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Natural reaction orbitals for characterizing electron transfer responsive to nuclear coordinate displacement
| Title: | Natural reaction orbitals for characterizing electron transfer responsive to nuclear coordinate displacement |
| Authors: | Ebisawa, Shuichi Browse this author | | Hasebe, Masatoshi Browse this author | | Tsutsumi, Takuro Browse this author →KAKEN DB | | Tsuneda, Takao Browse this author →KAKEN DB | | Taketsugu, Tetsuya Browse this author →KAKEN DB |
| Issue Date: | 14-Feb-2022 |
| Publisher: | Royal Society of Chemistry |
| Journal Title: | Physical chemistry chemical physics |
| Volume: | 24 |
| Issue: | 6 |
| Start Page: | 3532 |
| End Page: | 3545 |
| Publisher DOI: | 10.1039/d1cp04491e |
| Abstract: | The natural reaction orbital (NRO) is proposed as a new concept for analyzing chemical reactions from the viewpoint of the electronic theory. The pair of the occupied and virtual NROs that characterize electron transfer responsive to nuclear coordinate displacement along the reaction path is automatically extracted from the solution of the coupled-perturbed self-consistent-field (CPSCF) equation for the perturbation of the nuclear displacement. The NRO-based reaction analysis method is applied to several reactions. As a result, it is found that the sum of squares of the singular values, derived from the solution of the CPSCF equation, gives sharp peaks around the transition state structures and at the shoulders of the potential energy curve. The peaks around the transition states suggest a new physical meaning of transition state from the viewpoint of the electronic theory. Furthermore, the double peaks reveal the asynchronous processes of reactions, which are not always shown in potential energy analyses. Since the NRO-based reaction analysis method is universal and robust for describing reaction mechanisms from an electronic theory viewpoint, it is expected to lead to universal reaction analyses based on the electronic theory. |
| Type: | article (author version) |
| URI: | http://hdl.handle.net/2115/88185 |
| Appears in Collections: | 理学院・理学研究院 (Graduate School of Science / Faculty of Science) > 雑誌発表論文等 (Peer-reviewed Journal Articles, etc)
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Submitter: 武次 徹也
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