Long-range Corrected Fragment Molecular Orbital Density-Functional Tight-binding Method for Excited States in Large Molecular Systems

TL;DR

This paper introduces a novel long-range corrected fragment molecular orbital density-functional tight-binding method (FMO-LC-DFTB) for efficiently calculating excited states in large molecular systems, enabling studies of complex assemblies with hundreds of molecules.

Contribution

The paper develops and validates a new FMO-LC-DFTB method combining excitonic Hamiltonian with fragment-based calculations for large molecular assemblies, improving accuracy and efficiency.

Findings

Accurately reproduces spectra of anthracene clusters.

Demonstrates scalability to systems with over 300 molecules.

Enables analysis of excitonic participation in large aggregates.

Abstract

Herein, we present a new method to efficiently calculate electronically excited states in large molecular assemblies, consisting of hundreds of molecules. For this purpose, we combine the long-range corrected tight-binding density-functional fragment molecular orbital method (FMO-LC-DFTB) with an excitonic Hamiltonian, which is constructed in the basis of locally excited and charge-transfer configuration state functions calculated for embedded monomers and dimers and accounts explicitly for the electronic coupling between all types of excitons. We first evaluate both the accuracy and efficiency of our fragmentation approach for molecular dimers and aggregates by comparing with the full LC-TD-DFTB method. The comparison of the calculated spectra of an anthracene cluster shows a very good agreement between our method and the LC-TD-DFTB reference. The effective computational scaling of our method has been explored for anthracene clusters and for perylene bisimide aggregates. We demonstrate the applicability of our method by the calculation of the excited state properties of pentacene crystal models consisting of up to 319 molecules. Furthermore, the participation ratio of the monomer fragments to the excited states is analyzed by the calculation of natural transition orbital (NTO) participation numbers, which are verified by the hole and particle density for a chosen pentacene cluster. The use of our FMO-LC-TDDFTB method will allow for future studies of excitonic dynamics and charge transport to be performed on complex molecular systems consisting of thousands of atoms.