Improvement of d-d interactions in density functional tight binding for transition metal ions with a ligand field model: assessment of a DFTB3+U model on nickel coordination compounds

Physical Chemistry Chemical Physics : PCCP
Stepan StepanovićQiang Cui

Abstract

To improve the description of interactions among the localized d, f electrons in transition metals, we have introduced a ligand-field motivated contribution into the Density Functional Tight Binding (DFTB) model. Referred to as DFTB3+U, the approach treats the d, f electron repulsions with rotationally invariant orbital-orbital interactions and a Hartree-Fock model; this represents a major conceptual improvement over the original DFTB3 approach, which treats the d, f-shell interactions in a highly averaged fashion without orbital level of description. The DFTB3+U approach is tested using a series of nickel compounds that feature Ni(ii) and Ni(iii) oxidation states. By using parameters developed with the original DFTB3 Hamiltonian and empirical +U parameters (F0/2/4 Slater integrals), we observe that the DFTB3+U model indeed provides substantial improvements over the original DFTB3 model for a number of properties of the nickel compounds, including the population and spin polarization of the d-shell, nature of the frontier orbitals, ligand field splitting and the energy different between low and high spin states at OPBE optimized structures. This proof-of-concept study suggests that with self-consistent parameterization of the e...Continue Reading

References

Dec 15, 1994·Physical Review. B, Condensed Matter·I V SolovyevV I Anisimov
Aug 15, 1995·Physical Review. B, Condensed Matter·A I LiechtensteinJ Zaanen
Apr 1, 1991·Physical Review. B, Condensed Matter·V I Anisimov, O Gunnarsson
Jul 15, 1991·Physical Review. B, Condensed Matter·V I AnisimovO K Andersen
Apr 13, 2007·The Journal of Physical Chemistry. a·Christof KöhlerMichael Sternberg
Apr 19, 2007·The Journal of Physical Chemistry. a·G Seifert
Jun 15, 2007·The Journal of Physical Chemistry. a·M Elstner
Nov 20, 2009·Physical Chemistry Chemical Physics : PCCP·Christopher J Cramer, Donald G Truhlar
Dec 4, 2012·Journal of Chemical Theory and Computation·Michael GausMarcus Elstner
Jul 25, 2013·Nature Chemistry·Yuki KurashigeTakeshi Yanai
Feb 12, 2014·Philosophical Transactions. Series A, Mathematical, Physical, and Engineering Sciences·Marcus Elstner, Gotthard Seifert
Mar 22, 2014·Physical Chemistry Chemical Physics : PCCP·M Gruden-PavlovićM Swart
May 23, 2014·Physical Chemistry Chemical Physics : PCCP·Qiang Cui, Marcus Elstner
Sep 3, 2014·The Journal of Physical Chemistry. B·Xiya LuQiang Cui
Jun 27, 2015·The Journal of Physical Chemistry Letters·Katja HansenAlexandre Tkatchenko
Nov 18, 2015·Journal of Chemical Theory and Computation·Rebecca K CarlsonLaura Gagliardi
Nov 18, 2015·Journal of Chemical Theory and Computation·Michael GausQiang Cui
Sep 9, 2014·Journal of Chemical Theory and Computation·Giovanni Li ManniLaura Gagliardi
Dec 21, 2016·Accounts of Chemical Research·Marcel Swart, Maja Gruden
Jan 10, 2017·Nature Communications·Kristof T SchüttAlexandre Tkatchenko
Jul 6, 2017·Journal of Chemical Theory and Computation·Alberto BaiardiMarkus Reiher
Jun 22, 2018·Journal of Chemical Theory and Computation·Sheng GuoGarnet Kin-Lic Chan
Feb 15, 2019·The Journal of Physical Chemistry. a·Chen ZhouDonald G Truhlar
Aug 3, 2019·The Journal of Physical Chemistry. a·Xiya LuQiang Cui
Jan 22, 2020·The Journal of Physical Chemistry. a·Samuel J StoneburnerLaura Gagliardi
Feb 20, 2020·Journal of Chemical Theory and Computation·Sebastian DohmStefan Grimme
Feb 25, 2020·Annual Review of Physical Chemistry·Frank NoéCecilia Clementi
Jun 24, 2020·The Journal of Chemical Physics·Henry F SchurkusJohn F Stanton
Aug 19, 2020·Nature Communications·Alexandre Tkatchenko

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Citations

Jan 7, 2021·The Journal of Physical Chemistry. B·Qiang CuiLuke Xie

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Software Mentioned

DFTB
DMRG
hartree

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