Emergence of quasiequilibrium state and energy distribution for the beads-spring molecule interacting with a solvent.

Abstract

We study the energy distribution during the emergence of a quasiequilibrium (QE) state in the course of relaxation to equipartition in slow-fast Hamiltonian systems. A bead-spring model where beads (masses) are connected by springs is considered. The QE lasts for a long time because the energy exchange between the high-frequency vibrational and other motions is prevented when springs in the molecule become stiff. We numerically calculated the time-averaged kinetic energy and found that the kinetic energy of the solvent particles was always higher than that of the bead in a molecule. This is explained by adopting the equipartition theorem in QE, and it agrees well with the numerical results. The energy difference can help determine how far the system is from achieving equilibrium, and it can be used as an indicator of the number of frozen or inactive degrees existing in the molecule.