Physical clusters in an imperfect vapor

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Abstract
We examine the general problem of calculating the equation of state in terms of physical clusters, and direct attention to the two main components of the problem: (i) formulating a satisfactory definition of the physical cluster concept; (ii) developing a method to account for interference between clusters and to assess the importance of interference. For (i) we use Stillinger’s definition, which is based on the distance between molecular centers. To account for interference, we treat the clusters in a one‐dimensional vapor as a mixture of hard rods, each of which assumes its most probable length. We find that neglect of interference induces errors in the second virial coefficient down to a very low temperature, which depends on the strength of the pair attraction. Thus, we conclude that interference between clusters can never be neglected in a calculation of the equation of state when ordinary dispersion forces operate between molecules.

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