Premium
The half‐projected Hartree–Fock model for computing thermally “forbidden” pericyclic reactions
Author(s) -
Olivella Santiago,
Salvador José
Publication year - 1991
Publication title -
journal of computational chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.907
H-Index - 188
eISSN - 1096-987X
pISSN - 0192-8651
DOI - 10.1002/jcc.540120704
Subject(s) - pericyclic reaction , wave function , hartree–fock method , singlet state , mindo , hamiltonian (control theory) , electron , computation , chemistry , physics , computational chemistry , atomic physics , quantum mechanics , mathematics , excited state , molecule , mathematical optimization , algorithm
The possible use of a half‐projected Hartree–Fock (HPHF) wavefunction correlating a single pair of electrons is investigated in relation with the computation of potential energy hypersurfaces associated to pericyclic reactions of systems with an even number of electrons, in which the orbital configuration of the lowest‐energy singlet state is not conserved during the course of the reaction. The results of calculations, within the framework of the MINDO/3 Hamiltonian, for eleven stationary points on the potential energy hypersurfaces of three prototypical thermally “forbidden” pericyclic reactions indicate that, in general, the HPHF model provides a geometrical and energetical description that is equivalent to that obtained from a conventional two‐configuration self‐consistent‐field approach.