Förster resonance energy transfer, absorption and emission spectra in multichromophoric systems. III. Exact stochastic path integral evaluation

A numerically exact path integral treatment of the absorption and emission spectra of open quantum systems is presented that requires only the straightforward solution of a stochastic differential equation. The approach converges rapidly enabling the calculation of spectra of large excitonic systems...

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Bibliographic Details
Published in:The Journal of chemical physics 2015-03, Vol.142 (9)
Main Authors: Moix, Jeremy M., Ma, Jian, Cao, Jianshu
Format: Article
Language:English
Subjects:
ABSORPTION SPECTRA
BENCHMARKS
CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSICS
COUPLING
DIFFERENTIAL EQUATIONS
DIMERS
EMISSION
EMISSION SPECTRA
ENERGY TRANSFER
EVALUATION
EXPANSION
HYBRIDIZATION
INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY
MATHEMATICAL SOLUTIONS
PATH INTEGRALS
QUANTUM SYSTEMS
RESONANCE
SPECTRAL DENSITY
STOCHASTIC PROCESSES
TEMPERATURE DEPENDENCE
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Summary:A numerically exact path integral treatment of the absorption and emission spectra of open quantum systems is presented that requires only the straightforward solution of a stochastic differential equation. The approach converges rapidly enabling the calculation of spectra of large excitonic systems across the complete range of system parameters and for arbitrary bath spectral densities. With the numerically exact absorption and emission operators, one can also immediately compute energy transfer rates using the multi-chromophoric Förster resonant energy transfer formalism. Benchmark calculations on the emission spectra of two level systems are presented demonstrating the efficacy of the stochastic approach. This is followed by calculations of the energy transfer rates between two weakly coupled dimer systems as a function of temperature and system-bath coupling strength. It is shown that the recently developed hybrid cumulant expansion (see Paper II) is the only perturbative method capable of generating uniformly reliable energy transfer rates and emission spectra across a broad range of system parameters.
ISSN:0021-9606
1089-7690