In 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.
A correlated-polaron electronic propagator: Open electronic dynamics beyond the Born-Oppenheimer approximation
John A. Parkhill, Thomas Markovich, David G. Tempel, Alan Aspuru-Guzik; A correlated-polaron electronic propagator: Open electronic dynamics beyond the Born-Oppenheimer approximation. J. Chem. Phys. 14 December 2012; 137 (22): 22A547. https://doi.org/10.1063/1.4762441
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