Formation free energy of an i-mer at spinodal Academic Article uri icon

abstract

  • In statistical mechanics, the formation free energy of an i-mer can be understood as the Gibbs free energy change in a system consisting of pure monomers after and prior to the formation of the i-mer. For molecules interacting via Lennard-Jones potential, we have computed the formation free energy of a Stillinger i-mer [F. H. Stillinger, J. Chem. Phys. 38, 1486 (1963)] and a ten Wolde-Frenkel (tWF) [P. R. ten Wolde and D. Frenkel, J. Chem. Phys. 109, 9901 (1998)] i-mer at spinodal at reduced temperatures from 0.7 to 1.2. It turns out that the size of a critical Stillinger i-mer remains finite and its formation free energy is on the order of kBT, and the size of a critical tWF i-mer remains finite and its formation free energy is even higher. This can be explained by Binder's theory [K. Binder, Phys. Rev. A 29, 341 (1984)] that for a system, when approaching spinodal, if the Ginzburg criterion is not satisfied, a gradual transition will take place from nucleation to spinodal decomposition, where the free-energy barrier height is on the order of kBT.

published proceedings

  • The Journal of Chemical Physics

author list (cited authors)

  • Nie, C., Geng, J., & Marlow, W. H.

citation count

  • 0

complete list of authors

  • Nie, Chu||Geng, Jun||Marlow, William H

publication date

  • June 2021