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
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