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.
- Publication:
-
Journal of Chemical Physics
- Pub Date:
- December 2012
- DOI:
- 10.1063/1.4762441
- arXiv:
- arXiv:1206.2567
- Bibcode:
- 2012JChPh.137vA547P
- Keywords:
-
- ab initio calculations;
- approximation theory;
- electron correlations;
- master equation;
- polarons;
- vibronic states;
- 31.15.V-;
- 33.20.Wr;
- 31.15.B-;
- 31.15.A-;
- Electron correlation calculations for atoms ions and molecules;
- Vibronic rovibronic and rotation-electron-spin interactions;
- Approximate calculations;
- Ab initio calculations;
- Quantum Physics;
- Condensed Matter - Other Condensed Matter;
- Physics - Chemical Physics
- E-Print:
- 25 pages 7 figures