Non-additivity of intermolecular forces: effects on the fourth virial coefficient

Johnson, Chj; Spurling, Thomas H.

doi:10.1071/ch9740241

Cited by 24 publications

(30 citation statements)

References 0 publications

Supporting

Mentioning

Contrasting

Unclassified

Order By: Relevance

“…[34] Forn eon it was shown that already the classical triple-dipole (Axilrod-Teller) term is agood approximation in the long range.H ence we chose the four-body contribution derived from the classical Drude model [35,36,51,52] whereũ ij is the unit vector in direction from atom i to atom j.T he prefactor w was chosen according to Johnsson and Spurling (corrected for am issing factor of 8), [51] that is, w = À(45/32)ca 4 with as caling factor [53] c = 0.6963 and the dipole polarizability a = 11.07 a.u. and R ij being the internuclear distance of the dimer with atoms i, j.F or the three-body potential we took the potential of Cencek et al evaluated at the CCSDT(Q) level of theory including scalar relativistic effects.…”

Section: Computational Detailsmentioning

confidence: 99%

“…and R ij being the internuclear distance of the dimer with atoms i, j.F or the three-body potential we took the potential of Cencek et al evaluated at the CCSDT(Q) level of theory including scalar relativistic effects. [34] Forn eon it was shown that already the classical triple-dipole (Axilrod-Teller) term is agood approximation in the long range.H ence we chose the four-body contribution derived from the classical Drude model [35,36,51,52] whereũ ij is the unit vector in direction from atom i to atom j.T he prefactor w was chosen according to Johnsson and Spurling (corrected for am issing factor of 8), [51] that is, w = À(45/32)ca 4 with as caling factor [53] c = 0.6963 and the dipole polarizability a = 11.07 a.u. taken from experimental measurements.…”

Section: Computational Detailsmentioning

confidence: 99%

See 1 more Smart Citation

Towards J/mol Accuracy for the Cohesive Energy of Solid Argon

et al. 2016

View full text Add to dashboard Cite

The cohesive energies of argon in its cubic and hexagonal closed packed structures are computed with an unprecedented accuracy of about 5 J mol(-1) (corresponding to 0.05 % of the total cohesive energy). The same relative accuracy with respect to experimental data is also found for the face-centered cubic lattice constant deviating by ca. 0.003 Å. This level of accuracy was enabled by using high-level theoretical, wave-function-based methods within a many-body decomposition of the interaction energy. Static contributions of two-, three-, and four-body fragments of the crystal are all individually converged to sub-J mol(-1) accuracy and complemented by harmonic and anharmonic vibrational corrections. Computational chemistry is thus achieving or even surpassing experimental accuracy for the solid-state rare gases.

show abstract

Section: Computational Detailsmentioning

confidence: 99%

Section: Computational Detailsmentioning

confidence: 99%

Towards J/mol Accuracy for the Cohesive Energy of Solid Argon

et al. 2016

View full text Add to dashboard Cite

show abstract

“…32 However, expressions for nonadditive corrections have been reported only for the third through fifth virial coefficients. 33,34 Recently, Hellmann and Bich 35 presented a new derivation of the virial expansion, which is not restricted to pairwise-additive potentials. Furthermore, they provided explicit formulae for the numerical evaluation of the virial coefficients up to B 8 in terms of sums of newly defined cluster diagrams.…”

Section: Introductionmentioning

confidence: 99%

Ab initio virial equation of state for argon using a new nonadditive three-body potential

Jäger

Hellmann²,

Bich³

et al. 2011

The Journal of Chemical Physics

102

124

View full text Add to dashboard Cite

An ab initio nonadditive three-body potential for argon has been developed using quantum-chemical calculations at the CCSD(T) and CCSDT levels of theory. Applying this potential together with a recent ab initio pair potential from the literature, the third and fourth to seventh pressure virial coefficients of argon were computed by standard numerical integration and the Mayer-sampling Monte Carlo method, respectively, for a wide temperature range. All calculated virial coefficients were fitted separately as polynomials in temperature. The results for the third virial coefficient agree with values evaluated directly from experimental data and with those computed for other nonadditive three-body potentials. We also redetermined the second and third virial coefficients from the best experimental pρT data utilizing the computed higher virial coefficients as constraints. Thus, a significantly closer agreement of the calculated third virial coefficients with the experimental data was achieved. For different orders of the virial expansion, pρT data have been calculated and compared with results from high quality measurements in the gaseous and supercritical region. The theoretically predicted pressures are within the very small experimental errors of ±0.02% for p ≤ 12 MPa in the supercritical region near room temperature, whereas for subcritical temperatures the deviations increase up to +0.3%. The computed pressure at the critical density and temperature is about 1.3% below the experimental value. At pressures between 200 MPa and 1000 MPa and at 373 K, the calculated values deviate by 1% to 9% from the experimental results.

show abstract

“…8 The third virial coefficient, B 3 , is represented as the sum of additive and nonadditive parts, as in…”

Section: Formulas and Methodsmentioning

confidence: 99%

Fourth and Fifth Virial Coefficients of Polarizable Water

2009

View full text Add to dashboard Cite

We report values of the viral coefficients B4 and B5 for the Gaussian charge polarizable model (GCPM) of water using the overlap-sampling implementation of Mayer sampling molecular simulation. These results supplement values for the lower-order coefficients B2 and B3 reported previously, and in the present work, we provide more precise values of these coefficients as well. The precision of all viral coefficients is such that the standard error in the calculated pressure is significantly less than 1% for most temperatures, with the exception of temperatures near the critical, where the error approaches 100% at the critical density, and supercritical, where the uncertainty in B5 introduces an error of about 5% in the pressure at the critical density. We examine these coefficients in the context of the equation of state and molecular clustering. Comparisons are made to established molecular simulation data, quantum chemical calculations, and experimental data for real water. Over both sub- and supercritical temperatures, the viral series to B5 is accurate for densities only up to about half the critical density. In this regime, deviation is observed from experimental data for real water, and it is suggested that further development of the model might do well to further improve the relatively good agreement it has with the experimental second viral coefficient of water. The viral coefficients are used to characterize molecular clusters (dimers through pentamers) in GCPM water under supercritical and saturated vapor conditions between 210 and 673 K.

show abstract

Non-additivity of intermolecular forces: effects on the fourth virial coefficient

Cited by 24 publications

References 0 publications

Towards J/mol Accuracy for the Cohesive Energy of Solid Argon

Towards J/mol Accuracy for the Cohesive Energy of Solid Argon

Ab initio virial equation of state for argon using a new nonadditive three-body potential

Fourth and Fifth Virial Coefficients of Polarizable Water

Contact Info

Product

Resources

About