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

1974 ◽  
Vol 27 (2) ◽  
pp. 241 ◽  
Author(s):  
CHJ Johnson ◽  
TH Spurling
Keyword(s):  
Perturbation Theory ◽  
Long Range ◽  
Fourth Order ◽  
Virial Coefficient ◽  
Intermolecular Forces ◽  
The Third ◽  
Lennard Jones ◽  
Dipole Term ◽  
Third Virial Coefficient ◽  
Reduced Temperature

In this paper we give the results of computing the effect of non-additivity of long range forces on the fourth virial coefficient of a Lennard-Jones 12-6 gas. We have considered only dipolar effects but have included all terms up to the fourth order of perturbation theory. We have also calculated the effect of the fourth-order triple-dipole term on the third virial coefficient. For the fourth virial coefficient we find that the dispersion non-additivity, while being positive at low reduced temperatures, goes through a negative minimum at a reduced temperature of about 1.25 before becoming small and positive at high temperatures. This is in contradistinction to the behaviour of the third virial co-efficient where the dispersion non-additivity is always positive.

Multipolar third-order non-pairwise additivity of intermolecular forces: Effects on crystal properties and third virial coefficients

1971 ◽  
Vol 24 (11) ◽  
pp. 2205 ◽  
Author(s):  
CHJ Johnson ◽  
TH Spurling
Keyword(s):  
Cohesive Energy ◽  
Virial Coefficient ◽  
Virial Coefficients ◽  
Intermolecular Forces ◽  
Higher Order ◽  
The Third ◽  
Dipole Term ◽  
Third Virial Coefficient ◽  
Three Body ◽  
Body Potential

In this paper we give the results of computing the third virial coefficient and the cohesive energy of the crystal for argon taking into account the higher-order multipole terms in the long-range three- body interaction as recently calculated by Bell. The Barker-Pompe potential has been used as the two-body potential function. We find that the third virial coefficient values for argon computed with this more complete non-additive energy function agree very much better with the experimental values than when only the triple-dipole term is used. This is particularly true at lower temperatures. The results also show that better agreement would be obtained if some form of repulsive non- addivity were included in the computation. For the cohesive energy of the crystal we find that the dipole-dipole-quadrupole energy is one-third as large as the triple-dipole energy and so cannot be neglected in these lattice computations. Furthermore, we find that these higher- order three-body forces do not stabilize the face-centred-cubic lattice for argon, the hexagonal-close-packed lattice having a slightly lower energy.

scholarly journals Nonadditivity of Intermolecular Forces: Effects on the Third Virial Coefficient

1966 ◽  
Vol 44 (8) ◽  
pp. 2984-2994 ◽  
Author(s):  
A. E. Sherwood ◽  
Andrew G. De Rocco ◽  
E. A. Mason
Keyword(s):  
Virial Coefficient ◽  
Intermolecular Forces ◽  
The Third ◽  
Third Virial Coefficient

scholarly journals The Third Virial Coefficient of a Lennard‐Jones Gas by Kihara's Method with Tables for the 6—9 Potential

1954 ◽  
Vol 22 (3) ◽  
pp. 464-468 ◽  
Author(s):  
Leo F. Epstein ◽  
Celesta J. Hibbert ◽  
Marion D. Powers ◽  
Glenn M. Roe
Keyword(s):  
Virial Coefficient ◽  
The Third ◽  
Lennard Jones ◽  
Third Virial Coefficient

The third virial coefficient of hard discs of different sizes

1987 ◽  
Vol 61 (2) ◽  
pp. 525-528 ◽  
Author(s):  
John S. Rowlinson ◽  
Donald A. McQuarrie
Keyword(s):  
Virial Coefficient ◽  
The Third ◽  
Third Virial Coefficient

Intermolecular forces and properties of fluid. I. The automatic calculation of higher virial coefficients and some values of the fourth coefficient for the Lennard-Jones potential

1960 ◽  
Vol 254 (1279) ◽  
pp. 487-498 ◽  
Keyword(s):  
Virial Coefficient ◽  
Mathematical Problem ◽  
Virial Coefficients ◽  
Intermolecular Forces ◽  
Lennard Jones Potential ◽  
Intermolecular Potentials ◽  
Jones Potential ◽  
Lennard Jones ◽  
Experimental Values ◽  
First Time

The prediction of the virial coefficients for particular intermolecular potentials is generally regarded as a difficult mathematical problem. Methods have only been available for the second and third coefficient and in fact only few calculations have been made for the latter. Here a new method of successive approximation is introduced which has enabled the fourth virial coefficient to be evaluated for the first time for the Lennard-Jones potential. It is particularly suitable for automatic computation and the values reported here have been obtained by the use of the EDSAC I. The method is applicable to other potentials and some values for these will be reported subsequently. The values obtained cannot yet be compared with any experimental results since these have not been measured, but they can be used in the meantime to obtain more accurate experimental values of the lower coefficients.

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