Where Does the Density Localize in the Solid State? Divergent Behavior for Hybrids and DFT+U

Zhao, Qing; Kulik, Heather J.

doi:10.1021/acs.jctc.7b01061

Title: Where Does the Density Localize in the Solid State? Divergent Behavior for Hybrids and DFT+U

Journal Article · Fri Jan 26 00:00:00 EST 2018 · Journal of Chemical Theory and Computation

DOI:https://doi.org/10.1021/acs.jctc.7b01061· OSTI ID:1418190

Zhao, Qing ^[1];

^[1]

Department of Chemical Engineering and ‡Department of Mechanical Engineering, Massachusetts Institute of Technology, Cambridge, Massachusetts 02139, United States

Approximate density functional theory (DFT) is widely used in chemistry and physics, despite delocalization errors that affect energetic and density properties. DFT+U (i.e., semilocal DFT augmented with a Hubbard U correction) and global hybrid functionals are two commonly employed practical methods to address delocalization error. Recent work demonstrated that in transition-metal complexes both methods localize density away from the metal and onto surrounding ligands, regardless of metal or ligand identity. In this work, we compare density localization trends with DFT+U and global hybrids on a diverse set of 34 transition-metal-containing solids with varying magnetic state, electron configuration and valence shell, and coordinating-atom orbital diffuseness (i.e., O, S, Se). We also study open-framework solids in which the metal is coordinated by molecular ligands, i.e., MCO₃, M(OH)₂, M(NCNH)₂, K₃M(CN)₆ (M = V–Ni). As in transition-metal complexes, incorporation of Hartree–Fock exchange consistently localizes density away from the metal, but DFT+U exhibits diverging behavior, localizing density (i) onto the metal in low-spin and late transition metals and (ii) away from the metal in other cases in agreement with hybrids. To isolate the effect of the crystal environment, we extract molecular analogues from open-framework transition-metal solids and observe consistent localization of the density away from the metal in all cases with both DFT+U and hybrid exchange. These observations highlight the limited applicability of trends established for functional tuning on transition-metal complexes even to equivalent coordination environments in the solid state.

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

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: SC0018096

OSTI ID:: 1418190

Alternate ID(s):: OSTI ID: 1508565

Journal Information:: Journal of Chemical Theory and Computation, Journal Name: Journal of Chemical Theory and Computation Vol. 14 Journal Issue: 2; ISSN 1549-9618

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 50 works

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