Mail:
Dept. of Chemistry
Ohio State University
100 W. 18th Ave.
Columbus, OH 43210
Office:
412 CBEC
Email:
herbert@
chemistry.ohio-state.edu
A high-level ab initio electronic structure study of the unimolecular rearrangement of trans-FONO to fluoryl nitrate (FNO2) is presented. The FO + NO → [FONO]* → FNO2 reaction is found to proceed through a tight transition state with a calculated height of 22(3) kcal mol–1. The isomerization process is described qualitatively in terms of a two-state diabatic model that involves the fluorine atom and the ground and first excited σ states of NO2.