Finite-size effects in surface tension: Thermodynamics and the Gaussian interface model

It has been suggested by Kayser that finite-size effects associated with capillary waves might play a significant role in some surface tension measurements; for capillary rise between plates a distance D apart, an effect varying as 1/D and apparently observable in measurements, was proposed. In reconsidering this problem, one must analyze the thermodynamics of finite-size corrections to surface tension. In particular, one sees that capillary rise between plates does not measure the interfacial free energy density but, rather, a derivative of the interfacial free energy with respect to a system dimension. The quantity needed to draw definite conclusions, the finite-size residual free energy, can be calculated within the harmonic or Gaussian capillary wave model in d spatial dimensions with the aid of Poisson summation techniques and should yield the correct leading asymptotic behavior. For d=3 and experimentally relevant parameter values, the results are independent of the short-wavelength cutoff needed in the model and can be checked against the theory of conformai covariance at two-dimensional critical points. It is found that the finite-size effects in capillary-rise measurements of surface tension vary as 1/D² (with a universal coefficient) but are too small to be seen in current experiments.Invited paper presented at the Tenth Symposium on Thermophysical Properties, June 20–23, 1988, Gaithersburg, Maryland, U.S.A.