Document Type
Article
Publication Date
7-11-2012
Abstract
Derivative couplings are the essential quantities at the interface between electronic-structure calculations and nonadiabatic dynamics. Unfortunately, standard approaches for calculating these couplings usually neglect electronic motion, which can lead to spurious electronic transitions. Here we provide a general framework for correcting these anomalies by incorporating perturbative electron-translation factors (ETFs) into the atomic-orbital basis. For a range of representative organic molecules, we find that our ETF correction is often small but can be qualitatively important, especially for few-atom systems or highly symmetric molecules. Our method entails no additional computational cost, such that ETFs are “built-in,” and it is equivalent to a simple rule of thumb: We should set the antisymmetrized version of the nuclear overlap-matrix derivative to zero wherever it appears. Thus, we expect that built-in ETFs will be regularly incorporated into future studies of nonadiabatic dynamics.
Recommended Citation
Fatehi, S.; Subotnik, J. E. Derivative Couplings with Built-In Electron-Translation Factors: Application to Benzene. J. Phys. Chem. Lett. 2012, 3, 2039– 2043, DOI: 10.1021/jz300617
Publication Title
The Journal of Physical Chemistry Letters
DOI
10.1021/jz300617
Comments
This document is the unedited Author’s version of a Submitted Work that was subsequently accepted for publication in The Journal of Physical Chemistry Letters, copyright © American Chemical Society after peer review. To access the final edited and published work see http://pubs.acs.org/articlesonrequest/AOR-BKz8ZpAUtv2WiWTihkbk.