A comparison of QTP functionals against coupled-cluster methods for EAs of small organic molecules

Abigail Pavlicek; Zachary W. Windom; Ajith Perera; Rodney J. Bartlett

doi:10.1063/5.0177136

A comparison of QTP functionals against coupled-cluster methods for EAs of small organic molecules

Abigail Pavlicek
, Zachary W. Windom
, Ajith Perera
, Rodney J. Bartlett

Research output: Contribution to journal › Article › peer-review

7 Scopus citations

Abstract

EA-EOM-CCSD electron affinities and LUMO energies of various Kohn-Sham density functional theory (DFT) methods are calculated for an a priori IP benchmark set of 64 small, closed-shell molecules. The purpose of these calculations was to investigate whether the QTP KS-DFT functionals can emulate EA-EOM-CC with only a mean-field approximation. We show that the accuracy of DFT—relative to CCSD—improves significantly when elements of correlated orbital theory are introduced into the parameterization to define the QTP family of functionals. In particular, QTP(02), which has only a single range separation parameter, provides results accurate to a MAD of < 0.15 eV for the whole set of 64 molecules compared to EA-EOM-CCSD, far exceeding the results from the non-QTP family of density functionals.

Original language	English
Article number	014106
Journal	Journal of Chemical Physics
Volume	160
Issue number	1
DOIs	https://doi.org/10.1063/5.0177136
State	Published - Jan 7 2024
Externally published	Yes

Funding

The authors thank Dr. James Thorpe for his help in setting up continuum-orbital-based EA-EOM calculations within CFOUR. This work was supported by the Air Force Office of Scientific Research under AFOSR Award No. FA9550-23-1-0118. Z.W. acknowledges the National Science Foundation and the Molecular Sciences Software Institute for financial support under Grant No. CHE-2136142. Z.W. also acknowledges the support from the U.S. Department of Energy, Office of Science, Office of Workforce Development for Teachers and Scientists, Office of Science Graduate Student Research (SCGSR) program. The SCGSR program is administered by the Oak Ridge Institute for Science and Education (ORISE) for the DOE. ORISE is managed by ORAU under Contract No. DE-SC0014664. The authors thank Dr. James Thorpe for his help in setting up continuum-orbital-based EA-EOM calculations within CFOUR. This work was supported by the Air Force Office of Scientific Research under AFOSR Award No. FA9550-23-1-0118. Z.W. acknowledges the National Science Foundation and the Molecular Sciences Software Institute for financial support under Grant No. CHE-2136142. Z.W. also acknowledges the support from the U.S. Department of Energy, Office of Science, Office of Workforce Development for Teachers and Scientists, Office of Science Graduate Student Research (SCGSR) program. The SCGSR program is administered by the Oak Ridge Institute for Science and Education (ORISE) for the DOE. ORISE is managed by ORAU under Contract No. DE-SC0014664.

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10.1063/5.0177136

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abstract = "EA-EOM-CCSD electron affinities and LUMO energies of various Kohn-Sham density functional theory (DFT) methods are calculated for an a priori IP benchmark set of 64 small, closed-shell molecules. The purpose of these calculations was to investigate whether the QTP KS-DFT functionals can emulate EA-EOM-CC with only a mean-field approximation. We show that the accuracy of DFT—relative to CCSD—improves significantly when elements of correlated orbital theory are introduced into the parameterization to define the QTP family of functionals. In particular, QTP(02), which has only a single range separation parameter, provides results accurate to a MAD of < 0.15 eV for the whole set of 64 molecules compared to EA-EOM-CCSD, far exceeding the results from the non-QTP family of density functionals.",

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AU - Pavlicek, Abigail

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AB - EA-EOM-CCSD electron affinities and LUMO energies of various Kohn-Sham density functional theory (DFT) methods are calculated for an a priori IP benchmark set of 64 small, closed-shell molecules. The purpose of these calculations was to investigate whether the QTP KS-DFT functionals can emulate EA-EOM-CC with only a mean-field approximation. We show that the accuracy of DFT—relative to CCSD—improves significantly when elements of correlated orbital theory are introduced into the parameterization to define the QTP family of functionals. In particular, QTP(02), which has only a single range separation parameter, provides results accurate to a MAD of < 0.15 eV for the whole set of 64 molecules compared to EA-EOM-CCSD, far exceeding the results from the non-QTP family of density functionals.

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A comparison of QTP functionals against coupled-cluster methods for EAs of small organic molecules

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