(475g) Divergence Of Tolman's Length, A Curvature Correction To Surface Tension

For decades the behavior of Tolman's length has remained one of the most controversial issues in mesoscopic thermodynamics. The Tolman length is defined as a curvature-correction coefficient in the surface tension of a liquid or vapor droplet. Application of "complete scaling" [Kim et al., Phys. Rev. E 67, 061506 (2003); Anisimov and Wang, Phys. Rev. Lett. 97, 25703 (2006)] to the interfacial behavior of fluids shows that Tolman's length, a curvature correction to the surface tension, diverges at the critical point of fluid phase separation much more strongly than is commonly believed. The amplitude of the divergence depends on the degree of asymmetry in fluid phase coexistence. In highly asymmetric fluids and fluid mixtures the Tolman length may become large enough to significantly affect the interfacial behavior of curved surfaces. In polymer solutions, the divergence of Tolman's length is even more dramatic. The amplitude of this divergence is proportional to the radius of gyration which scales as square root of the degree of polymerization.