Abstract
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.
Publisher
Springer Science and Business Media LLC
Subject
Physical and Theoretical Chemistry
Cited by
1 articles.
订阅此论文施引文献
订阅此论文施引文献,注册后可以免费订阅5篇论文的施引文献,订阅后可以查看论文全部施引文献