A highly accurate interatomic potential for argon

Aziz, Ronald A.

doi:10.1063/1.466051

Cited by 364 publications

(252 citation statements)

References 38 publications

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“…As an illustration, consider noble gas atom dimers, for which interaction potentials of spectroscopic accuracy can be constructed solely from highly accurate vdW coefficients in conjunction with mean-field HF calculations. 73,74 One can then simply calculate that an error of 20% in the asymptotic vdW coefficients of the xenon atom results in an error of approximately 40% in the equilibrium binding energy ( Figure 3). Already this simple example highlights the importance of accuracy in the parameters used for including vdW interactions in electronic structure calculations.…”

Section: Conceptual Understanding Of Vdw Interactions In Molecules Anmentioning

confidence: 99%

First-Principles Models for van der Waals Interactions in Molecules and Materials: Concepts, Theory, and Applications

2017

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Noncovalent van der Waals (vdW) or dispersion forces are ubiquitous in nature and influence the structure, stability, dynamics, and function of molecules and materials throughout chemistry, biology, physics, and materials science. These forces are quantum mechanical in origin and arise from electrostatic interactions between fluctuations in the electronic charge density. Here, we explore the conceptual and mathematical ingredients required for an exact treatment of vdW interactions, and present a systematic and unified framework for classifying the current first-principles vdW methods based on the adiabatic-connection fluctuation−dissipation (ACFD) theorem (namely the Rutgers−Chalmers vdW-DF, Vydrov−Van Voorhis (VV), exchange-hole dipole moment (XDM), Tkatchenko−Scheffler (TS), many-body dispersion (MBD), and random-phase approximation (RPA) approaches). Particular attention is paid to the intriguing nature of many-body vdW interactions, whose fundamental relevance has recently been highlighted in several landmark experiments. The performance of these models in predicting binding energetics as well as structural, electronic, and thermodynamic properties is connected with the theoretical concepts and provides a numerical summary of the state-of-the-art in the field. We conclude with a roadmap of the conceptual, methodological, practical, and numerical challenges that remain in obtaining a universally applicable and truly predictive vdW method for realistic molecular systems and materials.

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Section: Conceptual Understanding Of Vdw Interactions In Molecules Anmentioning

confidence: 99%

First-Principles Models for van der Waals Interactions in Molecules and Materials: Concepts, Theory, and Applications

2017

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“…[4]) potentials represent a second class of potentials [4] accurate over a wider range of distances. Quantum chemists [5,6,7,8,9] have derived a third class that reproduce spectroscopic and thermodynamic data with impressive fidelity. But the potentials of this class involve many parameters and may be too cumbersome for use in large-scale simulations.…”

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confidence: 99%

Rydberg–London potential for diatomic molecules and unbonded atom pairs

Cahill

Parsegian

2004

The Journal of Chemical Physics

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We propose and test a pair potential that is accurate at all relevant distances and simple enough for use in large-scale computer simulations. A combination of the Rydberg potential from spectroscopy and the London inverse-sixth-power energy, the proposed form fits spectroscopically determined potentials better than the Morse, Varnshi, and Hulburt-Hirschfelder potentials and much better than the Lennard-Jones and harmonic potentials. At long distances, it goes smoothly to the correct London force appropriate for gases and preserves van der Waals's "continuity of the gas and liquid states," which is routinely violated by coefficients assigned to the Lennard-Jones 6-12 form.There are at least three classes of interatomic potentials. Commercial codes use the Lennard-Jonesand harmonicforms, which are accurate near the minimum at r = r 0 . But this first class of potentials may be too simple for complex materials away from from equilibrium.(β = (κr 2 0 − 1)/(2r 2 0 )), and Hulburt-Hirschfelder [3][4]) potentials represent a second class of potentials [4] accurate over a wider range of distances. Quantum chemists [5,6,7,8,9] have derived a third class that reproduce spectroscopic and thermodynamic data with impressive fidelity. But the potentials of this class involve many parameters and may be too cumbersome for use in large-scale simulations.We propose and test a formthat is nearly as accurate as the class-3 potentials but simpler than many class-2 potentials. It is a combination of the Rydberg formula used in spectroscopy and , and e = 47.6Å 12 ) (solid, red) fits the RKR spectral points for the ground state of molecular hydrogen (pluses, blue) and gives the correct London tail for r > 3Å. The Lennard-Jones VLJ (dashes, green) and harmonic VH (dots, magenta) forms fit only near the minimum.the London formula for pairs of atoms. In Eq.(6), the terms involving a, b, and c were proposed by Rydberg [10] to incorporate spectroscopic data, but were largely ignored until recently [11,12]. The constant d = C 6 is the coefficient of the London tail. The new term e r −6 cures the London singularity. As r → 0, V (r) → a, finite; as r → ∞, V (r) approaches the London term, V (r) → −d/r 6 = −C 6 /r 6 . In a perturbative analysis [13], the a, b, c terms arise in first order, and the d term in second order.To test whether the hybrid V (r) can represent covalent bonds far from equilibrium, we used Gnuplot [14] to fit Eq.(6) to empirical potentials for molecular H 2 , N 2 , and

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“…[9][10][11][12][13][14][15][16] The Ar 2 HF complex is ideally suited for the investigation of nonadditive forces in systems involving a molecular constituent. The Ar 2 and ArHF pair potentials are very accurately known, having been determined by accurate fitting to experimental data by Aziz 17 and Hutson, 18 respectively. Moreover there is a high-quality experimental data set available that is sensitive to the three-body part of the intermolecular potential.…”

Section: Introductionmentioning

confidence: 99%

Calculating energy levels of isomerizing tetra-atomic molecules. I. The rovibrational bound states of Ar2HF

Kozin

Law

Hutson

et al. 2003

The Journal of Chemical Physics

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A highly accurate interatomic potential for argon

Cited by 364 publications

References 38 publications

First-Principles Models for van der Waals Interactions in Molecules and Materials: Concepts, Theory, and Applications

First-Principles Models for van der Waals Interactions in Molecules and Materials: Concepts, Theory, and Applications

Rydberg–London potential for diatomic molecules and unbonded atom pairs

Calculating energy levels of isomerizing tetra-atomic molecules. I. The rovibrational bound states of Ar2HF

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