Quantum chemical investigation of the photo-rearrangement of allyl alcohol

Abstract

The geometries of the reactant, the intermediate, the transition state and the product in T1 state for the photo-rearrangement of allyl alcohol to propionaldehyde are optimized by gradient technique, based on UHF ab initio methods with 6-31G basis set. The whole reaction path (intrinsic reaction coordinate proposed by Fukui) is traced. Our results of calculation with correlation correction by means of MP2/6-31G method not only support that the photorearrangement of allyl alcohol proceeds via hydrogen shift in the excited electronic state, but also predict that the isomerization is a two step reaction via a diradical as an intermediate with the main primary product excited propenol.

Key words: REACTION MECHANISM, AB INITIO CALCULATION, ISOMERIZATION REACTION, SELF-CONSISTENT FIELD, ALLYL ALCOHOL

CLC Number:

O644

Cite this article

YU HAO;LIU RUOZHUANG. Quantum chemical investigation of the photo-rearrangement of allyl alcohol[J]. Acta Chimica Sinica, 1995, 53(8): 751-756.

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