Efficient Calculation of Electronic Absorption Spectra by Means of Intensity-Selected TD-DFTB

TL;DR

This paper introduces an intensity-based truncation method for TD-DFTB to efficiently compute electronic absorption spectra of large molecules, reducing computational cost while preserving spectral features.

Contribution

It proposes a novel oscillator strength-based truncation approach for TD-DFTB, significantly decreasing calculation time without losing spectral accuracy.

Findings

Truncation preserves key spectral features

Reduces computational effort for large molecules

Enables broader application of optical property calculations

Abstract

During the last two decades density functional based linear response approaches have become the de facto standard for the calculation of optical properties of small and medium-sized molecules. At the heart of these methods is the solution of an eigenvalue equation in the space of single-orbital transitions, whose quickly increasing number makes such calculations costly if not infeasible for larger molecules. This is especially true for time-dependent density functional tight binding (TD-DFTB), where the evaluation of the matrix elements is inexpensive. For the relatively large systems that can be studied the solution of the eigenvalue equation therefore determines the cost of the calculation. We propose to do an oscillator strength based truncation of the single-orbital transition space to reduce the computational effort of TD-DFTB based absorption spectra calculations. We show that even a sizeable truncation does not destroy the principal features of the absorption spectrum, while naturally avoiding the unnecessary calculation of excitations with small oscillator strengths. We argue that the reduced computational cost of intensity-selected TD-DFTB together with its ease of use compared to other methods lowers the barrier of performing optical properties calculations of large molecules, and can serve to make such calculations possible in a wider array of applications.