A systematic approach to symmetry breaking in molecular calculations is presented. Energy curves of the ground state (0') and the first excited state (1T) of the formyloxyl radical are analyzed. The 0' and 1T equilibrium structures are shown to be symmetric.
A systematic approach to symmetry breaking in molecular calculations is presented. Energy curves of the ground state (0') and the first excited state (1T) of the formyloxyl radical are analyzed. The 0' and 1T equilibrium structures are shown to be symmetric.
A systematic approach to symmetry breaking in molecular calculations is presented. Energy curves of the ground state (0') and the first excited state (1T) of the formyloxyl radical are analyzed. The 0' and 1T equilibrium structures are shown to be symmetric.
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 Downloaded 25 Mar 2011 to 200.20.3.72. Redistribution subject to AIP license or copyright; see http://jcp.aip.org/about/rights_and_permissions 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 J. Chem. Phys . Vol. 83, No.7, 1 October 1985 Downloaded 25 Mar 2011 to 200.20.3.72. Redistribution subject to AIP license or copyright; see http://jcp.aip.org/about/rights_and_permissions 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. J. Chern. Phys., Vol. 83, No.7, 1 October 1985 Downloaded 25 Mar 2011 to 200.20.3.72. Redistribution subject to AIP license or copyright; see http://jcp.aip.org/about/rights_and_permissions 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 J. Chern. Phys., Vol. 83, No.7, 1 October 1985 Downloaded 25 Mar 2011 to 200.20.3.72. Redistribution subject to AIP license or copyright; see http://jcp.aip.org/about/rights_and_permissions 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 J. Chern. Phys . Vol. 83. No. 7.1 October 1985 Downloaded 25 Mar 2011 to 200.20.3.72. Redistribution subject to AIP license or copyright; see http://jcp.aip.org/about/rights_and_permissions 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 Downloaded 25 Mar 2011 to 200.20.3.72. Redistribution subject to AIP license or copyright; see http://jcp.aip.org/about/rights_and_permissions 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 Downloaded 25 Mar 2011 to 200.20.3.72. Redistribution subject to AIP license or copyright; see http://jcp.aip.org/about/rights_and_permissions 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 J. Chern. Phys., Vol. 83, No.7, 1 October 1985 Downloaded 25 Mar 2011 to 200.20.3.72. Redistribution subject to AIP license or copyright; see http://jcp.aip.org/about/rights_and_permissions 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 Downloaded 25 Mar 2011 to 200.20.3.72. Redistribution subject to AIP license or copyright; see http://jcp.aip.org/about/rights_and_permissions 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. ID. Feller, E. Huyser, W. T. Borden, and E. R. Davidson, J. Am. Chern. Soc. lOS, 1459 (1983). 2C. F. Jackels and E. R. Davidson, J. Chern. Phys. 65, 2941 (1976). 3 A. Voter and W. Goddard, Chern. Phys. 57, 253 (1981); J. Chern. Phys. 75, 3638 (1981). 4L. Englebrecht and B. Liu, J. Chern. Phys. 78, 3097 (1983). 'E. R. Davidson and W. T. Borden, J. Phys. Chern. 87,4783 (1983). 6D. Feller, E. R. Davidson, and W. T. Borden, J. Am. Chern. Soc. 105, 3348 (1983). 7J. Paldus and A. VeiIlard, Mol. Phys. 35, 445 (1978). 8B. H. 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Phys. 77, 5584 (1982). 19S. D. Peyerimhoft", P. S. Ske1l, D. D. May, and R. J. Buenker, J. Am. Chern. Soc. 104,4515 (1982). J. Chern. Phys., Vol. 83, No. 7,1 October 1985 Downloaded 25 Mar 2011 to 200.20.3.72. Redistribution subject to AIP license or copyright; see http://jcp.aip.org/about/rights_and_permissions