Issue 6, 2022

Natural reaction orbitals for characterizing electron transfer responsive to nuclear coordinate displacement

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.

Graphical abstract: Natural reaction orbitals for characterizing electron transfer responsive to nuclear coordinate displacement

Article information

Article type
Paper
Submitted
30 Sep 2021
Accepted
03 Nov 2021
First published
03 Nov 2021

Phys. Chem. Chem. Phys., 2022,24, 3532-3545

Natural reaction orbitals for characterizing electron transfer responsive to nuclear coordinate displacement

S. Ebisawa, M. Hasebe, T. Tsutsumi, T. Tsuneda and T. Taketsugu, Phys. Chem. Chem. Phys., 2022, 24, 3532 DOI: 10.1039/D1CP04491E

To request permission to reproduce material from this article, please go to the Copyright Clearance Center request page.

If you are an author contributing to an RSC publication, you do not need to request permission provided correct acknowledgement is given.

If you are the author of this article, you do not need to request permission to reproduce figures and diagrams provided correct acknowledgement is given. If you want to reproduce the whole article in a third-party publication (excluding your thesis/dissertation for which permission is not required) please go to the Copyright Clearance Center request page.

Read more about how to correctly acknowledge RSC content.

Social activity

Spotlight

Advertisements