Real-time time-dependent density functional theory implementation of electronic circular dichroism applied to nanoscale metal-organic clusters

Electronic circular dichroism (ECD) is a powerful spectroscopy 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 within the projector augmented-wave method in a real-time-propagation TDDFT framework in the open-source GPAW code. Our implementation supports both local atomic basis sets 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 and discuss the chiroptical properties of the cluster.

Automated summary

ECD is a powerful spectroscopy method for studying molecular chiral properties, but calculations with LR-TDDFT can be costly. A new ECD implementation within the GPAW code was developed, supporting local atomic basis sets and finite-difference representations. The implementation was benchmarked against LR-TDDFT for small chiral molecules and showed efficiency for a large hybrid nanocluster, discussing its chiroptical properties.