It is argued that to arrive at a quantitative description of the surface
tension of a liquid drop as a function of its inverse radius, it is necessary
to include the bending rigidity k and Gaussian rigidity k_bar in its
description. New formulas for k and k_bar in the context of density functional
theory with a non-local, integral expression for the interaction between
molecules are presented. These expressions are used to investigate the
influence of the choice of Gibbs dividing surface and it is shown that for a
one-component system, the equimolar surface has a special status in the sense
that both k and k_bar are then the least sensitive to a change in the location
of the dividing surface. Furthermore, the equimolar value for k corresponds to
its maximum value and the equimolar value for k_bar corresponds to its minimum
value. An explicit evaluation using a short-ranged interaction potential
between molecules, shows that k is negative with a value around minus 0.5-1.0
kT and that k_bar is positive with a value which is a bit more than half the
magnitude of k. Finally, for dispersion forces between molecules, we show that
a term proportional to log(R)/R^2 replaces the rigidity constants and we
determine the (universal) proportionality constants.Comment: 28 pages; 5 figures; accepted for publication in J. Phys.: Condens.
Matter (2013
