Parkhill, John AnthonyMarkovich, Thomas LeeTempel, DavidAspuru-Guzik, Alan2014-01-312012Parkhill, 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/10.1063/1.4762441.0021-96061089-7690http://nrs.harvard.edu/urn-3:HUL.InstRepos:11639528In 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.en-USperturbation theorycorrelation functionsadiabatic theoremelectron correlation calculationsmany body problemspolaronscancermotion equationsexcited statesFourier transformsJournal Article2014-01-3110.1063/1.4762441