Search Menu
DOE PAGES title logo U.S. Department of Energy
Office of Scientific and Technical Information
Search Scholarly Publications

Title: A Comparison of Exact and Model Exchange–Correlation Potentials for Molecules

Journal Article · · Journal of Physical Chemistry Letters
 [1]; ORCiD logo [2]; ORCiD logo [2]
  1. University of Michigan, Ann Arbor, MI (United States); University of Michigan, Ann Arbor
  2. University of Michigan, Ann Arbor, MI (United States)
+ Show Author Affiliations

Accurate exchange–correlation (XC) potentials for three-dimensional systems–via solution of the inverse density functional theory (DFT) problem–are now available to test the quality of DFT approximations. Herein, the exact XC potential for seven molecules–dihydrogen at four different bond-lengths, lithium hydride, water, and ortho-benzyne–are computed from full configuration interaction reference densities. These are compared to model XC potentials from nonlocal (B3LYP, HSE06, SCAN0, and M08-HX) and semilocal/local (SCAN, PBE, and PW92) XC functionals. Whereas for most systems, relative errors in the ground-state densities are O(10–3–10–2) , the model XC potentials have much higher errors of O(10–1–100) . Among the model XC functionals, SCAN0 offers the best agreement with the exact XC potential, underlining the significance of satisfying exact conditions as well as including nonlocal effects in XC functionals. This work indicates that tests against the exact XC potential will provide a promising new direction for building more accurate XC functionals for DFT.

Research Organization:
University of Michigan, Ann Arbor, MI (United States)
Sponsoring Organization:
Army Research Office (ARO); USDOE Office of Science (SC), Basic Energy Sciences (BES)
Grant/Contract Number:
AC02-05CH11231; SC0022241
OSTI ID:
2409394
Journal Information:
Journal of Physical Chemistry Letters, Journal Name: Journal of Physical Chemistry Letters Journal Issue: 50 Vol. 12; ISSN 1948-7185
Publisher:
American Chemical SocietyCopyright Statement
Country of Publication:
United States
Language:
English

References (61)

Numerical methods for the inverse problem of density functional theory journal July 2017
Kohn-Sham potentials corresponding to Slater and Gaussian basis set densities
  • Schipper, P. R. T.; Gritsenko, O. V.; Baerends, E. J.
  • Theoretical Chemistry Accounts: Theory, Computation, and Modeling (Theoretica Chimica Acta), Vol. 98, Issue 1 https://doi.org/10.1007/s002140050273
journal October 1997
Assessment of exchange correlation functionals journal January 2000
Reduction of Hartree–Fock Wavefunctions to Kohn–Sham Effective Potentials Using Multiresolution Analysis journal February 2021
Unveiling the Physics Behind Hybrid Functionals journal June 2020
Singlet–Triplet Gaps through Incremental Full Configuration Interaction journal June 2017
Inverse Kohn–Sham Density Functional Theory: Progress and Challenges journal June 2021
Challenges for Density Functional Theory journal December 2011
Removal of Basis-Set Artifacts in Kohn–Sham Potentials Recovered from Electron Densities journal August 2013
Characterizing and Understanding the Remarkably Slow Basis Set Convergence of Several Minnesota Density Functionals for Intermolecular Interaction Energies journal September 2013
Exploring the Limit of Accuracy of the Global Hybrid Meta Density Functional for Main-Group Thermochemistry, Kinetics, and Noncovalent Interactions journal October 2008
Accurate first-principles structures and energies of diversely bonded systems from an efficient density functional journal June 2016
Exact exchange-correlation potentials from ground-state electron densities journal October 2019
A direct optimization method for calculating density functionals and exchange–correlation potentials from electron densities journal January 2003
Hybrid functionals based on a screened Coulomb potential journal May 2003
Screened hybrid density functionals applied to solids journal April 2006
Optimized effective potentials from electron densities in finite basis sets journal November 2007
Comparing ab initio density-functional and wave function theories: The impact of correlation on the electronic density and the role of the correlation potential journal September 2011
Unambiguous optimization of effective potentials in finite basis sets journal December 2011
Gaussian basis sets for use in correlated molecular calculations. I. The atoms boron through neon and hydrogen journal January 1989
A new mixing of Hartree–Fock and local density‐functional theories journal January 1993
Density‐functional thermochemistry. III. The role of exact exchange journal April 1993
Exchange‐correlation potentials journal November 1996
Accurate numerical determination of Kohn-Sham potentials from electronic densities: I. Two-electron systems journal June 1997
Determination of Kohn–Sham effective potentials from electron densities using the differential virial theorem journal October 2012
Toward reliable density functional methods without adjustable parameters: The PBE0 model journal April 1999
Perspective: Fifty years of density-functional theory in chemical physics journal May 2014
The individual and collective effects of exact exchange and dispersion interactions on the ab initio structure of liquid water journal August 2014
Kohn–Sham exchange-correlation potentials from second-order reduced density matrices journal December 2015
SCAN-based hybrid and double-hybrid density functionals from models without fitted parameters journal January 2016
Improved method for generating exchange-correlation potentials from electronic wave functions journal February 2017
Incremental full configuration interaction journal March 2017
Exact exchange-correlation potentials of singlet two-electron systems journal October 2017
Regularized SCAN functional journal April 2019
Fermi-Amaldi model for exchange-correlation: atomic excitation energies from orbital energy differences journal August 2005
Advances in molecular quantum chemistry contained in the Q-Chem 4 program package journal September 2014
Thirty years of density functional theory in computational chemistry: an overview and extensive assessment of 200 density functionals journal April 2017
Hybrid functionals applied to extended systems journal January 2008
Inhomogeneous Electron Gas journal November 1964
Self-Consistent Equations Including Exchange and Correlation Effects journal November 1965
Kohn-Sham potentials and wave functions from electron densities journal October 1992
Construction of exact Kohn-Sham orbitals from a given electron density journal March 1993
Exchange-correlation potential with correct asymptotic behavior journal April 1994
From electron densities to Kohn-Sham kinetic energies, orbital energies, exchange-correlation potentials, and exchange-correlation energies journal September 1994
Accurate exchange-correlation potentials and total-energy components for the helium isoelectronic series journal November 1994
Kohn-Sham potentials and exchange and correlation energy densities from one- and two-electron density matrices for Li 2 , N 2 , and F 2 journal March 1998
Algorithm to derive exact exchange-correlation potentials from correlated densities in atoms journal January 2003
Development of the Colle-Salvetti correlation-energy formula into a functional of the electron density journal January 1988
Accurate and simple analytic representation of the electron-gas correlation energy journal June 1992
Generalized Kohn-Sham schemes and the band-gap problem journal February 1996
Enhancing the efficiency of density functionals with an improved iso-orbital indicator journal January 2019
Strongly Constrained and Appropriately Normed Semilocal Density Functional journal July 2015
Reduction of Electronic Wave Functions to Kohn-Sham Effective Potentials journal August 2015
Generalized Gradient Approximation Made Simple journal October 1996
Climbing the Density Functional Ladder: Nonempirical Meta–Generalized Gradient Approximation Designed for Molecules and Solids journal September 2003
Optimized Effective Potentials in Finite Basis Sets journal June 2007
Performance of the strongly constrained and appropriately normed density functional for solid-state materials journal June 2018
Exact Generalized Kohn-Sham Theory for Hybrid Functionals journal May 2020
Orbital-dependent density functionals: Theory and applications journal January 2008
Density functional theory: Its origins, rise to prominence, and future journal August 2015
Density functional theory is straying from the path toward the exact functional journal January 2017

Similar Records

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Density Functional Theory
Electrical Properties
Electron Density
Molecular Modeling
Molecules