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Optimal diabatic states based on solvation parameters
- 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