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.
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28 August 2022
Research Article|
August 25 2022
Extension of natural reaction orbital approach to multiconfigurational wavefunctions
Special Collection:
Nature of the Chemical Bond
Shuichi Ebisawa;
Shuichi Ebisawa
(Conceptualization, Data curation, Formal analysis, Investigation, Methodology, Software, Validation, Writing – original draft)
1
Graduate School of Chemical Sciences and Engineering, Hokkaido University
, Sapporo 060-0810, Japan
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Takuro Tsutsumi
;
Takuro Tsutsumi
(Conceptualization, Investigation, Writing – review & editing)
2
Department of Chemistry, Faculty of Science, Hokkaido University
, Sapporo 060-0810, Japan
3
L-Station, Creative Research Institution (CRI), Hokkaido University
, Sapporo 060-0812, Japan
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Tetsuya Taketsugu
Tetsuya Taketsugu
a)
(Conceptualization, Funding acquisition, Investigation, Methodology, Project administration, Writing – review & editing)
2
Department of Chemistry, Faculty of Science, Hokkaido University
, Sapporo 060-0810, Japan
4
Institute for Chemical Reaction Design and Discovery (WPI-ICReDD), Hokkaido University
, Sapporo 001-0021, Japan
a)Author to whom correspondence should be addressed: [email protected]
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a)Author to whom correspondence should be addressed: [email protected]
Note: This paper is part of the JCP Special Topic on Nature of the Chemical Bond.
J. Chem. Phys. 157, 084118 (2022)
Article history
Received:
May 06 2022
Accepted:
August 01 2022
Citation
Shuichi Ebisawa, Takuro Tsutsumi, Tetsuya Taketsugu; Extension of natural reaction orbital approach to multiconfigurational wavefunctions. J. Chem. Phys. 28 August 2022; 157 (8): 084118. https://doi.org/10.1063/5.0098230
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