Interactions of 2P Atoms with Closed-Shell Diatomic Molecules: Alternative Diabatic Representations for the Electronic Anisotropy

Abstract

The matrices of electrostatic and spin-orbit Hamiltonians for the system of a 2P atom interacting with a closed shell diatomic molecule in uncoupled, coupled, and complex-valued representations for electronic diabatic basis functions are rederived, and the unitary transformations connecting them are given explicitly. The links to previous derivations are established and existing inconsistencies are identified and eliminated. It is proven that the block-diagonalization of a 6 x 6 matrix of the electronic Hamiltonian is a result of using the basis functions with well-defined properties with respect to time reversal. Consideration of time-reversal symmetry also enforces phase consistency relevant for applications to multisurface reactive scattering and photodetachment spectroscopy calculations, as well as for perspective studies of inelastic effects in cold and ultracold environments. These and further developments are briefly sketched.