Document Type
Article
Publication Date
2-14-2023
Abstract
We report a minimal auxiliary basis model for time-dependent density functional theory (TDDFT) with hybrid density functionals that can accurately reproduce excitation energies and absorption spectra from TDDFT while reducing cost by about \change{two} orders of magnitude. Our method, dubbed TDDFT-ris, employs the resolution-of-the-identity technique with just one $s$-type auxiliary basis function per atom for the linear response operator, where the Gaussian exponents are parametrized across the periodic table using %using tabulated atomic radii with a single global scaling factor. By tuning on a small test set, we determine a single functional-independent scale factor that balances errors in excitation energies and absorption spectra. Benchmarked on organic molecules and compared to standard TDDFT, TDDFT-ris has an average energy error of only 0.06 eV, and yields absorption spectra in close agreement with TDDFT. Thus, TDDFT-ris enables simulation of realistic absorption spectra in large molecules that would be inaccessible from standard TDDFT.
Keywords
time-dependent density functional theory, quantum chemistry, absorption spectra
Publication Title
The Journal of Physical Chemistry Letters
Volume
14
First Page
1968
Last Page
1976
Rights
This document is the unedited Author's version of a Submitted Work that was subsequently accepted for publication in The Journal of Physical Chemistry Letters, copyright © 2023 American Chemical Society after peer review. To access the final edited and published work see https://orcid.org/10.1021/acs.jpclett.2c03698.
Recommended Citation
Zhou, Zehao and Parker, Shane M., "Minimal Auxiliary Basis Set Approach for the Electronic Excitation Spectra of Organic Molecules" (2023). Faculty Scholarship. 71.
https://commons.case.edu/facultyworks/71
Supporting Information