Back to Search Start Over

Optimal diabatic states based on solvation parameters

Authors :
Ethan Alguire
Joseph E. Subotnik
Source :
The Journal of chemical physics. 137(19)
Publication Year :
2012

Abstract

A new method for obtaining diabatic electronic states of a molecular system in a condensed environment is proposed and evaluated. This technique, which we denote as Edmiston-Ruedenberg (ER)-ɛ diabatization, forms diabatic states as a linear combination of adiabatic states by minimizing an approximation to the total coupling between states in a medium with temperature T and with a characteristic Pekar factor C. ER-ɛ diabatization represents an improvement upon previous localized diabatization methods for two reasons: first, it is sensitive to the energy separation between adiabatic states, thus accounting for fluctuations in energy and effectively preventing over-mixing. Second, it responds to the strength of system-solvent interactions via parameters for the dielectric constant and temperature of the medium, which is physically reasonable. Here, we apply the ER-ɛ technique to both intramolecular and intermolecular excitation energy transfer systems. We find that ER-ɛ diabatic states satisfy three important properties: (1) they have small derivative couplings everywhere; (2) they have small diabatic couplings at avoided crossings, and (3) they have negligible diabatic couplings everywhere else. As such, ER-ɛ states are good candidates for so-called “optimal diabatic states.”

Details

ISSN :
10897690
Volume :
137
Issue :
19
Database :
OpenAIRE
Journal :
The Journal of chemical physics
Accession number :
edsair.doi.dedup.....2809a5baf6b9e489d37ad8a2d8eb2df5