Author ORCID Identifier

Zehao Zhou

Shane M. Parker

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.

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