On the alternatives for bath correlators and spectral densities from mixed quantum-classical simulations
Year: 2012
Type: article
Abstract: We investigate on the procedure of extracting a "spectral density" from mixed QM/MM calculations and employing it in open quantum systems models. In particular, we study the connection between the energy gap correlation function extracted from ground state QM/MM and the bath spectral density used as input in open quantum system approaches. We introduce a simple model which can give intuition on when the ground state QM/MM propagation will give the correct energy gap. We also discuss the role of higher order correlators of the energy-gap fluctuations which can provide useful information on the bath. Further, various semiclassical corrections to the spectral density, are applied and investigated. Finally, we apply our considerations to the photosynthetic Fenna-Matthews-Olson complex. For this system, our results suggest the use of the Harmonic prefactor for the spectral density rather than the Standard one, which was employed in the simulations of the system carried out to date.
Source: The Journal of Chemical Physics
DOI: 10.1063/1.4769079
Authors: Stéphanie Valleau, Alexander Eisfeld, Alán Aspuru-Guzik
Language: English
Subfield: Atomic and Molecular Physics, and Optics
Field: Physics and Astronomy
Domain: Physical Sciences
Open Access status: bronze
OpenAlex ID: W2009838210