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Computational investigation of the photochemical deoxygenation of thiophene- S-oxide and selenophene- Se-oxide

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Abstract

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(3P) 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(3P) 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 (T2) state.

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Authors and Affiliations

  1. University of Wisconsin-River Falls, River Falls, Wisconsin, USA

    Stacey A. Stoffregen & Stephanie Y. Lee

  2. Department of Chemistry, Iowa State University, Ames, Iowa, USA

    Pearl Dickerson & William S. Jenks

Authors
  1. Stacey A. Stoffregen
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  2. Stephanie Y. Lee
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  3. Pearl Dickerson
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  4. William S. Jenks
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Correspondence to Stacey A. Stoffregen or William S. Jenks.

Additional information

Electronic supplementary information (ESI) available: Geometries and absolute energies of compounds. See DOI: 10.1039/c3pp50382h

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Stoffregen, S.A., Lee, S.Y., Dickerson, P. et al. Computational investigation of the photochemical deoxygenation of thiophene- S-oxide and selenophene- Se-oxide. Photochem Photobiol Sci 13, 431–438 (2014). https://doi.org/10.1039/c3pp50382h

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