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Article
Model Space Diabatization for Quantum Photochemistry
Journal of Chemical Physics
  • Shaohong Li, University of Minnesota - Twin Cities
  • Donald G. Truhlar, University of Minnesota - Twin Cities
  • Michael Schmidt, Iowa State University
  • Mark S. Gordon, Iowa State University
Document Type
Article
Disciplines
Publication Version
Published Version
Publication Date
1-1-2015
DOI
10.1063/1.4907038
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.

Rights
Copyright 2015 American Institute of Physics. This article may be downloaded for personal use only. Any other use requires prior permission of the author and the American Institute of Physics.
Copyright Owner
American Institute of Physics
Language
en
File Format
application/pdf
Citation Information
Shaohong Li, Donald G. Truhlar, Michael Schmidt and Mark S. Gordon. "Model Space Diabatization for Quantum Photochemistry" Journal of Chemical Physics Vol. 142 (2015) p. 1 - 15
Available at: http://works.bepress.com/mark_gordon/419/