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A DFT and multi-configurational perturbation theory study on O-2 binding to a model heme compound via the spin-change barrier

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タイトル: A DFT and multi-configurational perturbation theory study on O-2 binding to a model heme compound via the spin-change barrier
著者: Kitagawa, Y. 著作を一覧する
Chen, Y. 著作を一覧する
Nakatani, Naoki 著作を一覧する
Nakayama, Akira 著作を一覧する
Hasegawa, Jun-ya 著作を一覧する
発行日: 2016年 7月21日
出版者: Royal Society of Chemistry
誌名: Physical chemistry chemical physics
巻: 18
号: 27
開始ページ: 18137
終了ページ: 18144
出版社 DOI: 10.1039/c6cp02329k
抄録: Dioxygen binding to a model heme compound via intersystem crossing (ISC) was investigated with a multi-state multi-configurational self-consistent field method with second-order perturbation theory (MS-CASPT2) and density functional theory (DFT) calculations. In elongated Fe-O distances, the energy levels of the S-0 and T-1 states are separated, which decreases the probability of intersystem crossing in these structures. At the DFT(B97D) level of calculation, the Fe-O distances of the S-0 and T-1 states were 1.91 and 2.92 angstrom, respectively. The minimum energy intersystem crossing point (MEISCP) was located as a transition state at a Fe-O distance of 2.17 angstrom with an energy barrier of 1.0 kcal mol(-1) from the T-1 minimum. The result was verified with MS-CASPT2 calculations including the spin-orbit interaction which also showed the intersystem crossing point at a Fe-O distance of 2.05 angstrom. An energy decomposition analysis on the reaction coordinate showed the important contribution of the ring-shrinking mode of the porphyrin ring, indicating that the reaction coordinates which control the relative energy level of the spin-states play a key role in intersystem crossing.
資料タイプ: article (author version)
URI: http://hdl.handle.net/2115/66640
出現コレクション:雑誌発表論文等 (Peer-reviewed Journal Articles, etc)

提供者: 長谷川 淳也

 

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