Origin-Independent Circular Dichroism Spectra for Molecular and Hybrid Systems with Real-Time Time-Dependent Density Functional Theory
Open Access
- 20 October 2026
- journal article
- Published by American Chemical Society (ACS) in The Journal of Physical Chemistry A
- Vol. 130 (44) , 8960-8971
Abstract
We present a velocity gauge implementation for real-time time-dependent density functional theory (RT-TDDFT) calculations of electronic circular dichroism (ECD) spectra within the linear combination of atomic orbitals framework of the GPAW code. In contrast to the commonly used length gauge, which exhibits a pronounced dependence on the origin of the coordinate system, our velocity gauge implementation produces origin-independent ECD spectra already for moderately sized basis sets. The computational efficiency of the RT-TDDFT implementation in GPAW enables efficient ECD simulations of large finite systems, making chiroptical analyses of molecular and molecule–nanoparticle assemblies exceeding 1000 atoms feasible.Keywords
Funding Information
- HORIZON EUROPE Marie Sklodowska-Curie Actions (101152999)
This publication has 54 references indexed in Scilit:
- Enantioselective Behaviors of Chiral Pesticides and Enantiomeric Signatures in Foods and the EnvironmentJournal of Agricultural and Food Chemistry, 2023
- Computing the electronic circular dichroism spectrum of DNA quadruple helices of different topology: A critical test for a generalized excitonic model based on a fragment diabatizationChirality, 2023
- Modeling of the spectroscopy of core electrons with density functional theoryWIREs Computational Molecular Science, 2021
- Electronic circular dichroism with real time time dependent density functional theory: Propagator formalism and gauge dependenceChemical Physics, 2019
- Chemical chiral pollution: Impact on the society and science and need of the regulations in the 21st centuryChirality, 2017
- A simplified time-dependent density functional theory approach for electronic ultraviolet and circular dichroism spectra of very large moleculesComputational and Theoretical Chemistry, 2014
- Time-dependent density-functional theory for molecules and molecular solidsJournal of Molecular Structure: THEOCHEM, 2009
- Ab initio calculation of molecular chiroptical propertiesTheoretical Chemistry Accounts, 2005
- Density functional theory calculation of electronic circular dichroism using London orbitalsChemical Physics Letters, 2004
- Optical rotation studied by density-functional and coupled-cluster methodsChemical Physics Letters, 2002