Intermolecular pair potential

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The intermolecular pair potential is a widely used approximation. Real intermolecular interactions consist of two-body interactions, three-body interactions, four-body interactions etc. However, the calculation of even three-body interactions is computationally time consuming, and the calculation of only two-body interactions is frequent. Such "effective" pair potentials often include the higher order interactions implicitly. Naturally the interaction potential between atoms or molecules remains unchanged regardless of where one is in the phase diagram, be it the low temperature solid, or a high temperature gas. However, when one only uses two-body interactions such 'transferability' is lost, and one may well need to modify the the potential or the parameters of the potential if one is studying a hot gas or a cooler high density liquid.

Axially symmetric molecules[edit]

In general, the intermolecular pair potential for axially symmetric molecules, \Phi_{12} , is a function of five coordinates:

\left. \Phi_{12} \right. = \Phi_{12}(r, \theta_1, \phi_1, \theta_2, \phi_2)

The angles \theta_i and \phi_i can be considered to be polar angles, with the intermolecular vector, r, as the common polar axis. Since the molecules are axially symmetric, the angles \psi_i do not influence the value of \Phi_{12} . A very powerful expansion of this pair potential is due to Pople (Ref. 1 Eq. 2.1):

\left. \Phi_{12} \right. = 4\pi \sum_{L_1 L_2 m} L_1 L_2 m (r) Y_{L_1}^m (\theta_1, \phi_1) Y_{L_2}^m * (\theta_2, \phi_2),

where Y_L^m(\theta, \phi) are the spherical harmonics.

See also[edit]


  1. J. A. Pople "The Statistical Mechanics of Assemblies of Axially Symmetric Molecules. I. General Theory", Proceedings of the Royal Society of London. Series A, Mathematical and Physical Sciences 221 pp. 498-507 (1954)