Model hysteresis dimer molecule II: deductions from probability profile due to system coordinates |
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Authors: | Christopher G Jesudason |
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Institution: | (1) Chemistry Department, University of Malaya, 50603 Kuala Lumpur, Peninsula Malaysia |
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Abstract: | The hysteresis dimer reaction of the first sequel is applied to test the Gibbs density-in-phase hypothesis for a canonical
distribution at equilibrium. The probability distribution of variously defined internal and external variables is probed using
the algorithms described, in particular the novel probing of the energy states of a labeled particle where it is found that
there is compliance with the Gibbs’ hypothesis for the stated equilibrium condition and where the probability data strongly
suggests that an extended equipartition principle may be formulated for some specific molecular coordinates, whose equipartition
temperature does not equal the mean system temperature and a conjecture concerning which coordinates may be suitable is provided.
Evidence of violations to the mesoscopic nonequilibrium thermodynamics (MNET) assumptions used without clear qualifications
for a canonical distribution for internal variables are described, and possible reasons outlined, where it is found that the
free dimer and atom particle kinetic energy distributions agree fully with Maxwell–Boltzmann statistics but the distribution
for the relative kinetic energy of bonded atoms does not. The principle of local equilibrium (PLE) commonly used in nonequilibrium
theories to model irreversible systems is investigated through NEMD simulation at extreme conditions of bond formation and
breakup at the reservoir ends in the presence of a temperature gradient, where for this study a simple and novel difference
equation algorithm to test the divergence theorem for mass conservation is utilized, where mass is found to be conserved from
the algorithm in the presence of flux currents, in contradiction to at least one aspect of PLE in the linear domain. It is
concluded therefore that this principle can be a good approximation at best, corroborating previous purely theoretical results
derived from the generalized Clausius Inequality, which proved that the PLE cannot be an exact principle for nonequilibrium
systems.
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Keywords: | kinetic energy probability profile Gibbs ensemble hypotheses extended equipartition principle NEMD principle of local equilibrium Clausius inequality |
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