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