title: A correlated-polaron electronic propagator: open electronic dynamics beyond the Born-Oppenheimer approximation.
abstract: 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.
authors.affiliation: Department of Chemistry and Chemical Biology, Harvard University, 12 Oxford St., Cambridge, Massachusetts 02138, USA. john.parkhill@gmail.com
authors.forename: John A
authors.initials: JA
authors.lastname: Parkhill
authors.forename: Thomas
authors.initials: T
authors.lastname: Markovich
authors.forename: David G
authors.initials: DG
authors.lastname: Tempel
authors.forename: Alan
authors.initials: A
authors.lastname: Aspuru-Guzik