Simultaneous determination of structures, vibrations, and frontier orbital energies from a self-consistent range-separated hybrid functional

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DOI	Resolve DOI: https://doi.org/10.1021/jz5010939
Author	Search for: Tamblyn, Isaac; Search for: Refaely-abramson, Sivan; Search for: Neaton, Jeffrey B.; Search for: Kronik, Leeor
Format	Text, Article
Subject	density functional theory; ionization energy; optimal tuning; range-separated hybrid functionals; structural optimization; zero-point energy
Abstract	A self-consistent optimally tuned range-separated hybrid density functional (scOT-RSH) approach is developed. It can simultaneously predict accurate geometries, vibrational modes, and frontier orbital energies. This is achieved by optimizing the range-separation parameter, γ, to both satisfy the ionization energy theorem and minimize interatomic forces. We benchmark our approach against an established hybrid functional, B3LYP, using the G2 test set. scOT-RSH greatly improves the accuracy of occupied frontier orbital energies, with a mean absolute error (MAE) of only 0.2 eV relative to experimental ionization energies compared to 2.96 eV with B3LYP. Geometries do not change significantly compared to those obtained from B3LYP, with a bond length MAE of 0.012 Å compared to 0.008 Å for B3LYP, and a 6.5% MAE for zero-point energies, slightly larger than that of B3LYP (3.1%). scOT-RSH represents a new paradigm in which accurate geometries and ionization energies can be predicted simultaneously from a single functional approach.
Publication date	2014-08-07
Publisher	American Chemical Society
In	The Journal of Physical Chemistry Letters 5, no. 15: 2734–2741.
Language	English
Peer reviewed	Yes
NRC publication	This is a non-NRC publication "Non-NRC publications" are publications authored by NRC employees prior to their employment by NRC.
NPARC number	23003154
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Record identifier	b4354087-b275-4f95-bd13-295106a04672
Record created	2018-05-02
Record modified	2020-05-30

Date modified:: 2025-11-09