Communication: Multiple-property-based diabatization for open-shell van der Waals molecules.

Abstract

We derive a new multiple-property-based diabatization algorithm. The transformation between adiabatic and diabatic representations is determined by requiring a set of properties in both representations to be related by a similarity transformation. This set of properties is determined in the adiabatic representation by rigorous electronic structure calculations. In the diabatic representation, the same properties are determined using model diabatic states defined as products of undistorted monomer wave functions. This diabatic model is generally applicable to van der Waals molecules in arbitrary electronic states. Application to locating seams of conical intersections and collisional transfer of electronic excitation energy is demonstrated for O2 - O2 in low-lying excited states. Property-based diabatization for this test system included all components of the electric quadrupole tensor, orbital angular momentum, and spin-orbit coupling.