title: On the alternatives for bath correlators and spectral densities from mixed quantum-classical simulations.
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.
authors.affiliation: Department of Chemistry and Chemical Biology, Harvard University, Cambridge, Massachusetts 02138, USA.
authors.forename: Stéphanie
authors.initials: S
authors.lastname: Valleau
authors.forename: Alexander
authors.initials: A
authors.lastname: Eisfeld
authors.forename: Alán
authors.initials: A
authors.lastname: Aspuru-Guzik
mesh_terms: D019414:Chlorobi / Q000201:enzymology; D005583:Fourier Analysis; D045342:Light-Harvesting Protein Complexes / Q000737:chemistry / Q000378:metabolism; D008958:Models, Molecular; D011789:Quantum Theory; D013057:Spectrum Analysis; D013696:Temperature; D013816:Thermodynamics
chemical_list: D045342:Light-Harvesting Protein Complexes