Solvent configuration-interaction calculations of intermolecular states in molecule-(atom)N clusters: application to Br2-4HeN.
We describe variational calculations of J=0 intermolecular states in Br(2)-(4)He(N) clusters. The method employed is analogous to configuration-interaction calculations in electronic-structure work and relies on the ability to express the intermolecular Hamiltonian H(v) as a sum of one- and two-body terms. A basis set is built up from solutions to the Schrödinger equation in which only the one-body terms of H(v) are included. These configurations are products of N=1 eigenstates. The matrix of H(v) in a symmetry-adapted configuration basis is then computed, the two-body terms of H(v) serving to couple different configurations. This computation involves integrals of dimension five or less. Filter diagonalization is then used to obtain energies and eigenfunctions within a selected energy range. Results on clusters having N=2-5 are reported.
Felker
Peter M
PM
Department of Chemistry and Biochemistry, University of California, Los Angeles, California 90095-1569, USA. felker@chem.ucla.edu