Quasi-classical alternatives in quantum chemistry

Abstract

The article contains an overview of authors achievements in development of alternative quantum-chemical approaches oriented towards revival of the classical tradition of qualitative chemical thinking instead of obtaining numerical results. The above-mentioned tradition is concluded to be based mainly on principles (rules) of additivity, transferability and locality of molecular properties. Accordingly, model Hamiltonian matrices are used in the approaches under development (called quasi-classical alternatives), wherein algebraic parameters play the role of matrix elements and these are assumed to be transferable for similar atoms and/or atomic orbitals in addition. Further, passing to delocalized descriptions of electronic structures (as usual) is expected to be the main origin of difficulties seeking to formulate quasi-classical alternatives. In the framework of the canonical method of molecular orbitals (MOs), delocalization is shown to be partially avoidable by invoking a recently-suggested approach to secular (eigenvalue) equations for model Hamiltonian matrices, wherein the usual initial imposing of the zero-determinant condition is replaced by a certain reformulation of the problem itself. The most efficient way of achieving the same end, however, is shown to consist in passing to non-canonical one-electron problems. The latter may be exemplified by the block-diagonalization problem for the relevant Hamiltonian matrix following from the Brillouin theorem and yielding non-canonical (localized) MOs and by the commutation equation for the respective one-electron density matrix (charge- bond order matrix). In this connection, most of attention is paid in the article to perturbative solutions of the above-mentioned non-canonical problems and to their implications, including common quantum-chemical descriptions of entire classes of chemical compounds.