Model Space Diabatization for Quantum Photochemistry

Thumbnail Image
Date
2015-01-01
Authors
Li, Shaohong
Truhlar, Donald
Schmidt, Michael
Gordon, Mark
Major Professor
Advisor
Committee Member
Journal Title
Journal ISSN
Volume Title
Publisher
Authors
Person
Research Projects
Organizational Units
Organizational Unit
Journal Issue
Is Version Of
Versions
Series
Department
Chemistry
Abstract

Diabatization is a procedure that transforms multiple adiabatic electronic states to a new representation in which the potential energy surfaces and the couplings between states due to the electronic Hamiltonian operator are smooth, and the couplings due to nuclear momentum are negligible. In this work, we propose a simple and general diabatization strategy, called model space diabatization, that is applicable to multi-configuration quasidegenerateperturbation theory (MC-QDPT) or its extended version (XMC-QDPT). An advantage over previous diabatization schemes is that dynamical correlation calculations are based on standard post-multi-configurational self-consistent field (MCSCF) multi-state methods even though the diabatization is based on state-averaged MCSCF results. The strategy is illustrated here by applications to LiH, LiF, and thioanisole, with the fourfold-way diabatization and XMC-QDPT, and the results illustrate its validity.

Comments

The following article appeared in Journal of Chemical Physics 142 (2015): 064106, and may be found at doi:10.1063/1.4907038.

Description
Keywords
Citation
DOI
Subject Categories
Copyright
Thu Jan 01 00:00:00 UTC 2015
Collections