skip to main content
OSTI.GOV title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: Can Kohn–Sham density functional theory predict accurate charge distributions for both single-reference and multi-reference molecules?

Abstract

This work investigates the performances of a variety of density functionals for their ability to accurately predict charge distributions of a range of single- and multi-reference molecules.

Authors:
ORCiD logo [1]; ORCiD logo [1]
  1. Department of Chemistry; Nanoporous Materials Genome Center; Chemical Theory Center, and Minnesota Supercomputing Institute; University of Minnesota; Minneapolis
Publication Date:
Research Org.:
Univ. of Minnesota, Minneapolis, MN (United States)
Sponsoring Org.:
USDOE Office of Science (SC)
OSTI Identifier:
1535194
DOE Contract Number:  
SC0008688
Resource Type:
Journal Article
Journal Name:
Physical Chemistry Chemical Physics. PCCP (Print)
Additional Journal Information:
Journal Volume: 19; Journal Issue: 20; Journal ID: ISSN 1463-9076
Publisher:
Royal Society of Chemistry
Country of Publication:
United States
Language:
English
Subject:
Chemistry; Physics

Citation Formats

Verma, Pragya, and Truhlar, Donald G. Can Kohn–Sham density functional theory predict accurate charge distributions for both single-reference and multi-reference molecules?. United States: N. p., 2017. Web. doi:10.1039/c7cp01576c.
Verma, Pragya, & Truhlar, Donald G. Can Kohn–Sham density functional theory predict accurate charge distributions for both single-reference and multi-reference molecules?. United States. doi:10.1039/c7cp01576c.
Verma, Pragya, and Truhlar, Donald G. Sun . "Can Kohn–Sham density functional theory predict accurate charge distributions for both single-reference and multi-reference molecules?". United States. doi:10.1039/c7cp01576c.
@article{osti_1535194,
title = {Can Kohn–Sham density functional theory predict accurate charge distributions for both single-reference and multi-reference molecules?},
author = {Verma, Pragya and Truhlar, Donald G.},
abstractNote = {This work investigates the performances of a variety of density functionals for their ability to accurately predict charge distributions of a range of single- and multi-reference molecules.},
doi = {10.1039/c7cp01576c},
journal = {Physical Chemistry Chemical Physics. PCCP (Print)},
issn = {1463-9076},
number = 20,
volume = 19,
place = {United States},
year = {2017},
month = {1}
}

Works referenced in this record:

Density functional theory in surface chemistry and catalysis
journal, January 2011

  • Norskov, J. K.; Abild-Pedersen, F.; Studt, F.
  • Proceedings of the National Academy of Sciences, Vol. 108, Issue 3
  • DOI: 10.1073/pnas.1006652108

Challenges for Density Functional Theory
journal, December 2011

  • Cohen, Aron J.; Mori-Sánchez, Paula; Yang, Weitao
  • Chemical Reviews, Vol. 112, Issue 1
  • DOI: 10.1021/cr200107z

Consistent descriptions of metal–ligand bonds and spin-crossover in inorganic chemistry
journal, January 2013


Perspective: Kohn-Sham density functional theory descending a staircase
journal, October 2016

  • Yu, Haoyu S.; Li, Shaohong L.; Truhlar, Donald G.
  • The Journal of Chemical Physics, Vol. 145, Issue 13
  • DOI: 10.1063/1.4963168

Electronic Structures of Molecules XI. Electroaffinity, Molecular Orbitals and Dipole Moments
journal, September 1935

  • Mulliken, Robert S.
  • The Journal of Chemical Physics, Vol. 3, Issue 9
  • DOI: 10.1063/1.1749731

Bonded-atom fragments for describing molecular charge densities
journal, January 1977


Charge Model 5: An Extension of Hirshfeld Population Analysis for the Accurate Description of Molecular Interactions in Gaseous and Condensed Phases
journal, February 2012

  • Marenich, Aleksandr V.; Jerome, Steven V.; Cramer, Christopher J.
  • Journal of Chemical Theory and Computation, Vol. 8, Issue 2, p. 527-541
  • DOI: 10.1021/ct200866d

Performance of density functionals for first row transition metal systems
journal, January 2007

  • Jensen, Kasper P.; Roos, Björn O.; Ryde, Ulf
  • The Journal of Chemical Physics, Vol. 126, Issue 1
  • DOI: 10.1063/1.2406071

Balanced basis sets of split valence, triple zeta valence and quadruple zeta valence quality for H to Rn: Design and assessment of accuracy
journal, January 2005

  • Weigend, Florian; Ahlrichs, Reinhart
  • Physical Chemistry Chemical Physics, Vol. 7, Issue 18, p. 3297-3305
  • DOI: 10.1039/b508541a

Density Functionals for Inorganometallic and Organometallic Chemistry
journal, December 2005

  • Schultz, Nathan E.; Zhao, Yan; Truhlar, Donald G.
  • The Journal of Physical Chemistry A, Vol. 109, Issue 49
  • DOI: 10.1021/jp0539223

A simple DFT-based diagnostic for nondynamical correlation
journal, December 2012

  • Fogueri, Uma R.; Kozuch, Sebastian; Karton, Amir
  • Theoretical Chemistry Accounts, Vol. 132, Issue 1
  • DOI: 10.1007/s00214-012-1291-y

Generalized Gradient Approximation Made Simple
journal, October 1996

  • Perdew, John P.; Burke, Kieron; Ernzerhof, Matthias
  • Physical Review Letters, Vol. 77, Issue 18, p. 3865-3868
  • DOI: 10.1103/PhysRevLett.77.3865

A new parametrization of exchange–correlation generalized gradient approximation functionals
journal, April 2001

  • Boese, A. Daniel; Handy, Nicholas C.
  • The Journal of Chemical Physics, Vol. 114, Issue 13
  • DOI: 10.1063/1.1347371

Left-right correlation energy
journal, March 2001


Restoring the Density-Gradient Expansion for Exchange in Solids and Surfaces
journal, April 2008


Toward improved density functionals for the correlation energy
journal, October 2009

  • Thakkar, Ajit J.; McCarthy, Shane P.
  • The Journal of Chemical Physics, Vol. 131, Issue 13
  • DOI: 10.1063/1.3243845

Generalized Gradient Approximation That Recovers the Second-Order Density-Gradient Expansion with Optimized Across-the-Board Performance
journal, July 2011

  • Peverati, Roberto; Zhao, Yan; Truhlar, Donald G.
  • The Journal of Physical Chemistry Letters, Vol. 2, Issue 16
  • DOI: 10.1021/jz200616w

HLE16: A Local Kohn–Sham Gradient Approximation with Good Performance for Semiconductor Band Gaps and Molecular Excitation Energies
journal, January 2017


Exchange–Correlation Functional with Good Accuracy for Both Structural and Energetic Properties while Depending Only on the Density and Its Gradient
journal, June 2012

  • Peverati, Roberto; Truhlar, Donald G.
  • Journal of Chemical Theory and Computation, Vol. 8, Issue 7
  • DOI: 10.1021/ct3002656

Nonseparable exchange–correlation functional for molecules, including homogeneous catalysis involving transition metals
journal, January 2015

  • Yu, Haoyu S.; Zhang, Wenjing; Verma, Pragya
  • Physical Chemistry Chemical Physics, Vol. 17, Issue 18
  • DOI: 10.1039/C5CP01425E

New exchange-correlation density functionals: The role of the kinetic-energy density
journal, June 2002

  • Boese, A. Daniel; Handy, Nicholas C.
  • The Journal of Chemical Physics, Vol. 116, Issue 22
  • DOI: 10.1063/1.1476309

Climbing the Density Functional Ladder: Nonempirical Meta–Generalized Gradient Approximation Designed for Molecules and Solids
journal, September 2003


A new local density functional for main-group thermochemistry, transition metal bonding, thermochemical kinetics, and noncovalent interactions
journal, November 2006

  • Zhao, Yan; Truhlar, Donald G.
  • The Journal of Chemical Physics, Vol. 125, Issue 19, Article No. 194101
  • DOI: 10.1063/1.2370993

M11-L: A Local Density Functional That Provides Improved Accuracy for Electronic Structure Calculations in Chemistry and Physics
journal, December 2011

  • Peverati, Roberto; Truhlar, Donald G.
  • The Journal of Physical Chemistry Letters, Vol. 3, Issue 1
  • DOI: 10.1021/jz201525m

Semilocal and hybrid meta-generalized gradient approximations based on the understanding of the kinetic-energy-density dependence
journal, January 2013

  • Sun, Jianwei; Haunschild, Robin; Xiao, Bing
  • The Journal of Chemical Physics, Vol. 138, Issue 4
  • DOI: 10.1063/1.4789414

HLE17: An Improved Local Exchange–Correlation Functional for Computing Semiconductor Band Gaps and Molecular Excitation Energies
journal, March 2017

  • Verma, Pragya; Truhlar, Donald G.
  • The Journal of Physical Chemistry C, Vol. 121, Issue 13
  • DOI: 10.1021/acs.jpcc.7b01066

MN15-L: A New Local Exchange-Correlation Functional for Kohn–Sham Density Functional Theory with Broad Accuracy for Atoms, Molecules, and Solids
journal, February 2016

  • Yu, Haoyu S.; He, Xiao; Truhlar, Donald G.
  • Journal of Chemical Theory and Computation, Vol. 12, Issue 3
  • DOI: 10.1021/acs.jctc.5b01082

Density‐functional thermochemistry. III. The role of exact exchange
journal, April 1993

  • Becke, Axel D.
  • The Journal of Chemical Physics, Vol. 98, Issue 7, p. 5648-5652
  • DOI: 10.1063/1.464913

Ab Initio Calculation of Vibrational Absorption and Circular Dichroism Spectra Using Density Functional Force Fields
journal, November 1994

  • Stephens, P. J.; Devlin, F. J.; Chabalowski, C. F.
  • The Journal of Physical Chemistry, Vol. 98, Issue 45, p. 11623-11627
  • DOI: 10.1021/j100096a001

Toward reliable adiabatic connection models free from adjustable parameters
journal, August 1997


Exchange functionals with improved long-range behavior and adiabatic connection methods without adjustable parameters: The mPW and mPW1PW models
journal, January 1998

  • Adamo, Carlo; Barone, Vincenzo
  • The Journal of Chemical Physics, Vol. 108, Issue 2
  • DOI: 10.1063/1.475428

Development and assessment of new exchange-correlation functionals
journal, October 1998

  • Hamprecht, Fred A.; Cohen, Aron J.; Tozer, David J.
  • The Journal of Chemical Physics, Vol. 109, Issue 15
  • DOI: 10.1063/1.477267

Toward reliable density functional methods without adjustable parameters: The PBE0 model
journal, April 1999

  • Adamo, Carlo; Barone, Vincenzo
  • The Journal of Chemical Physics, Vol. 110, Issue 13
  • DOI: 10.1063/1.478522

Adiabatic Connection for Kinetics
journal, June 2000

  • Lynch, Benjamin J.; Fast, Patton L.; Harris, Maegan
  • The Journal of Physical Chemistry A, Vol. 104, Issue 21
  • DOI: 10.1021/jp000497z

Reparameterization of hybrid functionals based on energy differences of states of different multiplicity
journal, December 2001

  • Reiher, Markus; Salomon, Oliver; Artur Hess, Bernd
  • Theoretical Chemistry Accounts: Theory, Computation, and Modeling (Theoretica Chimica Acta), Vol. 107, Issue 1
  • DOI: 10.1007/s00214-001-0300-3

A new hybrid exchange–correlation functional using the Coulomb-attenuating method (CAM-B3LYP)
journal, July 2004

  • Yanai, Takeshi; Tew, David P.; Handy, Nicholas C.
  • Chemical Physics Letters, Vol. 393, Issue 1-3, p. 51-57
  • DOI: 10.1016/j.cplett.2004.06.011

Semiempirical hybrid functional with improved performance in an extensive chemical assessment
journal, September 2005

  • Keal, Thomas W.; Tozer, David J.
  • The Journal of Chemical Physics, Vol. 123, Issue 12
  • DOI: 10.1063/1.2061227

Assessment of a long-range corrected hybrid functional
journal, December 2006

  • Vydrov, Oleg A.; Scuseria, Gustavo E.
  • The Journal of Chemical Physics, Vol. 125, Issue 23
  • DOI: 10.1063/1.2409292

Can short-range hybrids describe long-range-dependent properties?
journal, July 2009

  • Henderson, Thomas M.; Izmaylov, Artur F.; Scalmani, Giovanni
  • The Journal of Chemical Physics, Vol. 131, Issue 4
  • DOI: 10.1063/1.3185673

Influence of the exchange screening parameter on the performance of screened hybrid functionals
journal, December 2006

  • Krukau, Aliaksandr V.; Vydrov, Oleg A.; Izmaylov, Artur F.
  • The Journal of Chemical Physics, Vol. 125, Issue 22
  • DOI: 10.1063/1.2404663

A consistent and accurate ab initio parametrization of density functional dispersion correction (DFT-D) for the 94 elements H-Pu
journal, April 2010

  • Grimme, Stefan; Antony, Jens; Ehrlich, Stephan
  • The Journal of Chemical Physics, Vol. 132, Issue 15
  • DOI: 10.1063/1.3382344

Effect of the damping function in dispersion corrected density functional theory
journal, March 2011

  • Grimme, Stefan; Ehrlich, Stephan; Goerigk, Lars
  • Journal of Computational Chemistry, Vol. 32, Issue 7
  • DOI: 10.1002/jcc.21759

Screened-exchange density functionals with broad accuracy for chemistry and solid-state physics
journal, January 2012

  • Peverati, Roberto; Truhlar, Donald G.
  • Physical Chemistry Chemical Physics, Vol. 14, Issue 47
  • DOI: 10.1039/c2cp42576a

Comparative assessment of a new nonempirical density functional: Molecules and hydrogen-bonded complexes
journal, December 2003

  • Staroverov, Viktor N.; Scuseria, Gustavo E.; Tao, Jianmin
  • The Journal of Chemical Physics, Vol. 119, Issue 23
  • DOI: 10.1063/1.1626543

Exchange-correlation functional with broad accuracy for metallic and nonmetallic compounds, kinetics, and noncovalent interactions
journal, October 2005

  • Zhao, Yan; Schultz, Nathan E.; Truhlar, D. G.
  • The Journal of Chemical Physics, Vol. 123, Issue 16
  • DOI: 10.1063/1.2126975

Design of Density Functionals by Combining the Method of Constraint Satisfaction with Parametrization for Thermochemistry, Thermochemical Kinetics, and Noncovalent Interactions
journal, January 2006

  • Zhao, Yan; Schultz, Nathan E.; Truhlar, Donald G.
  • Journal of Chemical Theory and Computation, Vol. 2, Issue 2
  • DOI: 10.1021/ct0502763

Design of Density Functionals That Are Broadly Accurate for Thermochemistry, Thermochemical Kinetics, and Nonbonded Interactions
journal, June 2005

  • Zhao, Yan; Truhlar, Donald G.
  • The Journal of Physical Chemistry A, Vol. 109, Issue 25
  • DOI: 10.1021/jp050536c

Exploring the Limit of Accuracy of the Global Hybrid Meta Density Functional for Main-Group Thermochemistry, Kinetics, and Noncovalent Interactions
journal, October 2008

  • Zhao, Yan; Truhlar, Donald G.
  • Journal of Chemical Theory and Computation, Vol. 4, Issue 11
  • DOI: 10.1021/ct800246v

Improving the Accuracy of Hybrid Meta-GGA Density Functionals by Range Separation
journal, October 2011

  • Peverati, Roberto; Truhlar, Donald G.
  • The Journal of Physical Chemistry Letters, Vol. 2, Issue 21
  • DOI: 10.1021/jz201170d