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Simple and Efficient Theoretical Approach To Compute 2D Optical Spectra

Author:
Jain, Amber, Petit, Andrew S., Anna, Jessica M., Subotnik, Joseph E.
Source:
TheJournal of physical chemistry 2019 v.123 no.7 pp. 1602-1617
ISSN:
1520-5207
Subject:
models, physical chemistry, spectroscopy
Abstract:
A highly efficient scheme is proposed and benchmarked to compute 2D optical spectra. This scheme is ideally designed for electronic spectroscopy; however, the method can be applied in a straightforward way to vibrational spectroscopy as well. Our scheme performs dynamics only for the t₂ duration, eliminating explicit t₁ and t₃ coherent dynamics and thus can achieve dramatic improvements in efficiency. To gain this efficiency, we assume the system is in the inhomogeneous regime and that there is no significant nonadiabatic transfer of population during the t₁ and t₃ coherence times. Preliminary results are presented for the Frenkel Hamiltonian. We obtain excellent agreement with numerically exact results (which are possible for this simplistic model Hamiltonian), capturing all relevant trends at least qualitatively (and sometimes quantitatively).
Agid:
6313465