Diabatic potential energy curves for the $^4{\Pi} $ states of SH

D. Kashinski , J. Bohnemann , A. Hickman , Dahbia Talbi (1)

1 LUPM - Laboratoire Univers et Particules de Montpellier

We present a diabatic representation of the potential energy curves (PECs) for the 4Π states of SH. Multireference, configuration interaction (MRCI) calculations were used to determine high-accuracy adiabatic PECs of both SH and SH+ from which the diabatic representation is constructed for 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 states of 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.

Domaines: Autre

D. Kashinski, J. Bohnemann, A. Hickman, Dahbia Talbi. Diabatic potential energy curves for the $^4{\Pi} $ states of SH. Theoretical Chemistry Accounts: Theory, Computation, and Modeling, 2021, 140, pp.64. ⟨10.1007/s00214-021-02746-9⟩. ⟨hal-03339899⟩