A comparison of approximate techniques for the determination of potential energy surfaces of ion–molecule charge transfer systems

Abstract

The (HO2)+ molecular ion is used to experiment two approximate procedures which aim at reducing the computation effort that is needed for the determination of potential energy surfaces of ion–molecule charge transfer systems. The two procedures involve configuration interaction (CI) calculations of moderate sizes and are based on diagonal corrections of the electronic Hamiltonian matrix in a basis of projected‐valence bond (PVB) configuration‐state functions (CSF). The PVB‐CSF’s used in practice correspond to a full valence CI for each ionic or neutral partner as well as single excitations accounting for polarization and electron transfer. The diagonal corrections are of two sorts: (i) if insufficiently large orbital expansion bases are used they remove the relative ion–molecule basis set superposition error; (ii) if asymptotic energy levels of the involved neutrals or ions in their ground or valence excited states are misplaced they properly adjust these levels. When applied to (HO2)+ using a minimal or an extended orbital basis set expansion the proposed approaches yield concording results. The results also agree with the effective model potential (EMP) data of Grimbert et al. [Chem. Phys. 124, 187 (1988)] which have proved successful in the description of the H++O2 charge transfer dynamics. Comparison with fragmentary results from MRD‐CI calculations by Vazquez et al. [Mol. Phys. 59, 291 (1986)] and Schneider et al. [Chem. Phys. 128, 311 (1988)] is somewhat mitigated. The method should be particularly useful for bulky ion–molecule systems.