Symmetry breaking in molecular calculations and the reliable prediction of

equilibrium geometries. The formyloxyl radical as an example

A. D. McLean, B. H. Lengsfield lII,a) J. Pacansky, and Y. Ellinger')
IBM Research Laboratory, San Jose, California 95193
(Received 22 April 1985; accepted 25 June 1985)
A systematic approach to symmetry breaking in molecular calculations, based on MCSCF and
multireference CI (MRCI) wave functions, is presented. A series of MCSCF expansions is
generated by successively incorporating resonance effects and size effects into the wave functions.
The character of the potential surface obtained at each level is analyzed. As an example, the
energy curves of the ground state (0') and the first excited state (1T) of the formyloxyl
radIcal (HC0
2
) ar.e characterized. The 0' and 1T equilibrium structures are shown to be symmetric,
with an adiabatic 0' - 1T excitation energy of 9.2 kcallmol. Unlike earlier theoretical studies, our
MCSCF model produces a qualitatively correct potential surface. Therefore, we are able to
extract reliable vibrational frequencies from the MRCI potential surface.
INTRODUCTION
Determination of the equilibrium structure of O'-formy-
loxyl, HC0
2
, the radical produced from formic acid by re-
moval of the acid hydrogen atom, presents a fascinating
challenge to the computational chemist. The challenge is to
determine whether in the equilibrium structure the unpaired
electron is delocalized, shared equally between the two oxy-
gen atoms, or is localized on one of them. In the former case
the equilibrium structure will have equal CO bondlengths,
while in the latter the localized radical electron will force an
equilibrium structure with unequal CO bondlengths.
The challenge exists because of difficulties that arise
when the standard tools of the computational chemist, var-
ious levels of self-consistent-field (SCF), multiconfiguration
SCF (MCSCF) and configuration interaction (CI), generate
"symmetry broken" electronic wave functions whose sym-
metry is lower than that of the nuclear frame. The possibility
of symmetry broken solutions exists in an enormous variety
of open shell electronic states; all those, in fact, that can be
represented by more than one low energy structure in va-
lence-bond or localized orbital descriptions. In cases where
there is a key high symmetry coordinate in the calculation of
the potential energy surface (e 2v in HC0
2
, for example) it
will be obvious, for points along this coordinate, if the elec-
tronic wave function has broken symmetry. Deficiencies in
the model from which this wave function was computed can
then be remedied in more sophisticated models. But for re-
gions of a potential energy surface where there is no symme-
try, how are we to know whether a wave function is suffering
from similar deficiencies, with consequent qualitatively
wrong structural predictions? The symmetry breaking prob-
lem is a general one, not restricted to those simple cases
where calculations in a high symmetry nuclear framework
make the problem obvious. If it exists in 0'-HC0
2
, for exam-
1 Present address: Ballistic Research Laboratory, AMXBR-IBD APG
MD 21005-5066. '
bl Permanent address: Groupe de Chimie Theorique, L.E.D.S.S., Universite
Scientifique et Medicale, B.P. 68, 38402 Saint-Martin-d'Heres Cedex,
France.
pIe, it will exist in all 0' radicals generated by abstraction of a
carboxyl hydrogen even if there are no high symmetry con-
formations in the vicinity of the equilibrium structure, at
least as long as the CO
2
group is not interacting strongly
with other chemical groups.
In this paper we present steps in the successful solution
to the problem of the structure of the O'-formyloxyl radical,
with emphasis on the chemical arguments used in building
the computational models. The 0'-HC0
2
electronic state is
the ground state; a low lying 1T state also provides a symme-
try breaking challenge, more easily met, as we shall show,
than that presented by the 0' state. However, to obtain a
reliable 0'-1T separation the same model must be used for both
states; this has been done in the calculations we present.
These states are not known experimentally; our introduction
to the problem several years ago was, in fact, aimed at deter-
mining whether the 0' or 1T state was the ground state.
Unlike earlier theoretical studies of this system,
l
our
final MCSCF model yields a qualitatively correct potential
energy surface. The systematics of our stepwise procedure in
building this model can be applied in any theoretical study
where symmetry breaking might be found. For quantitative
predictions the MCSCF potential energy surfaces need cor-
recting, particularly for the 0'-1T excitation energy, and this is
done at the multireference CI (MRCI) level. Harmonic fre-
quencies extracted from our MRCI surfaces represent the
best theoretical values to date. The best previously reported
theoretical study, due to Feller et al., 1 obtained qualitatively
correct results at the CI level (a symmetric structure for the
radical, in both 0'- and 1T-electronic states) but these authors
did not report vibrational frequencies. The asymmetric C-O
stretching frequency is of particular interest, as it provides a
sensitive test of the accuracy of the theoretical model.
DISCUSSION
In this section, the terminology used to analyze the sym-
metry breaking problem will be defined. The notion of a
generalized potential energy surface will be introduced.
We illustrate these concepts with a discussion of a sim-
ple system that exhibits symmetry breaking, Hel . Hel pos-
sesses two resonance structures shown schematically in Fig.
J. Chern. Phys. 83 (7), 1 October 1985 0021-9606/85/193567-10$02.10 @ 1985 American Institute of Physics 3567
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3568 McLean et al. : Formyloxyl radical
He
s
Wavefunction

'l'L
2 ,
aA as
as

'l'R
' 2
aAaS
as
FIG. 1. Resonance structures for He,+.
1 with their associated wave functions 'l'L' with two elec-
trons localized on the left-hand atom, and the symmetrically
equivalent 'l'R' with two electrons localized on the right-
hand atom. For internuclear separations larger than -r. it
is possible to determine three single configuration SCF wave
functions for It is illuminating to relate these three
solutions to the structures of Fig. 1. (For this discussion we
can assume that the SCF orbitals are expanded in a complete
basis). The three wave functions are \}I L' 'l'R' and 'l's:
'l'L =
describing the first resonance structure, and
\}IR =
describing the second resonance structure in Fig. 1, and
which contains both resonance structures. \}I L and 'l'R are
symmetry broken wave functions (they do not have the D co h
symmetry, including inversion, of a homopolar diatomic
molecule) while \}Is is not symmetry broken [orbital (0";:
+ ui) is gerade, (0";:' - 0";') is ungeradeJ. Orthogonality
constraints are (0".1 = 0 in 'l'L' IO"B) = 0 in \}I R'
and the orthogonality forced by the g, u orbital symmetry in
\}Is. 0".1, 0";:, 0";:' and are essentially, distorted Is-type He
atomic orbitals in order of decreasing size, while 0" B' 0";, 0";',
and are, respectively, their symmetric counterparts.
Orbital size effects are one critical factor in determining
the relative energies of the localized wave functions 'l'L' \}I R ,
and the delocalized wave function 'l's. In \}I L and 'l'R the
orbital size effect is optimum; 0".1 looking like a distorted He
atomic orbital is considerably more diffuse (larger) than
which looks like a distorted He + atomic orbital in which the
electron sees the full unshielded nuclear charge. In 'l's, by
comparison, the orbital size effect contained in 0";:
2
0";', and
0"; 2 u:.;' has been severely compromised by the need, in the
variational SCF calculation, to reduce the effect of the high
energy ionic structures 0";:2 u:.;' and 0";2 0"'; which enter the
wave function with nonvariational mixing coefficients pre-
determined by the g, u orbital symmetry constraint. The ef-
fect is to make 0";: and u:.;' rather close in size, intermediate
between the sizes of 0".1 and .
Resonance effects are the other critical factor. \}Is does
contain the stabilizing resonance interaction of the two lo-
calized structures 0";: 2 0";' and 0"; 2 0";:', albeit with less than
optimal orbital sizes. \}I L and 'l'R do not contain this interac-
tion.
In the He
2
+ case, for nuclear separations less than some
value R the resonance effect is more important energetically
than the orbital size effect and 'l's is the low energy wave
function; for greater than R the relative importance reverses
and 'l'L' 'l'R are the low energy solutions. Of course, in a
homopolar diatomic molecule the g, u orbital symmetry can
always be imposed so that converging to a high energy SCF
wave function which does not break symmetry poses no
problems. This is not, in general, the case for polyatomic
molecules where symmetry breaking is much more difficult
to deal with. In dealing with it, however, the two key effects
to consider when building computational models are orbital
size effects tempered, in nonsymmetry broken wave func-
tions, by nonvariational mixing of high energy structures,
and resonance effects.
One attractive, compact wave functon for Het would
be the two configuration wave function (\}I L + 'l'R) involv-
ing four orbitals with only the two orthogonality constraints
(0".1 = IO"B) = O. Calculation of the energy in-
volves a 2X2 nonorthogonal CI. To span the same configu-
ration space in a basis of orthogonal orbitals requires a CI
expansion in the configuration state function (CSF) basis
generated by assigning three electrons in all possible ways to
the four orbitals obtained by orthogonalizing 0".1 , , 0" B ,
-the well known result of orbital doubling.
A number of different approaches to the symmetry
breaking problem have been examined in the past,I-7 em-
ploying both orthogonal and nonorthogonal orbitals. With
recent advances in MCSCF methodology,
8
it is now possible
to pursue the symmetry breaking problem with orthogonal
orbitals much further than was heretofore the case. We can
now examine a series MCSCF wave functions, consisting of
many thousands of CSF's generated by successively includ-
ing resonance and size effects in different orbital subspaces.
Orthogonal orbital methods have a distinct advantage in
characterizing potential energy surfaces, as techniques are
now available to obtain the first and second derivatives of the
energy with respect to nuclear displacements at both the
MCSCF
9
-
11
and CI
II
-
13
level. In addition, efficient methods
to perform the CI calculations needed to accurately charac-
terize the important aspects of a potential energy surface are
readily available.
I
4-18 Similar techniques employing non-
orthogonal orbitals have yet to be demonstrated.
Before proceeding with an examination of the potential
energy surface of HC0
2
, a framework is needed in which to
understand the behavior of the different models employed in
our study. To this end, we introduce the notion of a general-
ized potential energy surface. An example of such a surface
is given in Fig. 2. AR is a coordinate which follows one of the
nuclear motions, in this case the asymmetric CO stretch,
AR = (R co. - R co
2
), as is a symmetry breaking coordi-
nate which follows changes in the orbital and CI mixing
degrees offreedom, in this case according to the lowest non-
symmetric eigenvector of the MCSCF Hessian (the matrix of
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McLean sf al. : Formyloxyl radical 3569
Delocalized Solutions
H
I
C
O ~ - ~
o
H
I
H
C
/ - ~
0' '0
I
C
~ - ~
~ . 0
1
0
1
3
H
I
/
C ~
'\::0
o
Et ~ R
~
Localized Solutions
FIG. 2. Generalized potential energy surface for HC0
2

~ = (R co, - R co,), AS is a coordinate defined by an eigenvector of the
MCSCF Hessian with a negative eigenvalue; it can be thought of as a param-
eter which mixes the b
l
and Q2 (C 2v) 1T orbitals.
second derivatives of the energy with respect to these degrees
of freedom). For the purposes of this discussion AS may be
thought of as a parameter which mixes the hI and a2 1T orbi-
tals.
Several key points have been identified on the saddle
shaped surface of Fig. 2. The ridge 2'1 2 contains energy
points with AS = O. The valley 5 4 3, in front of the ridge
contains energy points with positive values of AS. Behind the
ridge is another valley, not shown, along which points E'
(M, - AS) have the same energy as points E ( - M, AS)
along the first valley. The surface contains four minima with
respect to M variation: 2(M, 0) and 2'( - M, 0) with equal
energiesontheridge,and3(M ',AS')and3'( - M', - AS')
with equal and lower energies in the valleys.
At point I, COl and CO
2
bondlengths are equal and the
wave function possesses the C 2v symmetry of the nuclear
frame, assuming that the hydrogen is symmetrically placed.
However, the wave function at this stationary point is unsta-
ble with respect to both breaking the symmetry of the orbi-
tals and of the nuclear frame. (The MCSCF Hessian and the
force constant matrix both possess a negative eigenvalue.)
Point 2, also a stationary point, is a minimum with respect to
nuclear displacements, but the wave function is still unstable
with respect to symmetry breaking orbital variations. At
point 4 the wave function is stable but the nuclear frame is
not; this point, like point I, has equal CO bondlengths but
the wave function does not possess the symmetry of the nu-
clear frame. Unlike point I, it is not stationary with respect
to M_ Point 3, with point 3', the lowest energy point on the
surface, is a minimum with respect to both orbital and nu-
clear displacements. Along the ridge 2'1 2 and valleys 5 4 3
and 3'4'5' the energies, and corresponding wave functions,
are self-consistent. Extending the use of the term symmetry
breaking to nuclear conformations with M =1= 0, we say that
the SCF wave functions along the ridge, connecting smooth-
ly to the wave function at point I, do not break symmetry;
those along the valley, connecting smoothly to the wave
function at point 3, do.
Using second order MCSCF procedures, it is possible to
converge to the nonsymmetry breaking wave functions
along the ridge. The dipole moment in the M direction
changes smoothly, from its value of zero at point 1, as we
move from point 1 to point 2. In cases where there is no high
symmetry point it is necessary to monitor properties such as
the dipole moment; sharp variations over a small conforma-
tional range can indicate a change from a nonsymmetry
broken to a symmetry broken wave function, or vice versa.
At point 4 the dipole moment in the M direction is not zero,
even though the CO bondlengths are equal, because the wave
function contains only one of the resonance structures. The
dipole moment of the SCF wave functions along the valley
changes smoothly from 4 to 3 where its value is larger than
that at point 2. Without a second order MCSCF algorithm
only the SCF solutions along the valley are readily accessi-
ble.
Any reliable prediction of an equilibrium structure must
start from SCF (or MCSCF) wave functions that do not
break symmetry; the prediction from the MCSCF calcula-
tions can then be confirmed by CI calculation in a configura-
tion space constructed from the occupied MCSCF orbitals
and additional orbitals which span the remainder of the
space of chosen basis. A good MCSCF model will give qual-
itatively the same results as the subsequent CI. We have
found that earlier studies of the ground state HC0
2
surface
employed unbalanced MCSCF solutions (symmetry retain-
ing for some conformations and symmetry broken for oth-
ers), an unsound practice, even though in the complete CI
limit it would not make any difference. The complete CI
limit is, of course, normally unachievable.
The surface depicted in Fig. 2 is an idealized case. It is
quite possible that the curve connecting points 1 and 2 be
stable with respect to symmetry breaking orbital variations,
but the barrier between 1-2 and 3-4 could be small, in which
case unbalanced MCSCF solutions could easily emerge. The
essential point is that, by using second order procedures we
can distinguish and control the different solutions that are
possible when symmetry breaking is a factor in molecular
structure calculation. In following different solutions it is
helpful and informative to monitor other properties of the
wave function, such as the electric moments and population
analysis. This is especially true if there is a small barrier
between the curve connecting points 1 and 2 and the curve
connecting points 3 and 4.
In the case of HC0
2
, the true potential energy surface
has a minimum for both the u and 1T states at a symmetric
geometry. But, if an inadequate wave function is employed a
potential energy surface similar to that shown in Fig. 2 could
result. The next section, reporting actual HC0
2
calcula-
tions, will give examples.
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3570
McLean et al. : Formyloxyl radical
HCOaCALCULATONS
MCSCF calculations on the u radical
The obvious starting point is to calculate single configu-
ration SCF wave functions with the orbitals expanded in a
reasonable basis, at least of double zeta polarized (DZP)
quality. That is, for u HC0
2
, we look for a wave function
which can be written as
KKKro, ro, A
The problems to be resolved immediately present themselves
in the three possible SCF wave functions which can be calcu-
lated with the electron assignment of configuration space A.
For calculations in the vicinity of the equilibrium structure
the critical features of the three solutions are shown schema-
tically in Fig. 3. Derived from a generalized potential energy
surface which considers orbital and configuration mixing
changes as degrees of freedom, as discussed in the previous
section, the curves of Fig. 3 are the projections onto a plane
of the ridge and valleys which follow SCF wave functions
and energies.
The C 2v point on curve I of Fig. 3 is the SCF energy
calculated when the orbitals are constrained to C 2v symme-
try. No lower energy can be calculated if this constraint on
the orbitals is imposed. The unpaired electron will be in a b
2
orbital with the qualitative description (Po, "Po,) where the P
functions are in the plane of the molecules, transverse to the
bonds, and the orbital has a node in the bridging region. The
tr electrons are in delocalized orbitals. If the orbital symme-
try constraint is relaxed and the energy behavior calculated
with respect to nonredundant orbital rotations, between oc-
cupied and occupied or between occupied and unoccupied
orbitals, that break the symmetry constraint, it will be found
H
H I H
I I
c C
I
o I 4/ 0
o 0
"-I
E
II
o
.:lR = (R
C01
- R
C02
)
FIG. 3. Schematic behavior of E SCF for the three possible SCF solution in
configuration spaces A and B (see text).
H H
I .. I
a /C", 0 a /C,\- 0
01 r:l 02 01 02
8c9
(a) (b)
FIG. 4. Valence bond structures of HC0
2

that the energy can be lowered; the MCSCF Hessian will
have a negative eigenvalue. Even so, the C 2v point on curve I
is still stationary with respect to orbital rotations; by defini-
tion, an SCF solution. Our study has not followed curve I
computationally, although, using Newton-Raphson sec-
ond-order procedures, it should be possible to do so; moving
short steps in AR and using neighbor orbitals as trial orbitals
for the current point should permit us to follow the SCF
solution with one negative eigenvalue of the MCSCF Hes-
sian.
The C 2v point on curve II in Fig. 3 has the unpaired
electron in an orbital which is essentially pure Po . This solu-
tion is the valence bond structure (a) of Fig. 4, with a double
bond between C and 01> a single bond between C and O
2
, and
a tr-lone pair on O
2
, The electronic charge density in struc-
ture (a), for C 2v geometries, does not have C 2v symmetry; the
wave function for curve II is a "symmetry broken" approxi-
mate solution of the SchrOdinger equation. For negative AR,
as the COl length shortens and the CO
2
length increases, in
the vicinity of equilibrium, the energy must decrease as the
double and single bonds move toward their optimum values.
The C 2v point on curve III in Fig. 3, equal in energy to
the point on curve II, is the solution symmetrically equiva-
lent to curve II; that is, the wave function is the valence bond
structure (b) of Fig. 4 which also is symmetry broken. A
point on curve III for negative AR corresponds to a long
double bond, short single bond solution obviously higher in
energy than the corresponding point on curve II. Even so, at
least for a limited distance, it is possible to compute points on
the curve, using neighbor SCF orbitals for trial orbitals at the
current point. The solution will still have, as it does for posi-
tive AR, all positive eigenvalues of the orbital Hessian.
A key aspect of the SCF descriptions of structures (a)
and (b) in configuration space A is the different optimum
sizes of the Po, and Po, orbitals. In fact, the discussion of the
u2q' space in configuration space A is the same as the He
2
+
discussion of the previous section with P orbitals substituted
for s orbitals. In structure (a) the doubly occupied Po, is
considerably expanded in comparison to the singly occupied
Po ,while in structure (b) the reverse is true. This orbital size
is the dominant reason why curves II and III lie below
curve I for calculations in configuration space A. The SCF
wave function for curve I at C 2v geometries can be rewritten,
in terms of localized orbitals, as an equally weighted linear
combination of structures (a) and (b) with approximately
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McLean 8t al. : Formyloxyl radical 3571
equally sized P orbitals on the two oxygens together with
ionic structures whose mixing coefficients are set by the orbi-
tal symmetry constraints. In fact, as shown in the He
2
+ anal-
ysis, the size of the P orbitals is adversely affected in the effort
to reduce the energy raising due to the too heavily weighted
ionic structures. This rewriting permits us to compare wave
functions corresponding to curves I, II, and III in chemical
terms, to explain their shapes, and to see how to progress to
the next step in solving the structure of HC0
2
Curve I, cor-
responding to SCF wave functions that do not break symme-
try, correctly contains the resonance of symmetrically equi-
valent structures but does not contain the optimum orbital
size effect. Curves II and III, by contrast, have taken advan-
tage of the orbital size effect which is clearly more important
than the resonance interaction. This is why, as curve I moves
away from IlR = 0, it is a virtual certainty that the energy
drop, one of the structures (a) or (b), becomes increasingly
dominant and even in the SCF wave function that does not
break symmetry, the orbital size effect can be more nearly
optimum. .
At this point we are in no position to make any predic-
tion of the equilibrium structure and its properties. The low-
est energy curve is II to the left of IlR = 0 and III to the
right. It has a cusp at C 2v geometries in the vicinity of equi-
librium; the wave function is discontinuous going through
IlR = 0, and breaks symmetry. The fact that II and III break
symmetry make them unsuitable starting points for large
scale CI since the symmetry broken SCF orbital space must
favor approximate wave functions for unequal equilibrium
CO} and CO
2
bond lengths over equal.
However, a prediction of a symmetric equilibrium
structure from large scale CI built from curves II or III
would be generally reliable; a starting point with a fairer
treatment of the symmetric structures would only
strengthen the prediction. But, because of the symmetry
broken starting point calculations of energy separations
between states may still be unreliable. Curve I predicts an
asymmetric equilibrium structure, but because of the neglect
of the orbital size effect, cannot be taken seriously. It is con-
ceivable however, that curve I be a satisfactory starting point
for large scale CI, both for calculating the true equilibrium
structure and relative energies. We must emphasize that we
have not computed curve I. We are drawing attention to the
possibility of doing so, and the utility of such a calculation.
How than to proceed? One approach that must be men-
tioned is that ofJackels and Davidson,2 first used in calcula-
tions on N0
2
. In this approach, wave functions II and III in
configuration space A would be variationally mixed in a
nonorthogonal CI. This is a powerful calculation. It clearly
includes, optimally, both resonance and orbital size effects.
It is a two configuration CI using a double set of orbitals,
because the orbitals of curve II, while qualitatively similar to
those of curve III, are quantitatively different. In fact, to do
this same calculation in an orthogonal orbital framework
would require orbital doubling, as explained in our earlier
discussion. In this paper we will find the solution to the
HC0
2
problem in the framework of orthogonal orbital cal-
culations, and it will be important, practically, to find a solu-
tion which avoids orbital doubling as much as possible. But
before we proceed, some problems with the Jackels and Da-
vidson
2
approach should be mentioned. There are two. First,
if both solutions II and III cannot be found for a particular
value of 1lR, and this may be true for strongly asymmetric
CO bondlengths, the calculation cannot be done, even
though one structure, either (a) and (b) will dominate for
such conformations; the mixing is needed for smooth energy
surfaces. We have pointed out however, that second order
procedures can probably eliminate this problem. Second,
and more important, in the nonorthogonal framework the
large scale CI needed to make quantitative calculation, espe-
cially of energy separations, is not practical at this time.
The next step is to investigate SCF wave functions in
configuration space B.
B
From the earlier discussion it is clear that the only way of
introducing the orbital size effect into the ((70') space is orbi-
tal doubling which, in an orthogonal orbital framework,
would be done by allowing correlatingp orbitals on O} and
02' transverse to the bonds and with the nodal structure of
3p functions, to enter the active space of an MCSCF calcula-
tion. We have not done so in configuration space B. While
not directly facing up to the orbital size effect, the use of
configuration space B is an effort to see if symmetry breaking
solutions can be avoided by introducing correlation into the
11' shells; done by assigning the four 11' electrons in all possible
ways to the three 11' orbitals which can be constructed from
2p functions on the carbon and two oxygens, denoted (11'11'11").
3
If the 11' correlation causes the 11' electrons to delocalize this
may induce the 0' electrons in Po, and Po, to delocalize for
C 2v geometries. But computation shows that this does not
happen; it is the delocalization of the 0' electrons that drives
the delocalization of the 11', and delocalization of the 0' elec-
trons in the lowest energy SCF wave functions requires orbi-
tal doubling. In configuration space B, the schematic behav-
ior of Fig. 3 again applies. There are two symmetry broken
symmetrically equivalent wave functions. One of these wave
functions will, at C 2v geometries near equilibrium, be predo-
minantly structure (a) with a very small amount of structure
(b) introduced through the 0'-11' correlation that, essentially,
permits the double bond to change sides as the hole in the
(Po,Po, ) space changes sides. But, as in configuration space
A, there is also a symmetry retaining high energy solution
easily calculated for IlR = 0 by imposing a C 2v symmetry
constraint on the orbitals. Again, as in configuration space
A, it should be possible to follow the solution to points with
IlR :;f0 if we use a quadratically convergent MCSCF proce-
dure which can follow solutions with negative eigenvalues of
the orbital Hessian. The quantitative details of Fig. 3 for
calculations in configuration spaces A and B will not be very
different; as regards answering the questions posed earlier
for HC0
2
, we have not progressed.
It is now evident that the orbital size effect must be faced
head on, and that is done in configuration space C:
KKKro, ro, CQi C
In a nonorthogonal orbital description, we would intro-
duce a Po, orbital optimum in size for double occupancy
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3572 McLean et al. : Formyloxyl radical
[structure (a)] and another Po, orbital strongly overlapping,
of smaller size, optimum for single occupancy [structure (b)),
and the symmetrically equivalent P0
2
pair as well. In the
orthogonal orbital description used here the same effects can
be introduced by orthogonalizing this set of four nonortho-
gonal orbitals, giving Pt,. and Pt,. with 3p nodal properties.
In this configuration space we can find only one SCF wave
function, one that retains symmetry in the electronic wave
function for C 2v geometries. The energy behavior of this
wave function, around equilibrium, is shown schematically
in Fig. 5. Compared with Fig. 3, the symmetry breaking
solutions have disappeared. In configuration space Conly
the high energy symmetry retaining solution of Fig. 3 is ob-
tained. There is no negative eigenvalue of the MCSCF Hes-
sian; no nonredundant orbital rotations, between occupied
orbitals or between occupied and unoccupied orbitals, can
cause the energy to drop at the calculated geometry. Thus,
there is no problem in calculating points along the curve of
Fig. 5. Again, comparing with the high energy curve of Fig.
3, the barrier between the symmetric double well will be
reduced because, at C 2v geometries, not only is the resonance
of structures (a) and (b) correctly described, but, by construc-
tion, the dominant orbital size effect in Po, and P0
2
has been
introduced. The added fiexibility in configuration space C
has also permitted, to a large extent, the variational mixing
of the higher energy ionic structures which appear when the
wave function is written in terms of localized orbitals. This
too has helped the symmetry retaining wave function to be-
come the lowest energy one.
At this point, we could make a tentative prediction of an
asymmetric equilibrium structure, but with the following
reservations. Looking at the asymmetric electron distribu-
tions in structures (a) and (b) of Fig. 4, even at C 2v geome-
tries, it is clear that the asymmetry in the P electrons will
induce an asymmetry into the bonds as well, and that we
should investigate orbital doubling in the description of the
bond orbitals. This will lower the barrier shown in Fig. 5,
possibly to the point that it will become a minimum instead
E
I
I
I
I
I
-----t---
I
I
I
I
I
o
LlR = (R
C01
- R
C02
)
FIG. S. Schematic behavior ofF SCF for the simple possible SCF solution in
configuration space C (see the text).
of a maximum in SCF calculation. We have carried out large
scale CI calculations with the SCF wave functions in config-
uration space C as a starting point. They too introduce the
orbital size effect for all the electrons, and much more effec-
tively than further SCF calculation. They show that the pre-
diction from Fig. 5 is false. The large scale CI calculations
show a symmetric equilibrium structure and we regard this
to be an unequivocal demonstration. At this point, then, we
have an MCSCF model which gives a qualitatively incorrect
equilibrium structure prediction, although it is a good start-
ing point for large scale CI, whose results can be trusted. The
key point is that the orbital basis for the large scale CI config-
uration space is from a symmetry retaining MCSCF calcula-
tion.
To carry our calculations to the point where the
MCSCF model gives the same qualitative behavior as large
scale CI built on it, we went one step further, to configura-
tion space 0:
KKK ~ . ~ . (CO
I
COt)2(C0
2
CO!)2
X (CH CH*)2(PO,pt"P0
2
Pt,2 )3(1T1T1Tt o
An important point about configuration space 0 is that
the attempt to introduce orbital doubling to describe the
"secondary" orbital size effects in the CO bonds has been
done through the same antibonding orbitals needed for bond
dissociation; while the pt,. , pt" needed for the "primary"
orbital size effect go outside the valence space (the space
which correlates with the strongly occupied separated atom
orbitals) the antibonding orbitals of configuration space C
are within it. We are attempting to describe the nonortho-
gonal orbital doubling without extending the dimension of
the active orthogonal orbitals, an important consideration in
controlling the dimension of the MCSCF configuration
space. Even configuration space 0 has a dimension greater
than 10 000; beyond our computational capacity when the
calculations were done in 1981. Our actual calculations,
which include all the effects we have discussed, were done in
configuration space D':
KKK ~ , ~ 2 (COl COni(C0
2
CO!)(CHCH*)ii(1T1T1T)1
X [(Po.pt,. )i(PO,pt,2)1 + (Po. pt,. ) I (Po,pt,. )i ]. 0'
In configuration space 0', the subscript S means that
electrons in the orbital subset so labeled are restricted to
singlet coupling. The dimension of this space is 1944. The
energy behavior of the wave function is shown in Fig. 6. The
wave function does not break symmetry. Since any further
introduction of orbital size effects will be more important at
resonance (C 2v conformations) further extension of the con-
figuration space can only make the well of Fig. 6 deeper.
Thus, finally, in MCSCF calculations we have an unequivo-
cal prediction of a symmetric eqUilibrium structure. It is
confirmed in subsequent large scale CI calculations, which,
as expected, deepens the well in the asymmetric stretch. The
energy behavior in other vibrational modes is already very
well described by the MCSCF wave function. Figure 7 shows
this in the comparison ofMCSCF structures and frequencies
for wave functions expanded in configuration space 0' with
large scale CI results based on these same MCSCF wave
functions.
J. Chern. Phys., Vol. 83, No.7, 1 October 1985
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McLean sf at. : Formyloxyl radical 3573
I
I
I
I

E I
I
I
I
I
I
o
= (R
C01
- R
C02
)
FIG. 6. Schematic behavior of E SCF in configuration space D' (see the text).
MCSCF calculations on the 1T radical
The 1T-radical MCSCF results of Fig. 7 are in the config-
uration space E:
KKK .ro .ro,(C0
1
COT)(C0
2
CO';)i
X (CHCH*)i(Po.Po. )i(1T1T1T)1, E
which is the obviously comparable space to D'. It too has a
dimension of 1944. (Subscript D on the (1T1T1T) subspace in E
designates that the three electrons are spin coupled doublet].
In this space, the wave function does not break symmetry
and, as shown in Fig. 7, predicts a symmetric equilibrium
structure. The 1T radical, similar to the well known allyl radi-
cal, needs only the (17"1T17")3 treatment of the 17" electron to
avoid symmetry breaking, in a configuration space compara-
ble to space B, but for calculating Il.E with large scale CI
based on an MCSCF starting point, the MCSCF starting
points must be comparable; hence configuration space E.
Correlation effects in the (Po. Po, ) and (17"17"17") subspaces
of the CT and 17" radicals will be different, and this cannot be
described quantitatively by MCSCF calculations in configu-
ration spaces D' and E. That is why the Il.E change from
MCSCF to large scale CI is so large (0.14 to 9.16 kcal/mol).
The CI, designed to include these effects is the result to be
taken seriously.
Large scale configuration Interaction calculations
Table I shows the orbital subsets and electron assign-
ments used in constructing configuration spaces for large
scale CI computations on the CT and 1T formyloxyl radicals.
The dimensions of the full configuration spaces given in Ta-
ble I need to be reduced in practical computation. This is
done by retaining only those members of the Table I configu-
ration space satisfying the constraints of Table II.
In setting up large scale CI calculations it is, of course,
desirable to build from the MCSCF plateau; we would like
the large scale CI wave function to contain the MCSCF wave
function and so the orbitals used in the CI configuration
space must come from the MCSCF calculation. In configu-
ration spaces A-E, used in our MCSCF calculations, the
MCSCF procedure uniquely determines the orbital sub-
spaces, not the orbitals spanning the subspaces; the MCSCF
wave functions are invariant to orbital rotations within sub-
spaces. If, in a subsequent CI calculation orbitals within a
subspace are not treated equivalently it will be essential to
have uniquely defined orbitals. The obvious set of uniquely
defined orbitals is the set of natural orbitals of the MCSCF
wave function. For MCSCF expansions in configuration
spaces A-E the subspaces spanned by the natural orbitals are
identical to the MCSCF subspaces, because the first order
density matrix blocks by orbital subset. This is an important
consequence of wave function invariance for rotation within
an orbital subset. If an MCSCF wave function does not have
this property the space of the natural orbitals will be differ-
ent to that of the MCSCF orbitals and the MCSCF wave
function will not be exactly contained in the CI expansion.
Thus, corrections in the CI are not from a well defined
MCSCF plateau and this may affect the quality of the calcu-
lation.
In the CI configuration spaces of Table I the orbital
subsets are not the same as in MCSCF configuration spaces
D' and E; the CI orbital subset structure (Po.Po, 1T1T17")
is different from the MCSCF subset structure )
(1T1T1T). This is one reason why the orbitals must be
uniquely defined in setting up the CI. The other reason, seen
in Table II, is that the reference configurations contain only
doubly occupied bonding orbitals; the members of
rr-HC0
2
MCSCF
H
1
1
.
099
119.4C
/..
o 121.2 0
471
699
1376
1451
3177
H
11.098
123.9 C
/.
o 112.2 0
594
649
1313
1479
3184
CI
H
1
1
.
101
119.5 C

o 121.0 0
757
696
1372
1437
3177
H
1
1
.
099
123.7 C
/ '-1.268

961
646
1314
1477
3197
FIG. 7. MCSCF and MRCI optimized structures and frequencies for (T- and
1T-HC0
2
The configuration spaces for MCSCF calculations are D' and E
(see the text). Orbitals are expanded in a DZP basis. CI configuration spaces
are given in Tables I and II. Distances in A, bond angles in degrees, harmon-
ic frequencies in cm -I. All optimized structures have C 2. symmetry.
J. Chern. Phys., Vol. 83, No.7, 1 October 1985
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3574 McLean 9t al. : Formyloxyl radical
T ABLB I. Configuration spaces for large scale CI calculations.-
Subspace (C0
1
C01) (C0
2
cot) (CHCH*)
fpo,Po,1MMT) (u ... ) (17'.,..)
1. 2 2 2 7 0 0 0
2. 2 2 1 8
2 1 2 8
1 2 2 8
1 2 0 9
2 0 2 0
0 2 2 9
3. 2 2 2 6 1
2 2 1 7 1
2 1 2 7 1
1 2 2 7 1
2 2 2 6 0 0 1
2 2 1 7 0 0 1
2 1 2 7 0 0 1
1 2 2 7 0 0 1
2 2 2 6 0 1 0
2 2 1 7 0 1 0
2 1 2 7 0 1 0
1 2 2 7 0 1 0
4. 2 2 2 5 2 0 0
2 2 1 6 2 0 0
2 1 2 6 2 0 0
1 2 2 6 2 0 0
2 2 2 5 0 0 2
2 2 1 6 0 0 2
2 1 2 6 0 0 2
1 2 2 6 0 0 2
5. 2 2 2 5 1 0
2 2 1 6 1 0
2 1 2 6 1 0
1 2 2 6 1 0
2 2 2 5 0 1
2 2 1 6 0 1
2 1 2 6 0 1
1 2 2 6 0 1
-The table shows assignments of electrons to orbital subsets. Not explicitly shown are the ten electrons KKK
common to all configurations. The orbital notation is that of the text. For the u radical, orbitals are
natural orbitals from the MCSCF wave function expanded in configuration space D'. For the 17' radical,
orbitals are natural orbitals from the MCSCF wave function expanded in configuration space B. In a DZP
basis there are 25 external u orbitals, reduced to 22 in (u ext) by the deletion of three K shell correlating
orbitals, and ten external 17' orbitals in (17' ext). For the u-radical calculations space and spin angular momenta
coupling to 2,4 '; for the 17' radical, to 2,4 In our actual calculations the dimension of the Table I configuration
space is reduced, as specified in Table II.
(COICOr) (C0
2
COr) (CHCH*) are not treated equivalently.
Noteworthy features of the large scale CI configuration
spaces are:
(1) Inclusion of the MCSCF configuration spaces except
for the omission of the unimportant configurations with
and occupations; we have not included electron
assignment 2 2 2 4 3 0 0 in Table I.
(2) Inclusion of all first order configurations (one elec-
tron in external orbitals) relative to reference configurations
containing all possible electron assignments to the most im-
portant Po, Po, 1NrTr orbitals.
(3) Inclusion of selected second order configurations
(two electrons in external orbitals) with two externalTr elec-
trons and with two external electrons, one in a q orbital and
the other in a Tr orbital.
This configuration space was designed to give an even-hand-
ed treatment of both q and Tr radicals. An essential ingre-
dient of the even-handed treatment is the use of multiple
reference configurations with an unbiased treatment of the
Po,Po,1NrTr orbitals.
RESULTS
Results of our MCSCF and MRCI calculations are giv-
en in Table III and in Fig. 7. The key points are the un-
equivocal demonstration that the equilibrium structures for
both q and 'IT radicals have C 2v symmetry and that the adia-
batic excitation energy, in our best calculation, from the
ground q-HC0
2
to excited Tr-HC0
2
is 9.16 kcal/mol. This
should be a more reliable value than the best previously pub-
lished values of 5.6 kcallmol
l
and 13.7 kcal/mol.l9 A
noteworthy feature of the data presented in Fig. 7 is the small
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McLean et al. : Formyloxyl radical
3575
TABLE II. Configuration spaces used in actual large scale CI calculations
on u- and 1/"-HC0
2

u-HC0
2
2 A ' configuration space ofTable I truncated so that only configura-
tions related to the 12 reference configurations below by single and double
orbital excitations are retained.
COl CO
2
CH
Po, Po,
1/" 1/" 1/"
2 2 2 2 1 2 2 0
2 2 2 2 1 2 0 2
Dimension 2 2 2 2 1 0 2 2
80160(DZP) 2 2 2 2 1 2 1 1
108 828 (TZP) 2 2 2 2 1 1 2 1
2 2 2 2 1 1 1 2
2 2 2 1 2 2 2 0
2 2 2 1 2 2 0 2
2 2 2 1 2 0 2 2
2 2 2 1 2 2 1 1
2 2 2 1 2 1 2 1
2 2 2 1 2 1 1 2
1/"-HC0
2
2
A configuration space of Table I truncated so that only configu-
rations related to the seven reference configurations below by single and
double orbital excitations are retained.
COl CO
2
CH
Po, Po,
1/" 1/" 1/"
2 2 2 2 2 2 1 0
Dimension 2 2 2 2 2 2 0 1
55165 (DZP) 2 2 2 2 2 0 2 1
76564 (TZP) 2 2 2 2 2 1 2 0
2 2 2 2 2 1 0 2
2 2 2 2 2 0 1 2
2 2 2 2 2 1 1 1
correction to the equilibrium geometry in going from
MCSCF to MRCI; the MCSCF wave function comes from a
model that indeed does contain all the effects that determine
the structure. This is further confirmed by the remarkably
similar harmonic frequencies, with the exception of the
asymmetric CO stretch. This is the one listed first in the set
of five in-plane frequencies shown in Fig. 7. But the asymme-
tric stretch coordinate is the one that gave all the trouble in
finding a satisfactory MCSCF model. All lesser models gave
entirely wrong energy profiles along this coordinate. It is
therefore. not surprising that this first model with the cor-
rect qualitative behavior still needs further correction in a
large scale CI calculation.
The energies of Table III show that the adiabatic U-1T
separation is not significantly changed when the basis for
orbital expansions is improved from DZP to TZP
polarized). Our quoted energy differences are probably a
good approximation to the values that would be obtained
with orbital expansions in a complete basis. The MCSCF
value for this energy separation, near zero, is much too small
because of an unbalanced treatment of correlation in the u-
configuration space compared with the 1T-configuration
space. Because of the introduction of and into the
active orbital space, the four electrons in Po, and Po, in the 1T
radical are better correlated than the three electrons in these
same orbitals in the u radical. The MCSCF calculation will
give a 1T energy too low relative to the u energy, decreasing
the excitation energy. This imbalance is corrected, and possi-
bly slightly overcorrected, in the MRCI wave functions us-
ing the configuration spaces of Tables I and II.
CONCLUSIONS
We have been successful in finding a compact model for
the u-HC0
2
radical which, in MCSCF calculations with or-
thogonal orbitals, yields a qualitatively correct potential en-
ergy surface. A novel, and essential, feature of this model is
the use of correlating orbitals in the active space of the
MCSCF calculation which come from outside of the valence
space of the constituent atoms. We have demonstrated,
through chemical arugments, the stepwise construction of
the model emphasizing the key effects of orbital size and
resonance. Our procedures are generally applicable to all
cases where symmetry breaking may occur.
We leave open the question of how necessary it is to have
a model that in MCSCF calculation gives the same qualita-
tive description of a potential energy surface as a subsequent
large scale CI based on it. What is absolutely clear is that the
MCSCF calculation must give orbitals which do not break
symmetry-in the general sense defined in our paper. It ap-
pears that large scale CI built from such orbitals can be trust-
ed to give reliable predictions of structures and energies even
when qualitatively different from the MCSCF predictions.
To carry out MCSCF calculations that do not break symme-
try will need the power of second-order procedures to con-
verge on wave functions which are not the lowest in energy.
More work is needed to thoroughly test the use of simple
MCSCF models to produce symmetry retaining orbitals as a
basis for large scale CI. If this procedure proves to be reliable
it is enormously simpler and more economical than develop-
ing a more sophisticated model. In addition, simpler
MCSCF models offer significant advantages when several
points on the potential energy surface need to be character-
ized in the course of a chemical reaction. In this case reac-
tants, transition states, and products must be treated equiv-
alently. More complicated MCSCF models with more
weakly occupied orbitals will satisfy this requirement with
more difficulty because of the possible changing role of the
weakly occupied orbitals across the surface. However, deriv-
TABLE III. MCSCF and MRCI energies for u- and 1/"-HC0
2
The configu-
ration spaces for MCSCF calculations are D' and E (see the text). Orbitals
are expanded in DZP and TZP bases, as noted. MRCI configuration spaces
are defined in Tables I and II. The nuclear conformations of Fig. 7, opti-
mum for DZP bases, are used to compute these energies. t:.E is the adiabatic
U-+1T excitation energy.
Calculation Energy (hartrees) t:.E (kcal!mol)
MCSCF(DZP) 1/" - 188.326288
u - 188.328968
dift' 0.002 680 1.68
MCSCF(TZP) 1/" - 188.343028
u - 188.343253
dift' 0.000225 0.14
MRCI(DZP) 1/" - 188.387333
u - 188.402308
dift' 0.014975 9.40
MRCI(TZP) 1/" - 188.412 110
u - 188.426715
dift' 0.014605 9.16
J. Chern. Phys., Vol. 83, No.7, 1 October 1985
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3576 McLean et al : Formyloxyl radical
ing the most compact model that does yield the correct key
features of a structure brings with it the satisfaction of hav-
ing really understood the system.
ACKNOWLEDGMENT
Without the critical comments and advice of our col-
league Bowen Liu our analysis of the symmetry breaking
problem would undoubtedly have been less convincing.
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J. Chern. Phys., Vol. 83, No. 7,1 October 1985
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