期刊
PHOTOCHEMICAL & PHOTOBIOLOGICAL SCIENCES
卷 13, 期 2, 页码 431-438出版社
SPRINGERNATURE
DOI: 10.1039/c3pp50382h
关键词
-
资金
- NSF [CHE-1039925]
- Midwest Undergraduate Computational Chemistry Consortium
CASSCF and multireference MP2 calculations were carried out on thiophene-S-oxide (TO) and selenophene-Se-oxide (SeO), comparing the energies of the ground state to the first two electronically excited singlet and triplet states, using constrained optimizations and multiple fixed S-O or Se-O distances. For both molecules, one of the two triplet states smoothly dissociates to yield O(P-3) with little or no barrier. Single point calculations are consistent with the same phenomenon occurring for dibenzothiophene-S-oxide (DBTO). This provides an explanation for the inefficient unimolecular photochemical dissociation of O(P-3) from DBTO despite a phosphorescence energy below that of S-O dissociation, i.e., that S-O scission probably occurs from a spectroscopically unobserved triplet (T-2) state.
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