A, -116.532 ‘A2 -116.517 3Bi -116.479
82 -116.528 3‘Ai -116.513 3‘Ai -116.470
2‘Bi -116.479 8Bx -116.503 4 3B2 -116.456
3 8B2 -116.469 3 sB2 -116.495 2‘Bií -116.453
% -116.434 2 3Ai -116.483 2 3Ai -116.452
2>Ai -116.425 ‘Bi -116.482 8A2 -116.449
‘B, -116.416 2‘Bi -116.479 ‘B2 -116.448
3‘B, -116.412 4‘Ai -116.459 ‘A, -116.434
“
Average values of 120°A and 120°B, or 140°A and 140°B (see Table VI).

example, a conventional doubly bonded system, goes
roughly from 120° to 111° upon its hydrogenation to
propane. While this behavior is usually explained
according to VB theory in terms of a change in hy-
bridization from sp2 to sp3, from the standpoint of MO
theory it is a straightforward consequence of going from
a {2bi2} electronic configuration of a 24 electron
molecule (ozone, <£000 116.8°) to that of eq 1
=
for a 26 electron system (F20, <£FOF 103°).
Thus the simplest answer to the question of why the
change in geometry from cyclopropane to propane is
much greater than that which occurs in the transition
from propene to propane is again that the slope of the
4b2 orbital energy curve is much greater than that of
the 2bi (Figure 2a).
VI. Conclusion
A study of the electronic structure of cyclopropane by
the MO method leads to a concise explanation of its
anomalous properties in terms of its distinctive ground-
state electronic configuration. The cyclopropane hy-
drogens, constrained from steric considerations to lie
either above or below the CCC plane of the molecule,
exert a preferential stabilizing influence on the t-
type MO’s (out-of-plane) relative to those of the
category. As a consequence it becomes energetically
favorable to exchange a MO for a in the ground-state
electronic configuration of this hydrocarbon relative
= to that of its isoelectronic counterparts ozone and
formate ion; thus cyclopropane exists in what is an
excited state for ozone (and formate ion) and vice
versa. Differences in the shapes of orbital energy
curves for the interchanged and MO’s are thus
easily shown to be largely responsible for the great
disparity found between the equilibrium geometries of
these systems.
The knowledge that the lowest-lying unoccupied
MO in cyclopropane is a orbital which strongly favors
more linear geometries is sufficient to explain the
anomalous reactivity of the molecule toward addition

The Journal of Physical Chemistry

Vacuum-Ultbaviolet Photolysis of C4H6 Isomers 1313

reactions. The extra electrons introduced by such
reactions clearly are expected to occupy this MO,
thereby causing a protracted increase in the equilib-
rium angle from reactant to product. An analogy
between the unsaturation observed for this compound
and that of ethylene and other doubly bonded systems
can thus be drawn in terms of the common existence of
a relatively low-lying excited MO; whereas the orbital
in question is a ir MO in C2H4, it is one of -type in
C,H«. Another distinction is that the cyclopropane
MO is sufficiently stable for such activity only for
geometries considerably removed from the ground-
state equilibrium structure, unlike the situation in
ethylene, for which the vertical excitation energy be-
tween highest occupied and lowest unoccupied orbitals
is relatively small.
Acknowledgment. The authors are most appreciative
of the hospitality shown them by Professor J. L.
Whitten during their stay in the Chemistry Depart-
ment of Michigan State University and are especially
grateful for his continued interest in this work. We
also thank Mr. J. Petke for his assistance in the execu-
tion of the various computations. Acknowledgment
is made to the donors of the Petroleum Research Fund,
administered by the American Chemical Society, and
to the Deutsche Forschungsgemeinschaft for financial
support. The services and computer time made
available by the Michigan State and the University of
Nebraska Computation Centers and the Deutsches
Rechenzentrum have been invaluable for this study.
Appendix
In Table AI, the total energy for several low-lying
states of cyclopropane C3H6 is given at different angles
CCC; the values are obtained from the (4 Exc) Cl
calculation. (All energy values are given in hartrees.)

Vacuum-Ultraviolet Photolysis of the C4H Isomers. 6 II. 1,2-Butadiene

by R. D. Doepker and K. L. Hill

Department of Chemistry, University of Miami, Coral Gables, Florida 33124 (Received August 14, 1968)

The photolysis of 1,2-butadiene was investigated using xenon (1470 Á) and krypton (1236 Á) resonance
radiation and compared with the 2200-2600-Á photolysis. The formation of methylacetylene, aliene, and
1,3-butadiene was attributed to a long-lived excited state of 1,2-butadiene. This state was pressure dependent
but unaffected by nitric oxide or oxygen. Products produced from a second nonpressure-dependent excited
state were acetylene, ethylene, vinylacetylene, and hydrogen. The use of H2S as a free-radical interceptor
demonstrated the presence of CH3, C2HS, and C4H3 radicals in the xenon and krypton photolysis. In the
krypton photolysis ionization is expected, but no products could be identified as originating exclusively from
an ion-molecule reaction.

Introduction Lossing4 also demonstrated that the C3H3 radical took

In the first paper of this series,1 the vacuum-uv predominately the propargyl structure (· 2
photolysis of 1,3-butadiene was investigated and com- CH), leading to 1-butyne when combining with a
pared with previous uv investigations.2 Unfortun- CH3 radical. Other observations noted the presence
ately, little has been reported in the literature for of small amounts of methylacetylene and aliene and
1,2-butadiene. Jones and Taylor3 reported the ab- the absence of the C4H5 and C2H3 radicals.
sorption spectra of 1,2-butadiene between 1650 and Since basic differences were found between direct
2100 Á but there has not been an assignment of the (2000-2500-Á) photolysis and mercury-photosensitized
excited states for the electronic transitions observed. decomposition of 1,3-butadiene,2 it was deemed neces-
Collin and Lossing4 studied the mercury-photo- sary, at least in a preliminary way, to investigate the
sensitized decomposition of 1,2-butadiene and pro- direct (2200-2600-Á) photolysis of 1,2-butadiene in
posed three primary processes (eq 1-3). Collin and addition to the vacuum-uv photolysis.
Hg(3Pi) + C4He(l, 2) =
C4H6(1, 2)* + HgOSo) (1)
C4H6(1, 2)* =
Hs + C4H4 (2) (1) R. D. Doepker, J. Phys. Chem., 72,4037 (1968).
(2) R. Srinivasan, Advan. Photochem., 3, 113 (1966).
=
CH, + C,H, (3)
(3) L. C. Jones, Jr., and L. W. Taylor, Anal. Chem., 27, 228 (1955).
=
polymer (4) (4) J. Collin and F. P. Lossing, Can. J. Chem., 35, 778 (1957).

Volume 73, Number 6 May 1969