Comparison of three methods to compute optical absorption spectra of organic molecules and solids

TL;DR

This paper compares a real frequency-dependent polarizability method with TD-DFT for calculating optical absorption spectra of organic molecules, oligomers, and molecular crystals, highlighting their relative accuracy and limitations.

Contribution

It introduces and evaluates a polarizability-based approach for spectra computation, comparing its performance to TD-DFT across various organic systems.

Findings

Polarizability method agrees well with TD-DFT for small molecules.

Redshift issues increase with oligomer length in the polarizability approach.

Dipole approximation significantly redshifts spectra compared to TD-DFT.

Abstract

We compare the performance of an approach using real frequency dependent polarizability to compute optical absorption spectra to linear-response time-dependent density functional theory (TD-DFT) for small organic dyes, oligomers of different length (oligothiophenes), and molecular clusters representing a molecular crystal (pentacene). For pentacene, the spectra computed with the two methods are also compared to the spectrum computed for clusters and the periodic solid using the dipole approximation. The approach based on real polarizability produces spectra in good agreement with TD-DFT for small molecules. The (artificial) redshift for longer oligomers is more significant with the polarizability-based method than with TD-DFT. For pentacene clusters, TD-DFT produces reasonable spectra with a hybrid functional, but a significant redshift is introduced with a GGA functional due to the presence of charge transfer transitions. This problem is slightly attenuated with the polarizability-based method. The dipole approximation results in spectra much redshifted vs both TD-DFT and the polarizability-based method and in a different trend with cluster size.