Reduced density matrix hybrid approach: Application to electronic energy transfer

Journal Article · Tue Feb 28 04:00:00 EST 2012 · Journal of Chemical Physics

DOI:https://doi.org/10.1063/1.3687342· OSTI ID:22047175

Berkelbach, Timothy C; Reichman, David R ^[1]; Markland, Thomas E ^[2]

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1. Department of Chemistry, Columbia University, 3000 Broadway, New York, New York 10027 (United States)
2. Department of Chemistry, Stanford University, 333 Campus Drive, Stanford, California 94305 (United States)

Electronic energy transfer in the condensed phase, such as that occurring in photosynthetic complexes, frequently occurs in regimes where the energy scales of the system and environment are similar. This situation provides a challenge to theoretical investigation since most approaches are accurate only when a certain energetic parameter is small compared to others in the problem. Here we show that in these difficult regimes, the Ehrenfest approach provides a good starting point for a dynamical description of the energy transfer process due to its ability to accurately treat coupling to slow environmental modes. To further improve on the accuracy of the Ehrenfest approach, we use our reduced density matrix hybrid framework to treat the faster environmental modes quantum mechanically, at the level of a perturbative master equation. This combined approach is shown to provide an efficient and quantitative description of electronic energy transfer in a model dimer and the Fenna-Matthews-Olson complex and is used to investigate the effect of environmental preparation on the resulting dynamics.

• OSTI ID: 22047175
• Journal Information: Journal of Chemical Physics, Journal Name: Journal of Chemical Physics Journal Issue: 8 Vol. 136; ISSN JCPSA6; ISSN 0021-9606
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
75 CONDENSED MATTER PHYSICS
SUPERCONDUCTIVITY AND SUPERFLUIDITY
ACCURACY
COMPLEXES
DENSITY MATRIX
ENERGY TRANSFER
PERTURBATION THEORY
PHOTOSYNTHESIS