A Correlated-Polaron Electronic Propagator: Open Electronic Dynamics beyond the Born-Oppenheimer Approximation
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CitationParkhill, John, Thomas Lee Markovich, David Gabriel Tempel, and Alan Aspuru-Guzik. 2012. “A correlated-polaron electronic propagator: Open electronic dynamics beyond the Born-Oppenheimer approximation.” Journal of Chemical Physics 137 (22): 22A547. doi:10.1063/1.4762441. http://dx.doi.org/10.1063/1.4762441.
AbstractIn this work, we develop an approach to treat correlated many-electron dynamics, dressed by the presence of a finite-temperature harmonic bath. Our theory combines a small polaron transformation with the second-order time-convolutionless master equation and includes both electronic and system-bath correlations on equal footing. Our theory is based on the ab initio Hamiltonian, and is thus well-defined apart from any phenomenological choice of basis states or electronic system-bath coupling model. The equation-of-motion for the density matrix we derive includes non-Markovian and non-perturbative bath effects and can be used to simulate environmentally broadened electronic spectra and dissipative dynamics, which are subjects of recent interest. The theory also goes beyond the adiabatic Born-Oppenheimer approximation, but with computational cost scaling such as the Born-Oppenheimer approach. Example propagations with a developmental code are performed, demonstrating the treatment of electron-correlation in absorption spectra, vibronic structure, and decay in an open system. An untransformed version of the theory is also presented to treat more general baths and larger systems.
Citable link to this pagehttp://nrs.harvard.edu/urn-3:HUL.InstRepos:11639528
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