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

Abstract

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., MCO 3, M(OH) 2, M(NCNH) 2, K 3M(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 localizationmore » 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.« less

Authors:
 [1]; ORCiD logo [1]
  1. Department of Chemical Engineering and ‡Department of Mechanical Engineering, Massachusetts Institute of Technology, Cambridge, Massachusetts 02139, United States
Publication Date:
Research Org.:
Massachusetts Inst. of Technology (MIT), Cambridge, MA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1418190
Alternate Identifier(s):
OSTI ID: 1508565
Grant/Contract Number:  
SC0018096
Resource Type:
Published Article
Journal Name:
Journal of Chemical Theory and Computation
Additional Journal Information:
Journal Name: Journal of Chemical Theory and Computation Journal Volume: 14 Journal Issue: 2; Journal ID: ISSN 1549-9618
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Zhao, Qing, and Kulik, Heather J. Where Does the Density Localize in the Solid State? Divergent Behavior for Hybrids and DFT+U. United States: N. p., 2018. Web. doi:10.1021/acs.jctc.7b01061.
Zhao, Qing, & Kulik, Heather J. Where Does the Density Localize in the Solid State? Divergent Behavior for Hybrids and DFT+U. United States. doi:10.1021/acs.jctc.7b01061.
Zhao, Qing, and Kulik, Heather J. Tue . "Where Does the Density Localize in the Solid State? Divergent Behavior for Hybrids and DFT+U". United States. doi:10.1021/acs.jctc.7b01061.
@article{osti_1418190,
title = {Where Does the Density Localize in the Solid State? Divergent Behavior for Hybrids and DFT+U},
author = {Zhao, Qing and Kulik, Heather J.},
abstractNote = {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.},
doi = {10.1021/acs.jctc.7b01061},
journal = {Journal of Chemical Theory and Computation},
number = 2,
volume = 14,
place = {United States},
year = {2018},
month = {1}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record
DOI: 10.1021/acs.jctc.7b01061

Citation Metrics:
Cited by: 6 works
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Works referencing / citing this record:

CSD 1865188: Experimental Crystal Structure Determination
dataset, January 2018

  • Zhao, Qing; Kulik, Heather J.
  • FIZ Karlsruhe – Leibniz Institute for Information Infrastructure
  • DOI: 10.25505/fiz.icsd.cc20lwcw

CSD 1865189: Experimental Crystal Structure Determination
dataset, January 2018

  • Zhao, Qing; Kulik, Heather J.
  • FIZ Karlsruhe – Leibniz Institute for Information Infrastructure
  • DOI: 10.25505/fiz.icsd.cc20lwdx

CSD 1865190: Experimental Crystal Structure Determination
dataset, January 2018

  • Zhao, Qing; Kulik, Heather J.
  • FIZ Karlsruhe – Leibniz Institute for Information Infrastructure
  • DOI: 10.25505/fiz.icsd.cc20lwfy

CSD 1865201: Experimental Crystal Structure Determination
dataset, January 2018

  • Zhao, Qing; Kulik, Heather J.
  • FIZ Karlsruhe – Leibniz Institute for Information Infrastructure
  • DOI: 10.25505/fiz.icsd.cc20lws9

CSD 1865202: Experimental Crystal Structure Determination
dataset, January 2018

  • Zhao, Qing; Kulik, Heather J.
  • FIZ Karlsruhe – Leibniz Institute for Information Infrastructure
  • DOI: 10.25505/fiz.icsd.cc20lwtb

CSD 1865203: Experimental Crystal Structure Determination
dataset, January 2018

  • Zhao, Qing; Kulik, Heather J.
  • FIZ Karlsruhe – Leibniz Institute for Information Infrastructure
  • DOI: 10.25505/fiz.icsd.cc20lwvc

CSD 1865204: Experimental Crystal Structure Determination
dataset, January 2018

  • Zhao, Qing; Kulik, Heather J.
  • FIZ Karlsruhe – Leibniz Institute for Information Infrastructure
  • DOI: 10.25505/fiz.icsd.cc20lwwd

CSD 1865205: Experimental Crystal Structure Determination
dataset, January 2018

  • Zhao, Qing; Kulik, Heather J.
  • FIZ Karlsruhe – Leibniz Institute for Information Infrastructure
  • DOI: 10.25505/fiz.icsd.cc20lwxf

CSD 1865206: Experimental Crystal Structure Determination
dataset, January 2018

  • Zhao, Qing; Kulik, Heather J.
  • FIZ Karlsruhe – Leibniz Institute for Information Infrastructure
  • DOI: 10.25505/fiz.icsd.cc20lwyg

CSD 1865207: Experimental Crystal Structure Determination
dataset, January 2018

  • Zhao, Qing; Kulik, Heather J.
  • FIZ Karlsruhe – Leibniz Institute for Information Infrastructure
  • DOI: 10.25505/fiz.icsd.cc20lwzh

CSD 1865208: Experimental Crystal Structure Determination
dataset, January 2018

  • Zhao, Qing; Kulik, Heather J.
  • FIZ Karlsruhe – Leibniz Institute for Information Infrastructure
  • DOI: 10.25505/fiz.icsd.cc20lx0k

CSD 1865209: Experimental Crystal Structure Determination
dataset, January 2018

  • Zhao, Qing; Kulik, Heather J.
  • FIZ Karlsruhe – Leibniz Institute for Information Infrastructure
  • DOI: 10.25505/fiz.icsd.cc20lx1l

CSD 1865210: Experimental Crystal Structure Determination
dataset, January 2018

  • Zhao, Qing; Kulik, Heather J.
  • FIZ Karlsruhe – Leibniz Institute for Information Infrastructure
  • DOI: 10.25505/fiz.icsd.cc20lx2m

CCDC 1865191: Experimental Crystal Structure Determination
dataset, January 2018


CCDC 1865192: Experimental Crystal Structure Determination
dataset, January 2018


CCDC 1865193: Experimental Crystal Structure Determination
dataset, January 2018


CCDC 1865197: Experimental Crystal Structure Determination
dataset, January 2018


CCDC 1865198: Experimental Crystal Structure Determination
dataset, January 2018


CCDC 1865199: Experimental Crystal Structure Determination
dataset, January 2018


CCDC 1865200: Experimental Crystal Structure Determination
dataset, January 2018


Computational Modeling of Transition Temperatures in Spin-Crossover Systems
journal, May 2019


Enumeration of de novo inorganic complexes for chemical discovery and machine learning
journal, January 2020

  • Gugler, Stefan; Janet, Jon Paul; Kulik, Heather J.
  • Molecular Systems Design & Engineering, Vol. 5, Issue 1
  • DOI: 10.1039/c9me00069k

Enumeration of de novo inorganic complexes for chemical discovery and machine learning
journal, January 2020

  • Gugler, Stefan; Janet, Jon Paul; Kulik, Heather J.
  • Molecular Systems Design & Engineering, Vol. 5, Issue 1
  • DOI: 10.1039/c9me00069k

Computational Modeling of Transition Temperatures in Spin-Crossover Systems
journal, May 2019