A correlatedpolaron electronic propagator: Open electronic dynamics beyond the BornOppenheimer approximation
Abstract
In this work, we develop an approach to treat correlated manyelectron dynamics, dressed by the presence of a finitetemperature harmonic bath. Our theory combines a small polaron transformation with the secondorder timeconvolutionless master equation and includes both electronic and systembath correlations on equal footing. Our theory is based on the ab initio Hamiltonian, and is thus welldefined apart from any phenomenological choice of basis states or electronic systembath coupling model. The equationofmotion for the density matrix we derive includes nonMarkovian and nonperturbative 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 BornOppenheimer approximation, but with computational cost scaling such as the BornOppenheimer approach. Example propagations with a developmental code are performed, demonstrating the treatment of electroncorrelation 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 rotationelectronspin interactions;
 Approximate calculations;
 Ab initio calculations;
 Quantum Physics;
 Condensed Matter  Other Condensed Matter;
 Physics  Chemical Physics
 EPrint:
 25 pages 7 figures