HUSCAP logo Hokkaido Univ. logo

Hokkaido University Collection of Scholarly and Academic Papers >
理学院・理学研究院  >
雑誌発表論文等  >

Solvent effects on the excited-state double proton transfer mechanism in the 7-azaindole dimer : a TDDFT study with the polarizable continuum model

フルテキスト
PCCP19-34 23289-23301.pdf3.91 MBPDF見る/開く
この文献へのリンクには次のURLを使用してください:http://hdl.handle.net/2115/71462

タイトル: Solvent effects on the excited-state double proton transfer mechanism in the 7-azaindole dimer : a TDDFT study with the polarizable continuum model
著者: Yu, Xue-fang 著作を一覧する
Yamazaki, Shohei 著作を一覧する
Taketsugu, Tetsuya 著作を一覧する
発行日: 2017年 9月14日
出版者: Royal Society of Chemistry
誌名: Physical chemistry chemical physics
巻: 19
号: 34
開始ページ: 23289
終了ページ: 23301
出版社 DOI: 10.1039/c7cp04942k
抄録: Solvent effects on the excited-state double proton transfer (ESDPT) mechanism in the 7-azaindole (7AI) dimer were investigated using the time-dependent density functional theory (TDDFT) method. Excited-state potential energy profiles along the reaction paths in a locally excited (LE) state and a charge transfer (CT) state were calculated using the polarizable continuum model (PCM) to include the solvent effect. A series of non-polar and polar solvents with different dielectric constants were used to examine the polarity effect on the ESDPT mechanism. The present results suggest that in a non-polar solvent and a polar solvent with a small dielectric constant, ESDPT follows a concerted mechanism, similar to the case in the gas phase. In a polar solvent with a relatively large dielectric constant, however, ESDPT is likely to follow a stepwise mechanism via a stable zwitterionic intermediate in the LE state on the adiabatic potential energy surface, although inclusion of zero-point vibrational energy (ZPE) corrections again suggests the concerted mechanism. In the meantime, the stepwise reaction path involving the CT state with neutral intermediates is also examined, and is found to be less competitive than the concerted or stepwise path in the LE state in both non-polar and polar solvents. The present study provides a new insight into the experimental controversy of the ESDPT mechanism of the 7AI dimer in a solution.
資料タイプ: article (author version)
URI: http://hdl.handle.net/2115/71462
出現コレクション:雑誌発表論文等 (Peer-reviewed Journal Articles, etc)

提供者: 武次 徹也

 

本サイトに関するご意見・お問い合わせは repo at lib.hokudai.ac.jp へお願いします。 - 北海道大学