Accurate and efficient computation of optical absorption spectra of molecular crystals: the case of the polymorphs of ROY

TL;DR

This paper introduces a spectral warping method that efficiently computes accurate optical absorption spectra of molecular crystals, demonstrated on ROY polymorphs, outperforming traditional methods in accuracy and computational cost.

Contribution

The authors develop a spectral warping approach combining supercell semi-local TDDFT with dimer-based transformations for high-accuracy spectra at reduced computational expense.

Findings

The method accurately reproduces experimental spectra of ROY polymorphs.

It outperforms both hybrid TDDFT dimer calculations and semi-local TDDFT supercell calculations.

The approach significantly reduces computational costs while maintaining high accuracy.

Abstract

When calculating the optical absorption spectra of molecular crystals from first principles, the influence of the crystalline environment on the excitations is of significant importance. For such systems, however, methods to describe the excitations accurately can be computationally prohibitive due to the relatively large system sizes involved. In this work, we demonstrate a method that allows optical absorption spectra to be computed both efficiently and at high accuracy. Our approach is based on the spectral warping method successfully applied to molecules in solvent. It involves calculating the absorption spectrum of a supercell of the full molecular crystal using semi-local TDDFT, before warping the spectrum using a transformation derived from smaller-scale semi-local and hybrid TDDFT calculations on isolated dimers. We demonstrate the power of this method on three polymorphs of the well known colour polymorphic compound ROY, and find that it outperforms both small-scale hybrid TDDFT dimer calculations and large-scale semi-local TDDFT supercell calculations, when compared to experiment.