|
Hokkaido University Collection of Scholarly and Academic Papers >
Graduate School of Science / Faculty of Science >
Peer-reviewed Journal Articles, etc >
Extension of natural reaction orbital approach to multiconfigurational wavefunctions
| Title: | Extension of natural reaction orbital approach to multiconfigurational wavefunctions |
| Authors: | Ebisawa, Shuichi Browse this author | | Tsutsumi, Takuro Browse this author | | Taketsugu, Tetsuya Browse this author →KAKEN DB |
| Issue Date: | 28-Aug-2022 |
| Publisher: | AIP Publishing |
| Journal Title: | Journal of chemical physics |
| Volume: | 157 |
| Issue: | 8 |
| Start Page: | 84118 |
| Publisher DOI: | 10.1063/5.0098230 |
| Abstract: | Recently, we proposed a new orbital analysis method, natural reaction orbital (NRO), which automatically extracts orbital pairs that characterize electron transfer in reaction processes by singular value decomposition of the first-order orbital response matrix to the nuclear coordinate displacements [Ebisawa et al., Phys. Chem. Chem. Phys. 24, 3532 (2022)]. NRO analysis along the intrinsic reaction coordinate (IRC) for several typical chemical reactions demonstrated that electron transfer occurs mainly in the vicinity of transition states and in regions where the energy profile along the IRC shows shoulder features, allowing the reaction mechanism to be explained in terms of electron motion. However, its application has been limited to single configuration theories such as Hartree-Fock theory and density functional theory. In this work, the concept of NRO is extended to multiconfigurational wavefunctions and formulated as the multiconfiguration NRO (MC-NRO). The MC-NRO method is applicable to various types of electronic structure theories, including multiconfigurational theory and linear response theory, and is expected to be a practical tool for extracting the essential qualitative features of a broad range of chemical reactions, including covalent bond dissociation and chemical reactions in electronically excited states. In this paper, we calculate the IRC for five basic chemical reaction processes at the level of the complete active space self-consistent field theory and discuss the phenomenon of electron transfer by performing MC-NRO analysis along each IRC. Finally, issues and future prospects of the MC-NRO method are discussed. |
| Rights: | This article may be downloaded for personal use only. Any other use requires prior permission of the author and AIP Publishing. This article appeared in J. Chem. Phys. 157, 084118 (2022) and may be found at https://doi.org/10.1063/5.0098230 |
| Type: | article |
| URI: | http://hdl.handle.net/2115/90320 |
| 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)
|
Submitter: 武次 徹也
|
