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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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Please use this identifier to cite or link to this item:http://hdl.handle.net/2115/66640

Title: A DFT and multi-configurational perturbation theory study on O-2 binding to a model heme compound via the spin-change barrier
Authors: Kitagawa, Y. Browse this author
Chen, Y. Browse this author
Nakatani, Naoki Browse this author
Nakayama, Akira Browse this author →KAKEN DB
Hasegawa, Jun-ya Browse this author →KAKEN DB
Issue Date: 21-Jul-2016
Publisher: Royal Society of Chemistry
Journal Title: Physical chemistry chemical physics
Volume: 18
Issue: 27
Start Page: 18137
End Page: 18144
Publisher DOI: 10.1039/c6cp02329k
PMID: 27328181
Abstract: 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.
Type: article (author version)
URI: http://hdl.handle.net/2115/66640
Appears in Collections:触媒科学研究所 (Institute for Catalysis) > 雑誌発表論文等 (Peer-reviewed Journal Articles, etc)

Submitter: 長谷川 淳也

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