Non-additive non-interacting kinetic energy of rare gas dimers
Abstract
We show approximations of the non-additive non-interacting kinetic energy (NAKE) as an explicit functional of the density are the basis of several electronic structure methods that provide improved computational efficiency over standard Kohn-Sham calculations. However, within most fragment-based formalisms, there is no unique exact NAKE, making it difficult to develop general, robust approximations for it. When adjustments are made to the embedding formalisms to guarantee uniqueness, approximate functionals may be more meaningfully compared to the exact unique NAKE. We use numerically accurate inversions to study the exact NAKE of several rare-gas dimers within partition density functional theory, a method that provides the uniqueness for the exact NAKE. We find that the NAKE decreases nearly exponentially with atomic separation for the rare-gas dimers. We compute the logarithmic derivative of the NAKE with respect to the bond length for our numerically accurate inversions as well as for several approximate NAKE functionals. We show that standard approximate NAKE functionals do not reproduce the correct behavior for this logarithmic derivative and propose two new NAKE functionals that do. The first of these is based on a re-parametrization of a conjoint Perdew-Burke-Ernzerhof (PBE) functional. The second is a simple, physically motivated non-decomposable NAKE functional thatmore »
- Authors:
-
[1];
- Purdue Univ., West Lafayette, IN (United States). Dept. of Physics and Astronomy
- Purdue Univ., West Lafayette, IN (United States). Dept. of Physics and Astronomy, and Dept. of Chemistry
- Publication Date:
- Research Org.:
- Univ. of California, Riverside, CA (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC)
- OSTI Identifier:
- 1540150
- Alternate Identifier(s):
- OSTI ID: 1426015
- Grant/Contract Number:
- SC0005291; FG02-10ER16191
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Journal of Chemical Physics
- Additional Journal Information:
- Journal Volume: 148; Journal Issue: 10; Journal ID: ISSN 0021-9606
- Publisher:
- American Institute of Physics (AIP)
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Chemistry; Physics
Citation Formats
Jiang, Kaili, Nafziger, Jonathan, and Wasserman, Adam. Non-additive non-interacting kinetic energy of rare gas dimers. United States: N. p., 2018.
Web. doi:10.1063/1.5016308.
Jiang, Kaili, Nafziger, Jonathan, & Wasserman, Adam. Non-additive non-interacting kinetic energy of rare gas dimers. United States. https://doi.org/10.1063/1.5016308
Jiang, Kaili, Nafziger, Jonathan, and Wasserman, Adam. Wed .
"Non-additive non-interacting kinetic energy of rare gas dimers". United States. https://doi.org/10.1063/1.5016308. https://www.osti.gov/servlets/purl/1540150.
@article{osti_1540150,
title = {Non-additive non-interacting kinetic energy of rare gas dimers},
author = {Jiang, Kaili and Nafziger, Jonathan and Wasserman, Adam},
abstractNote = {We show approximations of the non-additive non-interacting kinetic energy (NAKE) as an explicit functional of the density are the basis of several electronic structure methods that provide improved computational efficiency over standard Kohn-Sham calculations. However, within most fragment-based formalisms, there is no unique exact NAKE, making it difficult to develop general, robust approximations for it. When adjustments are made to the embedding formalisms to guarantee uniqueness, approximate functionals may be more meaningfully compared to the exact unique NAKE. We use numerically accurate inversions to study the exact NAKE of several rare-gas dimers within partition density functional theory, a method that provides the uniqueness for the exact NAKE. We find that the NAKE decreases nearly exponentially with atomic separation for the rare-gas dimers. We compute the logarithmic derivative of the NAKE with respect to the bond length for our numerically accurate inversions as well as for several approximate NAKE functionals. We show that standard approximate NAKE functionals do not reproduce the correct behavior for this logarithmic derivative and propose two new NAKE functionals that do. The first of these is based on a re-parametrization of a conjoint Perdew-Burke-Ernzerhof (PBE) functional. The second is a simple, physically motivated non-decomposable NAKE functional that matches the asymptotic decay constant without fitting.},
doi = {10.1063/1.5016308},
journal = {Journal of Chemical Physics},
number = 10,
volume = 148,
place = {United States},
year = {Wed Mar 14 00:00:00 EDT 2018},
month = {Wed Mar 14 00:00:00 EDT 2018}
}
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Works referenced in this record:
Non-local relation between kinetic and exchange energy densities in Hartree-Fock theory
journal, April 1991
- March, N. H.; Santamaria, R.
- International Journal of Quantum Chemistry, Vol. 39, Issue 4
Libxc: A library of exchange and correlation functionals for density functional theory
journal, October 2012
- Marques, Miguel A. L.; Oliveira, Micael J. T.; Burnus, Tobias
- Computer Physics Communications, Vol. 183, Issue 10
Accurate frozen-density embedding potentials as a first step towards a subsystem description of covalent bonds
journal, April 2010
- Fux, Samuel; Jacob, Christoph R.; Neugebauer, Johannes
- The Journal of Chemical Physics, Vol. 132, Issue 16
Density-Based Partitioning Methods for Ground-State Molecular Calculations
journal, July 2014
- Nafziger, Jonathan; Wasserman, Adam
- The Journal of Physical Chemistry A, Vol. 118, Issue 36
Quantum mechanical embedding theory based on a unique embedding potential
journal, April 2011
- Huang, Chen; Pavone, Michele; Carter, Emily A.
- The Journal of Chemical Physics, Vol. 134, Issue 15
The calculation of atomic fields
journal, January 1927
- Thomas, L. H.
- Mathematical Proceedings of the Cambridge Philosophical Society, Vol. 23, Issue 5
Nonadditive kinetic potentials from inverted Kohn-Sham problem
journal, June 2017
- Banafsheh, Mojdeh; Adam Wesolowski, Tomasz
- International Journal of Quantum Chemistry, Vol. 118, Issue 1
Nonlocal van der Waals density functional: The simpler the better
journal, December 2010
- Vydrov, Oleg A.; Van Voorhis, Troy
- The Journal of Chemical Physics, Vol. 133, Issue 24
The Energy-Density Functional of an Electron Gas in Locally Linear Approximation of the One-Body Potential
journal, September 1972
- Baltin, R.
- Zeitschrift für Naturforschung A, Vol. 27, Issue 8-9
Accurate Reference Data for the Nonadditive, Noninteracting Kinetic Energy in Covalent Bonds
journal, January 2017
- Nafziger, Jonathan; Jiang, Kaili; Wasserman, Adam
- Journal of Chemical Theory and Computation, Vol. 13, Issue 2
Zur Theorie der Kernmassen
journal, July 1935
- Weizs�cker, C. F. v.
- Zeitschrift f�r Physik, Vol. 96, Issue 7-8
Semiclassical Neutral Atom as a Reference System in Density Functional Theory
journal, May 2011
- Constantin, Lucian A.; Fabiano, E.; Laricchia, S.
- Physical Review Letters, Vol. 106, Issue 18
Conjoint gradient correction to the Hartree-Fock kinetic- and exchange-energy density functionals
journal, July 1991
- Lee, Hsing; Lee, Chengteh; Parr, Robert G.
- Physical Review A, Vol. 44, Issue 1
On the Foundations of Chemical Reactivity Theory
journal, March 2007
- Cohen, Morrel H.; Wasserman, Adam
- The Journal of Physical Chemistry A, Vol. 111, Issue 11
Obtaining a gradient-corrected kinetic-energy functional from the Perdew-Wang exchange functional
journal, December 1994
- Lembarki, A.; Chermette, H.
- Physical Review A, Vol. 50, Issue 6
Link between the kinetic- and exchange-energy functionals in the generalized gradient approximation
journal, January 2002
- Tran, Fabien; Weso?owski, Tomasz A.
- International Journal of Quantum Chemistry, Vol. 89, Issue 5
Further evidence of the conjoint correction to the local kinetic and exchange energy density functionals
journal, January 1995
- Fuentealba, P.; Reyes, O.
- Chemical Physics Letters, Vol. 232, Issue 1-2
Performance of Kinetic Energy Functionals for Interaction Energies in a Subsystem Formulation of Density Functional Theory
journal, November 2009
- Götz, Andreas W.; Beyhan, S. Maya; Visscher, Lucas
- Journal of Chemical Theory and Computation, Vol. 5, Issue 12
Exact nonadditive kinetic potentials for embedded density functional theory
journal, August 2010
- Goodpaster, Jason D.; Ananth, Nandini; Manby, Frederick R.
- The Journal of Chemical Physics, Vol. 133, Issue 8
Partition density-functional theory
journal, August 2010
- Elliott, Peter; Burke, Kieron; Cohen, Morrel H.
- Physical Review A, Vol. 82, Issue 2
Generalized Gradient Approximations of the Noninteracting Kinetic Energy from the Semiclassical Atom Theory: Rationalization of the Accuracy of the Frozen Density Embedding Theory for Nonbonded Interactions
journal, July 2011
- Laricchia, S.; Fabiano, E.; Constantin, L. A.
- Journal of Chemical Theory and Computation, Vol. 7, Issue 8
Reply to “Comment on ‘Single-point kinetic energy density functionals: A pointwise kinetic energy density analysis and numerical convergence investigation’ ”
journal, September 2015
- Xia, Junchao; Carter, Emily A.
- Physical Review B, Vol. 92, Issue 11
Numerical methods for the inverse problem of density functional theory
journal, July 2017
- Jensen, Daniel S.; Wasserman, Adam
- International Journal of Quantum Chemistry, Vol. 118, Issue 1
Subsystem density-functional theory: Subsystem density-functional theory
journal, July 2014
- Jacob, Christoph R.; Neugebauer, Johannes
- Wiley Interdisciplinary Reviews: Computational Molecular Science, Vol. 4, Issue 4
Frozen density functional approach for ab initio calculations of solvated molecules
journal, July 1993
- Wesolowski, Tomasz Adam; Warshel, Arieh
- The Journal of Physical Chemistry, Vol. 97, Issue 30
The Importance of Being Inconsistent
journal, May 2017
- Wasserman, Adam; Nafziger, Jonathan; Jiang, Kaili
- Annual Review of Physical Chemistry, Vol. 68, Issue 1
Comment on “Single-point kinetic energy density functionals: A pointwise kinetic energy density analysis and numerical convergence investigation”
journal, September 2015
- Trickey, S. B.; Karasiev, Valentin V.; Chakraborty, Debajit
- Physical Review B, Vol. 92, Issue 11
Statistical Theory of Many-Electron Systems. General Considerations Pertaining to the Thomas-Fermi Theory
journal, January 1957
- Golden, Sidney
- Physical Review, Vol. 105, Issue 2
Molecular binding energies from partition density functional theory
journal, December 2011
- Nafziger, Jonathan; Wu, Qin; Wasserman, Adam
- The Journal of Chemical Physics, Vol. 135, Issue 23
On the Weizsäcker Correction to the Thomas-Fermi Theory of the Atom
journal, June 1965
- Yonei, Katsumi; Tomishima, Yasuo
- Journal of the Physical Society of Japan, Vol. 20, Issue 6
Comparison of kinetic-energy density functionals
journal, December 1992
- Thakkar, Ajit J.
- Physical Review A, Vol. 46, Issue 11
Orbital-free kinetic-energy density functionals with a density-dependent kernel
journal, December 1999
- Wang, Yan Alexander; Govind, Niranjan; Carter, Emily A.
- Physical Review B, Vol. 60, Issue 24
Self-consistently determined properties of solids without band-structure calculations
journal, October 1991
- Cortona, Pietro
- Physical Review B, Vol. 44, Issue 16
Thomas-fermi and related theories of atoms and molecules
journal, October 1981
- Lieb, Elliott H.
- Reviews of Modern Physics, Vol. 53, Issue 4
Van der Waals density functional theory with applications: Van Der Waals DFT
journal, October 2004
- Langreth, D. C.; Dion, M.; Rydberg, H.
- International Journal of Quantum Chemistry, Vol. 101, Issue 5
Modified Fourth-Order Kinetic Energy Gradient Expansion with Hartree Potential-Dependent Coefficients
journal, August 2017
- Constantin, Lucian A.; Fabiano, Eduardo; Della Sala, Fabio
- Journal of Chemical Theory and Computation, Vol. 13, Issue 9
NWChem: A comprehensive and scalable open-source solution for large scale molecular simulations
journal, September 2010
- Valiev, M.; Bylaska, E. J.; Govind, N.
- Computer Physics Communications, Vol. 181, Issue 9, p. 1477-1489
Single-point kinetic energy density functionals: A pointwise kinetic energy density analysis and numerical convergence investigation
journal, January 2015
- Xia, Junchao; Carter, Emily A.
- Physical Review B, Vol. 91, Issue 4
Testing the kinetic energy functional: Kinetic energy density as a density functional
journal, May 2003
- Sim, Eunji; Larkin, Joe; Burke, Kieron
- The Journal of Chemical Physics, Vol. 118, Issue 18
Nonlocal orbital-free kinetic energy density functional for semiconductors
journal, January 2010
- Huang, Chen; Carter, Emily A.
- Physical Review B, Vol. 81, Issue 4
Nonlocal van der Waals density functional: The simpler the better
text, January 2010
- Vydrov, Oleg A.; Van Voorhis, Troy
- arXiv
Molecular Binding Energies from Partition Density Functional Theory
text, January 2011
- Nafziger, Jonathan; Wu, Qin; Wasserman, Adam
- arXiv
Density-Based Partitioning Methods for Ground-State Molecular Calculations
journal, July 2014
- Nafziger, Jonathan; Wasserman, Adam
- The Journal of Physical Chemistry A, Vol. 118, Issue 36
Molecular binding energies from partition density functional theory
journal, December 2011
- Nafziger, Jonathan; Wu, Qin; Wasserman, Adam
- The Journal of Chemical Physics, Vol. 135, Issue 23
Comparison of kinetic-energy density functionals
journal, December 1992
- Thakkar, Ajit J.
- Physical Review A, Vol. 46, Issue 11
Obtaining a gradient-corrected kinetic-energy functional from the Perdew-Wang exchange functional
journal, December 1994
- Lembarki, A.; Chermette, H.
- Physical Review A, Vol. 50, Issue 6
Frank Discussion of the Status of Ground-state Orbital-free DFT
text, January 2015
- Karasiev, Valentin V.; Trickey, S. B.
- arXiv
Nonlocal Kinetic Energy Functionals By Functional Integration
text, January 2017
- Mi, Wenhui; Genova, Alessandro; Pavanello, Michele
- arXiv
Works referencing / citing this record:
An accurate analytical formula for the van der Waals potentials of homonuclear rare-gas dimers with one adjustable parameter
journal, September 2018
- Sheng, Xiaowei; Zhu, Hongjuan; Zhang, Zixuan
- International Journal of Quantum Chemistry, Vol. 119, Issue 3
Orbital-free approximations to the kinetic-energy density in exchange-correlation MGGA functionals: Tests on solids
journal, October 2018
- Tran, Fabien; Kovács, Péter; Kalantari, Leila
- The Journal of Chemical Physics, Vol. 149, Issue 14
Constructing a non-additive non-interacting kinetic energy functional approximation for covalent bonds from exact conditions
journal, October 2018
- Jiang, Kaili; Nafziger, Jonathan; Wasserman, Adam
- The Journal of Chemical Physics, Vol. 149, Issue 16
Constructing a Non-additive Non-interacting Kinetic Energy Functional Approximation for Covalent Bonds from Exact Conditions
text, January 2018
- Jiang, Kaili; Nafziger, Jonathan; Wasserman, Adam
- arXiv