The initial and final states of electron and energy transfer processes: Diabatization as motivated by system-solvent interactions

Journal Article · Sun Jun 21 00:00:00 EDT 2009 · Journal of Chemical Physics

DOI:https://doi.org/10.1063/1.3148777· OSTI ID:21559728

Subotnik, Joseph E ^[1]; Cave, Robert J ^[2]; Steele, Ryan P; Shenvi, Neil ^[3]

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1. School of Chemistry, Tel-Aviv University, Tel-Aviv 69978 (Israel)
2. Department of Chemistry, Harvey Mudd College, Claremont, California 91711 (United States)
3. Department of Chemistry, Yale University, New Haven, Connecticut 06520 (United States)

For a system which undergoes electron or energy transfer in a polar solvent, we define the diabatic states to be the initial and final states of the system, before and after the nonequilibrium transfer process. We consider two models for the system-solvent interactions: A solvent which is linearly polarized in space and a solvent which responds linearly to the system. From these models, we derive two new schemes for obtaining diabatic states from ab initio calculations of the isolated system in the absence of solvent. These algorithms resemble standard approaches for orbital localization, namely, the Boys and Edmiston-Ruedenberg (ER) formalisms. We show that Boys localization is appropriate for describing electron transfer [Subotnik et al., J. Chem. Phys. 129, 244101 (2008)] while ER describes both electron and energy transfer. Neither the Boys nor the ER methods require definitions of donor or acceptor fragments and both are computationally inexpensive. We investigate one chemical example, the case of oligomethylphenyl-3, and we provide attachment/detachment plots whereby the ER diabatic states are seen to have localized electron-hole pairs.

• OSTI ID: 21559728
• Journal Information: Journal of Chemical Physics, Vol. 130, Issue 23; Other Information: DOI: 10.1063/1.3148777; (c) 2009 American Institute of Physics; ISSN 0021-9606
• Country of Publication: United States
• Language: English

Related Subjects

75 CONDENSED MATTER PHYSICS
SUPERCONDUCTIVITY AND SUPERFLUIDITY
37 INORGANIC
ORGANIC
PHYSICAL AND ANALYTICAL CHEMISTRY
36 MATERIALS SCIENCE
ALGORITHMS
CHARGE EXCHANGE
ELECTRON TRANSFER
ELECTRONS
ENERGY TRANSFER
HOLES
INTERACTIONS
LIQUIDS
ORGANIC COMPOUNDS
SOLVENTS
ELEMENTARY PARTICLES
FERMIONS
FLUIDS
LEPTONS
MATHEMATICAL LOGIC