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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
| 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)
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Submitter: 長谷川 淳也
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