ISSN:
1432-2234
Schlagwort(e):
MoCr(O2CH)4
;
ab initio SCF, CI
;
energy functional
;
double minimum
Quelle:
Springer Online Journal Archives 1860-2000
Thema:
Chemie und Pharmazie
Notizen:
Abstract Ab initio restricted Hartree-Fock (RHF) calculations carried out on the ground state of MoCr(O2CH)4 lead to two distinct energy minima according to the initial guess made for the set of trial vectors. It is shown that these two symmetry-adapted wavefunctions can be correlated with a twofold degenerate broken-symmetry solution previously characterized for the related system of higher symmetry Cr2(O2CH)4. Complete CI expansions have been carried out from either RHF polarized wavefunction using as a basis the set of eight frontier MO's with high metal character. These expansions yield poorly resymmetrized wavefunctions. A similar CI expansion has finally been carried out from a wavefunction resymmetrized at the SCF level and corresponding to a saddle point of the RHF energy hypersurface. The total energy associated with this latter expansion is the lowest obtained in the present work. The natural orbital analysis corresponds to (σ)1.86(π)3.58(δ)1.54(δ)0.46(π)0.42 (δ*)0.14 and shows that this resymmetrized CI expansion is in many respects similar to the correlated wavefunctions obtained for the homobinuclear parent systems.
Materialart:
Digitale Medien
URL:
http://dx.doi.org/10.1007/BF00577140
Permalink
