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
- ,
- ,
- 巻
- 13
- 号
- 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
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- 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