Diabatic potential energy curves for the ⁴Π states of SH

This is the authors' abstract. We don't add key points for this paper.

We present a diabatic representation of the potential energy curves (PECs) for the ⁴Π 4 Π states of SH SH . Multireference, configuration interaction (MRCI) calculations were used to determine high-accuracy adiabatic PECs of both SH SH and SH⁺ SH + from which the diabatic representation is constructed for SH SH . The adiabatic PECs exhibit many avoided crossings due to strong Rydberg-valence mixing. We employ the block diagonalization method, an orthonormal rotation of the adiabatic Hamiltonian, to disentangle the valence autoionizing and Rydberg ⁴Π 4 Π states of SH SH by constructing a diabatic Hamiltonian. The diagonal elements of the diabatic Hamiltonian matrix at each nuclear geometry render the diabatic PECs and the off-diagonal elements are related to the state-to-state coupling. Care is taken to assure smooth variation and consistency of chemically significant molecular orbitals across the entire geometry domain.