Accuracy of approximate methods for the calculation of absorption-type linear spectra with a complex system-bath coupling

The accuracy of approximate methods for calculating linear optical spectra depends on many variables. In this study, we fix most of these parameters to typical values found in photosynthetic light-harvesting complexes of plants and determine the accuracy of approximate spectra with respect to exact calculation as a function of the energy gap and interpigment coupling in a pigment dimer. We use a spectral density with the first eight intramolecular modes of chlorophyll a and include inhomogeneous disorder for the calculation of spectra. We compare the accuracy of absorption, linear dichroism, and circular dichroism spectra calculated using the Full Cumulant Expansion (FCE), coherent time-dependent Redfield (ctR), and time-independent Redfield and modified Redfield methods. As a reference we use spectra calculated with the Exact Stochastic Path Integral Evaluation method. We find the FCE method to be the most accurate for the calculation of all spectra. The ctR method performs well for the qualitative calculation of absorption and linear dichroism spectra when pigments are moderately coupled (\(\sim 15\text{ cm}^{-1}\)), but ctR spectra may differ significantly from exact spectra when strong interpigment coupling (\(\sim 100\text{ cm}^{-1}\)) is present. The dependence of the quality of Redfield and modified Redfield spectra on molecular parameters is similar, and these methods almost always perform worse than ctR, especially when the interpigment coupling is strong or the excitonic energy gap is small (for a given coupling). The accuracy of approximate spectra is not affected by resonance between the excitonic energy gap and intramolecular modes when realistic inhomogeneous disorder is included.