Real-Time Time-Dependent Density Functional Theory Implementation of Electronic Circular Dichroism Applied to Nanoscale Metal-Organic Clusters

TL;DR

This paper introduces a real-time TDDFT implementation for electronic circular dichroism calculations in GPAW, enabling efficient analysis of large nanoscale metal-organic clusters by reducing computational costs compared to traditional methods.

Contribution

The authors develop and benchmark a real-time TDDFT approach for ECD in GPAW, supporting both basis sets and demonstrating improved efficiency for large systems.

Findings

Efficient real-time TDDFT implementation for ECD in GPAW.

Benchmark shows comparable accuracy to LR-TDDFT for small molecules.

Successful application to large nanoclusters demonstrates scalability.

Abstract

Electronic circular dichroism (ECD) is a powerful spectroscopical method for investigating chiral properties at the molecular level. ECD calculations with the commonly used linear-response time-dependent density functional theory (LR-TDDFT) framework can be prohibitively costly for large systems. To alleviate this problem, we present here an ECD implementation for the projector augmented-wave method in the real-time-propagation TDDFT (RT-TDDFT) framework in the open-source GPAW code. Our implementation supports both local atomic basis set and real-space finite-difference representations of wave functions. We benchmark our implementation against an existing LR-TDDFT implementation in GPAW for small chiral molecules. We then demonstrate the efficiency of our local atomic basis set implementation for a large hybrid nanocluster.