論文

査読有り
2011年

A theoretical study on excited state double proton transfer reaction of a 7-azaindole dimer: an ab initio potential energy surface and its empirical valence bond model

PHYSICAL CHEMISTRY CHEMICAL PHYSICS
  • Kohei Ando
  • ,
  • Shigehiko Hayashi
  • ,
  • Shigeki Kato

13
23
開始ページ
11118
終了ページ
11127
記述言語
英語
掲載種別
研究論文(学術雑誌)
DOI
10.1039/c1cp20420c
出版者・発行元
ROYAL SOC CHEMISTRY

Double proton transfer (DPT) reaction of a 7-azaindole dimer in the first pi pi* electronically excited state was studied theoretically. We investigated the reaction mechanism through constructing a full dimensional empirical valence bond potential energy function (PEF) based on potential energies evaluated by ab initio molecular orbital methods, and carrying out quantum dynamics calculations with the PEF. Potential energy surfaces of the DPT obtained at the multi-reference perturbation level of theory favors a concerted DPT mechanism, although a stepwise channel is suggested to open for an excited initial vibrational state. Reduced two dimensional quantum dynamics calculations for a reaction surface Hamiltonian of DPT coordinates were performed. Time constants of the reaction were evaluated to be on the order of picoseconds, which is consistent with experiments. On the other hand, the computed kinetic isotope effect deviates from experimental evidence, suggesting the importance of intermolecular stretching motion, which is not explicit in the present calculations for the quantum effect.

リンク情報
DOI
https://doi.org/10.1039/c1cp20420c
J-GLOBAL
https://jglobal.jst.go.jp/detail?JGLOBAL_ID=201102235621679438
PubMed
https://www.ncbi.nlm.nih.gov/pubmed/21552642
Web of Science
https://gateway.webofknowledge.com/gateway/Gateway.cgi?GWVersion=2&SrcAuth=JSTA_CEL&SrcApp=J_Gate_JST&DestLinkType=FullRecord&KeyUT=WOS:000291113200027&DestApp=WOS_CPL
ID情報
  • DOI : 10.1039/c1cp20420c
  • ISSN : 1463-9076
  • J-Global ID : 201102235621679438
  • PubMed ID : 21552642
  • Web of Science ID : WOS:000291113200027

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