Title: Examination of How Well Long-Range-Corrected Density Functionals Satisfy the Ionization Energy Theorem

Abstract

For this work, we calculated the vertical ionization energies (VIE) of 99 species in two ways to examine the accuracy of several long-range-corrected (LC) hybrid meta functionals in comparison with a gradient approximation (GA), global hybrids, and doubly hybrids. In the category of LC functionals, we examined both those with meta ingredients (i.e., that depend on the kinetic energy density) and those without them. The LC-hybrid meta functionals examined are M11, revM11, M11plus, and ωB97M-V. The reference data used to assess accuracy consist of 95 molecules and 4 atoms in the GW100 set. The two methods studied are the ΔSCF method (involving the difference of neutral and cation self-consistent field (SCF) energies) and the ionization energy theorem (involving the orbital energy of the highest occupied molecular orbital, HOMO). We calculated linear correlation coefficients (r²) and mean absolute deviations (MADs) between each approach and the reference VIE value from the CCSD(T)/def2-TZVPP level of theory. We compared the new LC-hybrid meta calculations to calculations with the 10 functionals in a previous VIE study by Brémond et al. and to the calculations with LC-BLYP (LC-Becke, Lee–Yang–Parr), CAM-B3LYP (Coulomb-attenuating-method Becke-3-parameter Lee–Yang–Parr), LC-ωHPBE, and ωB97X-D. The results show that Minnesota LC-hybrid meta functionals have themore » smallest mean absolute deviation of ionization energy theorem VIEs with the reference data; the LC-ωHPBE functional also does quite well in this test. This is very encouraging and indicates that LC-hybrid meta functionals would be the best starting points for the tuning strategy that has been shown to be a very good procedure for improving time-dependent density functional calculations, and it also helps explain the good success of LC-hybrid meta functionals for molecular excitation energies.« less

Authors:

Kanchanakungwankul, Siriluk  ^[1];

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• Search DOE PAGES for ORCID "0000-0003-4906-020X"

Truhlar, Donald G.  ^[1]

• Search DOE PAGES for author "Truhlar, Donald G."
• Search DOE PAGES for ORCID "0000-0002-7742-7294"

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+ Show Author Affiliations

1. Univ. of Minnesota, Minneapolis, MN (United States)

Publication Date:

Wed Jul 28 00:00:00 EDT 2021

Research Org.:

Univ. of Minnesota, Minneapolis, MN (United States)

Sponsoring Org.:

USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division (CSGB)

OSTI Identifier:

2311166

Grant/Contract Number:  

SC0008688; FG02-17ER16362

Resource Type:

Accepted Manuscript

Journal Name:

Journal of Chemical Theory and Computation

Additional Journal Information:

Journal Volume: 17; Journal Issue: 8; Journal ID: ISSN 1549-9618

Publisher:

American Chemical Society

Country of Publication:

United States

Language:

English

Subject:

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; chemical calculations; electronic properties; energy; ionization; liquid chromatography