Insights into the spurious long-range nature of local rs-dependent non-local exchange-correlation kernels
Abstract
A systematic route to go beyond the exact exchange plus random phase approximation (RPA) is to include a physical exchange-correlation kernel in the adiabatic-connection fluctuation-dissipation theorem. Previously, [D. Lu, J. Chem. Phys. 140, 18A520 (2014)], we found that non-local kernels with a screening length depending on the local Wigner-Seitz radius, rs(r), suffer an error associated with a spurious long-range repulsion in van der Waals bounded systems, which deteriorates the binding energy curve as compared to RPA. Here, we analyze the source of the error and propose to replace rs(r) by a global, average rs in the kernel. Exemplary studies with the Corradini, del Sole, Onida, and Palummo kernel show that while this change does not affect the already outstanding performance in crystalline solids, using an average rs significantly reduces the spurious long-range tail in the exchange-correlation kernel in van der Waals bounded systems. Finally, when this method is combined with further corrections using local dielectric response theory, the binding energy of the Kr dimer is improved three times as compared to RPA.
- Authors:
-
- Brookhaven National Lab. (BNL), Upton, NY (United States). Center for Functional Nanomaterials
- Publication Date:
- Research Org.:
- Brookhaven National Laboratory (BNL), Upton, NY (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC)
- OSTI Identifier:
- 1303020
- Alternate Identifier(s):
- OSTI ID: 1283417
- Report Number(s):
- BNL-112515-2016-JA
Journal ID: ISSN 0021-9606; JCPSA6; R&D Project: 16068; KC0403020
- Grant/Contract Number:
- SC00112704; AC02-05CH11231; SC0012704
- Resource Type:
- Journal Article: Accepted Manuscript
- Journal Name:
- Journal of Chemical Physics
- Additional Journal Information:
- Journal Volume: 145; Journal Issue: 5; Journal ID: ISSN 0021-9606
- Publisher:
- American Institute of Physics (AIP)
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 36 MATERIALS SCIENCE
Citation Formats
Lu, Deyu. Insights into the spurious long-range nature of local rs-dependent non-local exchange-correlation kernels. United States: N. p., 2016.
Web. doi:10.1063/1.4960381.
Lu, Deyu. Insights into the spurious long-range nature of local rs-dependent non-local exchange-correlation kernels. United States. https://doi.org/10.1063/1.4960381
Lu, Deyu. 2016.
"Insights into the spurious long-range nature of local rs-dependent non-local exchange-correlation kernels". United States. https://doi.org/10.1063/1.4960381. https://www.osti.gov/servlets/purl/1303020.
@article{osti_1303020,
title = {Insights into the spurious long-range nature of local rs-dependent non-local exchange-correlation kernels},
author = {Lu, Deyu},
abstractNote = {A systematic route to go beyond the exact exchange plus random phase approximation (RPA) is to include a physical exchange-correlation kernel in the adiabatic-connection fluctuation-dissipation theorem. Previously, [D. Lu, J. Chem. Phys. 140, 18A520 (2014)], we found that non-local kernels with a screening length depending on the local Wigner-Seitz radius, rs(r), suffer an error associated with a spurious long-range repulsion in van der Waals bounded systems, which deteriorates the binding energy curve as compared to RPA. Here, we analyze the source of the error and propose to replace rs(r) by a global, average rs in the kernel. Exemplary studies with the Corradini, del Sole, Onida, and Palummo kernel show that while this change does not affect the already outstanding performance in crystalline solids, using an average rs significantly reduces the spurious long-range tail in the exchange-correlation kernel in van der Waals bounded systems. Finally, when this method is combined with further corrections using local dielectric response theory, the binding energy of the Kr dimer is improved three times as compared to RPA.},
doi = {10.1063/1.4960381},
url = {https://www.osti.gov/biblio/1303020},
journal = {Journal of Chemical Physics},
issn = {0021-9606},
number = 5,
volume = 145,
place = {United States},
year = {Fri Aug 05 00:00:00 EDT 2016},
month = {Fri Aug 05 00:00:00 EDT 2016}
}
Works referenced in this record:
The RPA Atomization Energy Puzzle
journal, November 2009
- Ruzsinszky, Adrienn; Perdew, John P.; Csonka, Gábor I.
- Journal of Chemical Theory and Computation, Vol. 6, Issue 1
Cohesive Properties and Asymptotics of the Dispersion Interaction in Graphite by the Random Phase Approximation
journal, November 2010
- Lebègue, S.; Harl, J.; Gould, Tim
- Physical Review Letters, Vol. 105, Issue 19
Density-Functional Theory with Screened van der Waals Interactions for the Modeling of Hybrid Inorganic-Organic Systems
journal, April 2012
- Ruiz, Victor G.; Liu, Wei; Zojer, Egbert
- Physical Review Letters, Vol. 108, Issue 14
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
Accurate surface and adsorption energies from many-body perturbation theory
journal, July 2010
- Schimka, L.; Harl, J.; Stroppa, A.
- Nature Materials, Vol. 9, Issue 9
Cubic scaling algorithm for the random phase approximation: Self-interstitials and vacancies in Si
journal, August 2014
- Kaltak, Merzuk; Klimeš, Jiří; Kresse, Georg
- Physical Review B, Vol. 90, Issue 5
Accurate Ground-State Energies of Solids and Molecules from Time-Dependent Density-Functional Theory
journal, May 2014
- Olsen, Thomas; Thygesen, Kristian S.
- Physical Review Letters, Vol. 112, Issue 20
van der Waals Interactions in Molecular Assemblies from First-Principles Calculations
journal, February 2010
- Li, Yan; Lu, Deyu; Nguyen, Huy-Viet
- The Journal of Physical Chemistry A, Vol. 114, Issue 4
Adiabatic-connection fluctuation-dissipation DFT for the structural properties of solids—The renormalized ALDA and electron gas kernels
journal, September 2015
- Patrick, Christopher E.; Thygesen, Kristian S.
- The Journal of Chemical Physics, Vol. 143, Issue 10
Exchange and correlation in atoms, molecules, and solids by the spin-density-functional formalism
journal, May 1976
- Gunnarsson, O.; Lundqvist, B. I.
- Physical Review B, Vol. 13, Issue 10
A density functional for sparse matter
journal, January 2009
- Langreth, D. C.; Lundqvist, B. I.; Chakarova-Käck, S. D.
- Journal of Physics: Condensed Matter, Vol. 21, Issue 8
Energy-optimized local exchange-correlation kernel for the electron gas: Application to van der Waals forces
journal, October 2000
- Dobson, John F.; Wang, Jun
- Physical Review B, Vol. 62, Issue 15
Basis set convergence of molecular correlation energy differences within the random phase approximation
journal, February 2012
- Eshuis, Henk; Furche, Filipp
- The Journal of Chemical Physics, Vol. 136, Issue 8
Microscopic Characterization of the Interface between Aromatic Isocyanides and Au(111): A First-Principles Investigation
journal, April 2008
- Li, Yan; Lu, Deyu; Swanson, Sally A.
- The Journal of Physical Chemistry C, Vol. 112, Issue 16
Nature and Strength of Interlayer Binding in Graphite
journal, November 2009
- Spanu, Leonardo; Sorella, Sandro; Galli, Giulia
- Physical Review Letters, Vol. 103, Issue 19
Molecular tests of the random phase approximation to the exchange-correlation energy functional
journal, October 2001
- Furche, Filipp
- Physical Review B, Vol. 64, Issue 19
Simple model of the static exchange-correlation kernel of a uniform electron gas with long-range electron-electron interaction
journal, July 2005
- Toulouse, Julien
- Physical Review B, Vol. 72, Issue 3
Maximally localized generalized Wannier functions for composite energy bands
journal, November 1997
- Marzari, Nicola; Vanderbilt, David
- Physical Review B, Vol. 56, Issue 20
Communication: Beyond the random phase approximation on the cheap: Improved correlation energies with the efficient “radial exchange hole” kernel
journal, September 2012
- Gould, Tim
- The Journal of Chemical Physics, Vol. 137, Issue 11
Beyond the random phase approximation: Improved description of short-range correlation by a renormalized adiabatic local density approximation
journal, September 2013
- Olsen, Thomas; Thygesen, Kristian S.
- Physical Review B, Vol. 88, Issue 11
Evaluation of model exchange-correlation kernels in the adiabatic connection fluctuation-dissipation theorem for inhomogeneous systems
journal, May 2014
- Lu, Deyu
- The Journal of Chemical Physics, Vol. 140, Issue 18
Accurate Molecular Van Der Waals Interactions from Ground-State Electron Density and Free-Atom Reference Data
journal, February 2009
- Tkatchenko, Alexandre; Scheffler, Matthias
- Physical Review Letters, Vol. 102, Issue 7
The exchange-correlation energy of a metallic surface
journal, December 1975
- Langreth, D. C.; Perdew, J. P.
- Solid State Communications, Vol. 17, Issue 11
Local representation of the electronic dielectric response function
journal, December 2015
- Ge, Xiaochuan; Lu, Deyu
- Physical Review B, Vol. 92, Issue 24
Accurate description of van der Waals complexes by density functional theory including empirical corrections
journal, January 2004
- Grimme, Stefan
- Journal of Computational Chemistry, Vol. 25, Issue 12
Cohesive energy curves for noble gas solids calculated by adiabatic connection fluctuation-dissipation theory
journal, January 2008
- Harl, Judith; Kresse, Georg
- Physical Review B, Vol. 77, Issue 4
Role of Dispersion Interactions in the Polymorphism and Entropic Stabilization of the Aspirin Crystal
journal, July 2014
- Reilly, Anthony M.; Tkatchenko, Alexandre
- Physical Review Letters, Vol. 113, Issue 5
Simple dynamic exchange-correlation kernel of a uniform electron gas
journal, June 2007
- Constantin, Lucian A.; Pitarke, J. M.
- Physical Review B, Vol. 75, Issue 24
Improved description of metal oxide stability: Beyond the random phase approximation with renormalized kernels
journal, September 2015
- Jauho, Thomas S.; Olsen, Thomas; Bligaard, Thomas
- Physical Review B, Vol. 92, Issue 11
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
Dynamical local-field factors and effective interactions in the three-dimensional electron liquid
journal, September 1994
- Richardson, C. F.; Ashcroft, N. W.
- Physical Review B, Vol. 50, Issue 12
State-of-the-art correlated ab initio potential energy curves for heavy rare gas dimers: Ar2, Kr2, and Xe2
journal, July 2003
- Slavı́ček, Petr; Kalus, René; Paška, Petr
- The Journal of Chemical Physics, Vol. 119, Issue 4
Fast computation of molecular random phase approximation correlation energies using resolution of the identity and imaginary frequency integration
journal, June 2010
- Eshuis, Henk; Yarkony, Julian; Furche, Filipp
- The Journal of Chemical Physics, Vol. 132, Issue 23
Closed-shell ring coupled cluster doubles theory with range separation applied on weak intermolecular interactions
journal, August 2011
- Toulouse, Julien; Zhu, Wuming; Savin, Andreas
- The Journal of Chemical Physics, Vol. 135, Issue 8
Extending the random-phase approximation for electronic correlation energies: The renormalized adiabatic local density approximation
journal, August 2012
- Olsen, Thomas; Thygesen, Kristian S.
- Physical Review B, Vol. 86, Issue 8
Exchange-correlation energy of a metallic surface: Wave-vector analysis
journal, March 1977
- Langreth, David C.; Perdew, John P.
- Physical Review B, Vol. 15, Issue 6
Accurate Bulk Properties from Approximate Many-Body Techniques
journal, July 2009
- Harl, Judith; Kresse, Georg
- Physical Review Letters, Vol. 103, Issue 5
Random-phase approximation and its applications in computational chemistry and materials science
journal, June 2012
- Ren, Xinguo; Rinke, Patrick; Joas, Christian
- Journal of Materials Science, Vol. 47, Issue 21
Calculation of dispersion energies
journal, January 2012
- Dobson, John F.; Gould, Tim
- Journal of Physics: Condensed Matter, Vol. 24, Issue 7
Power series expansion of the random phase approximation correlation energy: The role of the third- and higher-order contributions
journal, October 2010
- Lu, Deyu; Nguyen, Huy-Viet; Galli, Giulia
- The Journal of Chemical Physics, Vol. 133, Issue 15
Accurate and Efficient Method for Many-Body van der Waals Interactions
journal, June 2012
- Tkatchenko, Alexandre; DiStasio, Robert A.; Car, Roberto
- Physical Review Letters, Vol. 108, Issue 23
Exchange functional that tests the robustness of the plasmon description of the van der Waals density functional
journal, January 2014
- Berland, Kristian; Hyldgaard, Per
- Physical Review B, Vol. 89, Issue 3
Nonlocal energy-optimized kernel: Recovering second-order exchange in the homogeneous electron gas
journal, January 2016
- Bates, Jefferson E.; Laricchia, Savio; Ruzsinszky, Adrienn
- Physical Review B, Vol. 93, Issue 4
Adiabatic-Connection Fluctuation-Dissipation Density-Functional Theory Based on Range Separation
journal, March 2009
- Toulouse, Julien; Gerber, Iann C.; Jansen, Georg
- Physical Review Letters, Vol. 102, Issue 9
Van der Waals Density Functional for General Geometries
journal, June 2004
- Dion, M.; Rydberg, H.; Schröder, E.
- Physical Review Letters, Vol. 92, Issue 24
Assessment of correlation energies based on the random-phase approximation
journal, April 2012
- Paier, Joachim; Ren, Xinguo; Rinke, Patrick
- New Journal of Physics, Vol. 14, Issue 4
Semiempirical GGA-type density functional constructed with a long-range dispersion correction
journal, January 2006
- Grimme, Stefan
- Journal of Computational Chemistry, Vol. 27, Issue 15, p. 1787-1799
Density functional theory with London dispersion corrections: Density functional theory with London dispersion corrections
journal, March 2011
- Grimme, Stefan
- Wiley Interdisciplinary Reviews: Computational Molecular Science, Vol. 1, Issue 2
Exchange and correlation in silicon
journal, April 1998
- Hood, Randolph Q.; Chou, M. Y.; Williamson, A. J.
- Physical Review B, Vol. 57, Issue 15
Static Response and Local Field Factor of the Electron Gas
journal, July 1995
- Moroni, Saverio; Ceperley, David M.; Senatore, Gaetano
- Physical Review Letters, Vol. 75, Issue 4
Spectral representation analysis of dielectric screening in solids and molecules
journal, April 2013
- Kaur, Amandeep; Ylvisaker, Erik R.; Lu, Deyu
- Physical Review B, Vol. 87, Issue 15
Many-Body Dispersion Interactions in Molecular Crystal Polymorphism
journal, May 2013
- Marom, Noa; DiStasio, Robert A.; Atalla, Viktor
- Angewandte Chemie International Edition, Vol. 52, Issue 26
Fluctuations of the Inverse Participation Ratio at the Anderson Transition
journal, April 2000
- Evers, F.; Mirlin, A. D.
- Physical Review Letters, Vol. 84, Issue 16
Density-functional correction of random-phase-approximation correlation with results for jellium surface energies
journal, April 1999
- Kurth, Stefan; Perdew, John P.
- Physical Review B, Vol. 59, Issue 16
Perspective on density functional theory
journal, April 2012
- Burke, Kieron
- The Journal of Chemical Physics, Vol. 136, Issue 15
Long-range-corrected hybrids including random phase approximation correlation
journal, February 2009
- Janesko, Benjamin G.; Henderson, Thomas M.; Scuseria, Gustavo E.
- The Journal of Chemical Physics, Vol. 130, Issue 8
Nonlocal van der Waals Density Functional Made Simple
journal, August 2009
- Vydrov, Oleg A.; Van Voorhis, Troy
- Physical Review Letters, Vol. 103, Issue 6
Range-separated density-functional theory with the random-phase approximation: Detailed formalism and illustrative applications
journal, September 2010
- Toulouse, Julien; Zhu, Wuming; Ángyán, János G.
- Physical Review A, Vol. 82, Issue 3
Optical spectra of solids obtained by time-dependent density functional theory with the jellium-with-gap-model exchange-correlation kernel
journal, May 2013
- Trevisanutto, Paolo E.; Terentjevs, Aleksandrs; Constantin, Lucian A.
- Physical Review B, Vol. 87, Issue 20
Maximally localized Wannier functions for entangled energy bands
journal, December 2001
- Souza, Ivo; Marzari, Nicola; Vanderbilt, David
- Physical Review B, Vol. 65, Issue 3
Electron correlation methods based on the random phase approximation
journal, January 2012
- Eshuis, Henk; Bates, Jefferson E.; Furche, Filipp
- Theoretical Chemistry Accounts, Vol. 131, Issue 1
Effects beyond the random-phase approximation in calculating the interaction between metal films
journal, November 2004
- Jung, J.; García-González, P.; Dobson, J. F.
- Physical Review B, Vol. 70, Issue 20
Inverse participation ratio in 2+? dimensions
journal, September 1980
- Wegner, F.
- Zeitschrift f�r Physik B Condensed Matter and Quanta, Vol. 36, Issue 3
Analytical expressions for the local-field factor and the exchange-correlation kernel of the homogeneous electron gas
journal, June 1998
- Corradini, Massimiliano; Del Sole, Rodolfo; Onida, Giovanni
- Physical Review B, Vol. 57, Issue 23