Theoretical Study of the Low-Lying Excited States of Butoxy Radicals and Non-Radiative Decay Routes

• 来源期刊: 中国化学(英文版)
• 年，卷（期）: 2007,（10）
• 页码范围: 1467-1473
• 页数: 7页
• 语种: 英文

摘要

The potential energy surfaces for the butoxy radical dissociation into R·+O on the six low-lying electronic states have been determined with the combined CASSCF and MR-CI methods. The isomerization reactions between the different conformers of 1- and 2-butoxy radicals at the (X) and (B) states have been also investigated with the MP2, B3LYP, and CASSCF methods. The non-radiative decay mechanisms of butoxy radicals at the (B) state have been characterized with the computed potential energy surfaces and intersections. Supported by recent LIF experimental results, it was predicted that the t-butoxy radical would predissociate via the (B)/(C) intersection. As to 1-and 2-butoxy radicals, the relative energies of the transition states for the isomerization reactions between conformers at the (B) state are much lower than those of the (B)/(C) intersections, resulting in the predominance of the isomerization in the decay of the (B) state for 1- and 2-butoxy radicals.