Davydov-Type Excitonic Effects on the Absorption Spectra of Parallel-Stacked and Herringbone Aggregates of Pentacene: Time-Dependent Density-Functional Theory and Time-Dependent Density-Functional Tight Binding

TL;DR

This study evaluates the capabilities of TD-DFT and TD-DFTB methods, including dispersion corrections and range-separated hybrids, to accurately describe Davydov excitonic effects in pentacene aggregates, comparing results with experimental data.

Contribution

It systematically assesses the performance of advanced TD-DFT and TD-DFTB approaches in modeling excitonic effects in pentacene, highlighting the importance of dispersion and range-separated functionals.

Findings

Range-separated hybrids significantly affect charge-transfer excitons.

B3LYP and B3LYP-parameterized TD-DFTB yield best agreement with experiments.

Overcorrection by CAM-B3LYP may reduce accuracy for certain structures.

Abstract

Exciton formation leads to J-bands in solid pentacene. Describing these exciton bands represents a challenge for both time-dependent (TD) density-functional theory (DFT) and for its semiempirical analogue, namely for TD density-functional tight binding (DFTB) for three reasons (i) solid pentacene and pentacene aggregates are bound only by van der Waals forces which are notoriously difficult to describe with DFT and DFTB, (ii) the proper description of the long-range coupling between molecules, needed to describe Davydov splitting, is not easy to include in TD-DFT with traditional functionals and in TD-DFTB, and (iii) mixing may occur between local and charge transfer excitons, which may, in turn, require special functionals. We assess how far TD-DFT and TD-DFTB have progressed towards a correct description of this type of exciton by including both a dispersion correction for the ground state and a range-separated hybrid functional for the excited state. Analytic results for parallel-stacked ethylene are derived which go beyond Kasha's exciton model in that we are able to make a clear distinction between charge transfer and energy transfer excitons. This is further confirmed when it is shown that range-separated hybrids have a markedly greater effect on charge-transfer excitons than on energy-transfer excitons in the case of parallel-stacked pentacenes. TD-DFT calculations with the CAM-B3LYP functional and TD-lc-DFT calculations lead to negligeable excitonic corrections for the herringbone crystal structure, possibly because of an overcorrection of charge-transfer effects. In this case, TD-DFT calculations with the B3LYP functional or TD-DFTB calculations parameterized to B3LYP give the best results for excitonic corrections for the herringbone crystal structure as judged from comparison with experimental spectra and with Bethe-Salpeter equation calculations from the literature.