Popular Kohn-Sham density functionals strongly overestimate many-body interactions in van der Waals systems

Tkatchenko, Alexandre; Lilienfeld, O. Anatole von

doi:10.1103/physrevb.78.045116

Cited by 78 publications

(99 citation statements)

References 68 publications

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“…Threecenter dispersion interactions, in addition to two-center interactions, are being studied. 176,[181][182][183] Screening effects are being studied as well. 184 I think the jury is still out on the importance of three-center interactions and screening.…”

Section: Dispersion Interactions: the Floodgates Openmentioning

confidence: 99%

Perspective: Fifty years of density-functional theory in chemical physics

Becke

2014

The Journal of Chemical Physics

1,286

964

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Since its formal inception in 1964-1965, Kohn-Sham density-functional theory (KS-DFT) has become the most popular electronic structure method in computational physics and chemistry. Its popularity stems from its beautifully simple conceptual framework and computational elegance. The rise of KS-DFT in chemical physics began in earnest in the mid 1980s, when crucial developments in its exchange-correlation term gave the theory predictive power competitive with welldeveloped wave-function methods. Today KS-DFT finds itself under increasing pressure to deliver higher and higher accuracy and to adapt to ever more challenging problems. If we are not mindful, however, these pressures may submerge the theory in the wave-function sea. KS-DFT might be lost. I am hopeful the Kohn-Sham philosophical, theoretical, and computational framework can be preserved. This Perspective outlines the history, basic concepts, and present status of KS-DFT in chemical physics, and offers suggestions for its future development. © 2014 AIP Publishing LLC.

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Section: Dispersion Interactions: the Floodgates Openmentioning

confidence: 99%

Perspective: Fifty years of density-functional theory in chemical physics

Becke

2014

The Journal of Chemical Physics

1,286

964

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“…While there is no definitive value for the amount of exact exchange that should be added to a hybrid, there is some motivation for a value of 25%, 73 and the important aspect of PBE0 (and PBE) is that it is not fitted to any experimental or theoretical data and is therefore not artificially biased towards or against specific systems. PBE0 also has a small short-range many-body correlation error, 74 which allows it to cleanly couple with the MBD method.…”

Section: Role Of Exact Exchangementioning

confidence: 99%

“…For instance, it is known that PBE0 has smaller short-range errors for interactions in van der Waals systems compared to PBE. 74 Systems such as CO 2 and adamantane clearly require additional contributions, whether higher-order multipole terms or improved density functionals and they therefore are useful targets for method development. However, the excellent performance of PBE0+MBD for the remainder of the X23 database demonstrates that it is a powerful approach for predicting lattice energies and stabilities of organic molecular crystals.…”

Section: Higher-order Multipole Contributions To Van Der Waals Intmentioning

confidence: 99%

Understanding the role of vibrations, exact exchange, and many-body van der Waals interactions in the cohesive properties of molecular crystals

Reilly

Tkatchenko

2013

The Journal of Chemical Physics

Self Cite

293

498

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The development and application of computational methods for studying molecular crystals, particularly density-functional theory (DFT), is a large and ever-growing field, driven by their numerous applications. Here we expand on our recent study of the importance of many-body van der Waals interactions in molecular crystals [A. M. Reilly and A. Tkatchenko, J. Phys. Chem. Lett. 4, 1028 (2013)], with a larger database of 23 molecular crystals. Particular attention has been paid to the role of the vibrational contributions that are required to compare experiment sublimation enthalpies with calculated lattice energies, employing both phonon calculations and experimental heat-capacity data to provide harmonic and anharmonic estimates of the vibrational contributions. Exact exchange, which is rarely considered in DFT studies of molecular crystals, is shown to have a significant contribution to lattice energies, systematically improving agreement between theory and experiment. When the vibrational and exact-exchange contributions are coupled with a many-body approach to dispersion, DFT yields a mean absolute error (3.92 kJ/mol) within the coveted "chemical accuracy" target (4.2 kJ/mol). The role of many-body dispersion for structures has also been investigated for a subset of the database, showing good performance compared to X-ray and neutron diffraction crystal structures. The results show that the approach employed here can reach the demanding accuracy of crystal-structure prediction and organic material design with minimal empiricism. © 2013 AIP Publishing LLC. [http://dx

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“…Apart from PBE, the authors also considers the AM05 functional 81 to be a potential candidate for such an effort. We do not know yet if such an GGA+FCACP+DCACP approach can account for all the many-body interactions present, recently found to be relevant even for van der Waals interactions [82][83][84] . Another critical issue is to more rigorously address the somewhat arbitrary choice of reference systems (molecules and geometries) and methods (other than hybrid DFT).…”

Section: Discussionmentioning

confidence: 99%

Force correcting atom centred potentials for generalised gradient approximated density functional theory: Approaching hybrid functional accuracy for geometries and harmonic frequencies in small chlorofluorocarbons

Lilienfeld

2013

Molecular Physics

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Generalized gradient approximated (GGA) density functional theory (DFT) typically overestimates polarizability and bond-lengths, and underestimates force constants of covalent bonds. To overcome this problem we show that one can use empirical force correcting atom centered potentials (FCACPs), parameterized for every nuclear species. Parameters are obtained through minimization of a penalty functional that explicitly encodes hybrid DFT forces and static polarizabilities of reference molecules. For hydrogen, fluorine, chlorine, and carbon the respective reference molecules consist of H2, F2, Cl2, and CH4. The transferability of this approach is assessed for harmonic frequencies in a small set of chlorofluorocarbon molecules. Numerical evidence, gathered for CF4, CCl4, CCl3F, CCl2F2, CClF3, ClF, HF, HCl, CFH3, CF2H2, CF3H, CHCl3, CH2Cl2, CH3Cl indicates that the GGA+FCACP level of theory yields harmonic frequencies that are significantly more consistent with hybrid DFT values, as well as slightly reduced molecular polarizability.

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Popular Kohn-Sham density functionals strongly overestimate many-body interactions in van der Waals systems

Cited by 78 publications

References 68 publications

Perspective: Fifty years of density-functional theory in chemical physics

Perspective: Fifty years of density-functional theory in chemical physics

Understanding the role of vibrations, exact exchange, and many-body van der Waals interactions in the cohesive properties of molecular crystals

Force correcting atom centred potentials for generalised gradient approximated density functional theory: Approaching hybrid functional accuracy for geometries and harmonic frequencies in small chlorofluorocarbons

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