Theoretical Study of the Photoisomerization of 2-Methylthiophene to 3-Methylthiophene

Abstract

Abstract: The photoisomerization of 2-methylthiophene to 3-methylthiophene was studied at the CASSCF level with a 6-31G* basis set. The reaction channels on the ground state(S₀) and excited state(T₁) were investigated. The reaction proceeds via two diradical intermediates, one intermediate product and four transitions states on the T₁ surface. The two-diradical T₁/S₀ intersystem crossing points were located along the reaction path. It is most likely that the intersystem crossing from T₁ to S₀ occurs near the second crossing point because 3-methylthiophene can be formed very easily. Based on the computation we come to the conclusion that the intersystem crossing from T₁ to S₀ is the rate-determining step in the reaction.

Key words: Methylthiophene, 3-Methylthiophene, CASSCF, Intersystem crossng point, Reaction path, Photoisomerization

CLC Number:

O641

TrendMD:

WANG Yan-Xia, CHEN Yi-Shan, YE Song . Theoretical Study of the Photoisomerization of 2-Methylthiophene to 3-Methylthiophene[J]. Chem. J. Chinese Universities, 2005, 26(4): 747.

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Theoretical Study of the Photoisomerization of 2-Methylthiophene to 3-Methylthiophene

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