Theoretical verification of nonthermal microwave effects on intramolecular reactions

Manabu Kanno, Kosuke Nakamura, Eri Kanai, Kunihito Hoki, Hirohiko Kono, Motohiko Tanaka

Research output: Contribution to journalArticlepeer-review

11 Citations (Scopus)

Abstract

There have been a growing number of articles that report dramatic improvements in the experimental performance of chemical reactions by microwave irradiation compared to that under conventional heating conditions. We theoretically examined whether nonthermal microwave effects on intramolecular reactions exist or not, in particular, on Newman-Kwart rearrangements and intramolecular Diels-Alder reactions. The reaction rates of the former calculated by the transition state theory, which consider only the thermal effects of microwaves, agree quantitatively with experimental data, and thus, the increases in reaction rates can be ascribed to dielectric heating of the solvent by microwaves. In contrast, for the latter, the temperature dependence of reaction rates can be explained qualitatively by thermal effects but the possibility of nonthermal effects still remains regardless of whether competitive processes are present or not. The effective intramolecular potential energy surface in the presence of a microwave field suggests that nonthermal effects arising from potential distortion are vanishingly small in intramolecular reactions. It is useful in the elucidation of the reaction mechanisms of microwave synthesis to apply the present theoretical approach with reference to the experiments where thermal and nonthermal effects are separated by screening microwave fields.

Original languageEnglish
Pages (from-to)2177-2183
Number of pages7
JournalJournal of Physical Chemistry A
Volume116
Issue number9
DOIs
Publication statusPublished - 2012 Mar 8

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry

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