A correlated-polaron electronic propagator: open electronic dynamics beyond the Born-Oppenheimer approximation

Abstract

In this work we develop a theory of correlated many-electron dynamics dressed by the presence of a finite-temperature harmonic bath. The theory is based on the ab-initio Hamiltonian, and thus well-defined apart from any phenomenological choice of collective basis states or electronic coupling model. The equation-of-motion includes some bath effects non-perturbatively, and can be used to simulate line- shapes beyond the Markovian approximation and open electronic dynamics which are subjects of renewed recent interest. Energy conversion and transport depend critically on the ratio of electron-electron coupling to bath-electron coupling, which is a fitted parameter if a phenomenological basis of many-electron states is used to develop an electronic equation of motion. Since the present work doesn't appeal to any such basis, it avoids this ambiguity. The new theory produces a level of detail beyond the adiabatic Born-Oppenheimer states, but with cost scaling like the Born-Oppenheimer approach. While developing this model we have also applied the time-convolutionless perturbation theory to correlated molecular excitations for the first time. Resonant response properties are given by the formalism without phenomenological parameters. Example propagations with a developmental code are given demonstrating the treatment of electron-correlation in absorption spectra, vibronic structure, and decay in an open system.

25 pages 7 figures

References in corpus (10)

• Correlation-dependent coherent to incoherent transitions in resonant energy transfer dynamics
• A canonical transformation theory from extended normal ordering
• Super-fermion representation of the Lindblad master equation for the electron transport problem
• Electronic excitation dynamics in multichromophoric systems described via a polaron-representation master equation
• A variational description of the quantum phase transition in the sub-Ohmic spin-boson model
• Consistent treatment of coherent and incoherent energy transfer dynamics using a variational master equation
• Time-convolutionless master equation for quantum dots: Perturbative expansion to arbitrary order
• Time-convolutionless master equation for mesoscopic electron-phonon systems
• Wick Theorem for General Initial States
• Exciton coherence lifetimes from electronic structure

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• Dissipative time-dependent quantum transport theory: quantum interference and phonon induced decoherence dynamics
• A stochastic reorganizational bath model for electronic energy transfer
• Second-order correlations in an exciton-polariton Rabi oscillator