Effect of three-body interactions on third virial coefficients of rare gases

Pospíšil, Roman; Malijevský, Alexandr; Labı́k, Stanislav

doi:10.1080/00268978800100023

Cited by 16 publications

(6 citation statements)

References 45 publications

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“…Even though some features of the ATM model deviate fundamentally from the true ab initio nonadditive three-body potential, especially for triplet configurations with small interatomic distances, a large amount of error cancellation within the ATM model can be assumed to be the reason for this agreement. However, Pospisil et al 56 reported rather large contributions to the third virial coe cients of krypton arising from dispersion terms beyond the triple-dipole approximation. Therefore, we chose to use not only the pure ATM model but also the so-called extended ATM (EATM) nonadditive potential for the computation of the third virial coe cient and the discussion of the corresponding uncertainty.…”

Section: G Nonadditive Three-body Interactionsmentioning

confidence: 99%

“…65 Explicit expressions for the contributions to the third virial coe cient can be found elsewhere. 56,64,65 All integrals for the computation of the second and third virial coe cients were solved by means of standard numerical integration methods. The results for B 2 (T) and B 3 (T) are converged to within ±0.001 cm 3 mol 1 and ±0.1 cm 6 mol 2 , respectively.…”

Section: Virial Coefficientsmentioning

confidence: 99%

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State-of-the-art ab initio potential energy curve for the krypton atom pair and thermophysical properties of dilute krypton gas

Jäger

Hellmann

Bich

et al. 2016

The Journal of Chemical Physics

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A new reference krypton-krypton interatomic potential energy curve was developed by means of quantum-chemical ab initio calculations for 36 interatomic separations. Highly accurate values for the interaction energies at the complete basis set limit were obtained using the coupled-cluster method with single, double, and perturbative triple excitations as well as t-aug-cc-pV5Z and t-aug-cc-pV6Z basis sets including mid-bond functions, with the 6Z basis set being newly constructed for this study. Higher orders of coupled-cluster terms were considered in a successive scheme up to full quadruple excitations. Core-core and core-valence correlation effects were included. Furthermore, relativistic effects were studied not only at a scalar relativistic level using second-order direct perturbation theory, but also utilizing full four-component and Gaunt-effect computations. An analytical pair potential function was fitted to the interaction energies, which is characterized by a depth of 200.88 K with an estimated standard uncertainty of 0.51 K. Thermophysical properties of low-density krypton were calculated for temperatures up to 5000 K. Second and third virial coefficients were obtained from statistical thermodynamics. Viscosity and thermal conductivity as well as the self-diffusion coefficient were computed using the kinetic theory of gases. The theoretical results are compared with experimental data and with results for other pair potential functions from the literature, especially with those calculated from the recently developed ab initio potential of Waldrop et al. [J. Chem. Phys. 142, 204307 (2015)]. Highly accurate experimental viscosity data indicate that both the present ab initio pair potential and the one of Waldrop et al. can be regarded as reference potentials, even though the quantum-chemical methods and basis sets differ. However, the uncertainties of the present potential and of the derived properties are estimated to be considerably lower.

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Section: G Nonadditive Three-body Interactionsmentioning

confidence: 99%

Section: Virial Coefficientsmentioning

confidence: 99%

State-of-the-art ab initio potential energy curve for the krypton atom pair and thermophysical properties of dilute krypton gas

Jäger

Hellmann

Bich

et al. 2016

The Journal of Chemical Physics

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“…B 3 /s 6 for the third virial coefficient, L ! L/s for the bond length and 5 ) for the squared quadrupole.…”

Section: Resultsmentioning

confidence: 99%

“…Indeed, for a long time the measurement of second virial coefficients provided one of the few sources that allowed to test two body forces. 1 Although in principle a study of third virial coefficients could provide a means for the understanding of three body forces, 4,5 such studies have been considerably limited, for several reasons. Firstly, the experimental measurement of third virial coefficients has proved to be extremely difficult, due to instrumental and technical difficulties.…”

Section: Introductionmentioning

confidence: 99%

Third virial coefficients and critical properties of quadrupolar two center Lennard-Jones models

MacDowell

Menduiña

Vega

et al. 2003

Phys. Chem. Chem. Phys.

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We report numerical results for the third virial coefficient of two center Lennard-Jones quadrupolar molecules. Calculations are performed for 35 models with different elongations and quadrupoles over a temperature range from half to twice the critical temperature. It is found that increasing the elongation at fixed quadrupole has the effect of increasing B 3 . On the other hand, at fixed elongation B 3 first decreases with increasing quadrupole at low temperatures, then increases with increasing quadrupole at higher temperatures. We estimate the temperature at which the third virial coefficient vanishes. Although both this temperature and the critical temperature increase with the quadrupole moment, their ratio remains almost constant. We predict the critical properties using two different truncated virial series. The first one employs the exact second and third virial coefficients. The second one approximates the fourth order contribution by using estimates obtained for hard diatomics. It is found that both methods yield fairly good predictions, with a somewhat better performance of the approximate fourth order expansion. The two methods are complementary, however, because they consistently bracket the exact value as determined from computer simulations.

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“…The nonadditive interaction part of the many body potential can play an important role in determining the various properties of the matter including third virial coefficients of fluids, absorption spectra of fluids, and binding energies of solids. − In this paper, by incorporating the well-known basis set convergence behavior of the monomer correlation energies of He and Ne at the MP2, CCSD, and CCSD(T) level into the aforementioned extrapolation scheme, we compute the binding energies and nonadditive three body potentials of rare gas trimers He 3 and Ne 3 as well as the closer investigation of the binding energies of the dimers He 2 and Ne 2 . We also examine the performance of the two-point 1/X 3 extrapolation schemes in estimating the binding energies and nonadditive three body potentials of these clusters and investigate the most appropriate extrapolation method for these kinds of complexes.…”

Section: Introductionmentioning

confidence: 99%

Binding Energies and Three Body Potentials of He₃ and Ne₃: A Hierarchical Approach toward the Basis Set and Correlation Limit

Huh

Lee

2002

J. Phys. Chem. A

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The basis set limit electronic binding energies of small rare gas clusters X n (X ) He and Ne; n ) 2 and 3) and nonadditive three body potential at the MP2, CCSD, and CCSD(T) levels (coupled cluster single and double excitations with perturbative triples correction) were obtained assuming the correlation energies of the monomer and cluster have the same convergence behavior toward the corresponding basis set limits with correlation consistent aug-cc-pVXZ (X ) D(2), T(3), Q(4), 5, 6) basis set. The comparison of the estimated basis set limits with the estimates obtained from 1/X 3 extrapolation schemes and the exact (reference) basis set limits shows that the new extrapolation scheme is capable of yielding a much more accurate estimate to the basis set limit than two-point 1/X 3 extrapoation scheme with small basis sets, though estimated basis set limits by both extrapolation schemes appear to converge as the basis set increases. The three body potentials of He 3 and Ne 3 are found negligible at their equilateral configurations near equilibrium. An effective procedure is explored to derive the basis set limit binding energies at the CCSD(T) level from the results at the MP2 level in a hierarchical manner based on the appropriate extrapolation of correlation consistent energies.

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Effect of three-body interactions on third virial coefficients of rare gases

Cited by 16 publications

References 45 publications

State-of-the-art ab initio potential energy curve for the krypton atom pair and thermophysical properties of dilute krypton gas

State-of-the-art ab initio potential energy curve for the krypton atom pair and thermophysical properties of dilute krypton gas

Third virial coefficients and critical properties of quadrupolar two center Lennard-Jones models

Binding Energies and Three Body Potentials of He₃ and Ne₃: A Hierarchical Approach toward the Basis Set and Correlation Limit

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Effect of three-body interactions on third virial coefficients of rare gases

Cited by 16 publications

References 45 publications

State-of-the-art ab initio potential energy curve for the krypton atom pair and thermophysical properties of dilute krypton gas

State-of-the-art ab initio potential energy curve for the krypton atom pair and thermophysical properties of dilute krypton gas

Third virial coefficients and critical properties of quadrupolar two center Lennard-Jones models

Binding Energies and Three Body Potentials of He3 and Ne3: A Hierarchical Approach toward the Basis Set and Correlation Limit

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Binding Energies and Three Body Potentials of He₃ and Ne₃: A Hierarchical Approach toward the Basis Set and Correlation Limit