Molecular orbital projectors in non-empirical jmDFT recover exact conditions in transition-metal chemistry

Bajaj, Akash; Duan, Chenru; Nandy, Aditya; Taylor, Michael G.; Kulik, Heather J.

doi:10.1063/5.0089460

Title: Molecular orbital projectors in non-empirical jmDFT recover exact conditions in transition-metal chemistry

Journal Article · 14 May 2022 · Journal of Chemical Physics

DOI: https://doi.org/10.1063/5.0089460 · OSTI ID:1979073

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^[2]; Taylor, Michael G. ^[2];

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Massachusetts Inst. of Technology (MIT), Cambridge, MA (United States); Massachusetts Inst. of Technology, Cambridge, MA (United States)
Massachusetts Inst. of Technology (MIT), Cambridge, MA (United States)

Low-cost, non-empirical corrections to semi-local density functional theory are essential for accurately modeling transition-metal chemistry. Here, we demonstrate the judiciously modified density functional theory (jmDFT) approach with non-empirical U and J parameters obtained directly from frontier orbital energetics on a series of transition-metal complexes. We curate a set of nine representative Ti(III) and V(IV) d¹transition-metal complexes and evaluate their flat-plane errors along the fractional spin and charge lines. We demonstrate that while jmDFT improves upon both DFT+U and semi-local DFT with the standard atomic orbital projectors (AOPs), it does so inefficiently. We rationalize these inefficiencies by quantifying hybridization in the relevant frontier orbitals. To overcome these limitations, we introduce a procedure for computing a molecular orbital projector (MOP) basis for use with jmDFT. We demonstrate this single set of d¹MOPs to be suitable for nearly eliminating all energetic delocalization and static correlation errors. In all cases, MOP jmDFT outperforms AOP jmDFT, and it eliminates most flat-plane errors at non-empirical values. Unlike DFT+U or hybrid functionals, jmDFT nearly eliminates energetic delocalization and static correlation errors within a non-empirical framework.

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Research Organization:: Massachusetts Inst. of Technology (MIT), Cambridge, MA (United States)

Sponsoring Organization:: USDOE Office of Science (SC); National Science Foundation (NSF)

Grant/Contract Number:: SC0018096

OSTI ID:: 1979073

Journal Information:: Journal of Chemical Physics, Journal Name: Journal of Chemical Physics Journal Issue: 18 Vol. 156; ISSN 0021-9606

Publisher:: American Institute of Physics (AIP)Copyright Statement

Country of Publication:: United States

Language:: English

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