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Spin‐Orbit coupling in aromatic hydrocarbons: A semiempirical evaluation of the radiative lifetimes of naphtalene and anthracene
Author(s) -
Bendazzoli G. L.,
Orlandi G.,
Palmieri P.
Publication year - 1976
Publication title -
international journal of quantum chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.484
H-Index - 105
eISSN - 1097-461X
pISSN - 0020-7608
DOI - 10.1002/qua.560100409
Subject(s) - anthracene , singlet state , chemistry , hamiltonian (control theory) , spin–orbit interaction , radiative transfer , ab initio , atomic orbital , molecule , triplet state , molecular orbital , molecular physics , computational chemistry , atomic physics , electron , physics , photochemistry , excited state , quantum mechanics , organic chemistry , mathematical optimization , mathematics
Singlet‐triplet spin‐orbit matrix elements, which govern the lowest 3 B 1 u ← 1 A g transition in typical aromatic molecules like naphtalene and anthracene, are calculated with INDO molecular orbitals and the conventional spin‐orbit one‐electron hamiltonian. The correct order of magnitude of the triplet radiative lifetimes is obtained for the two molecules, when INDO MO coefficients are referred to a symmetrically orthogonalized basis. The possibility of using the semiempirical Hamiltonian is explored using ab initio wave‐functions for a few test cases. Reasonably accurate doublet‐doublet and singlet‐triplet matrix elements have been computed.