On Polymer Statistical Mechanics: From Gaussian Distribution to Maxwell-Boltzmann Distribution to Fermi-Dirac Distribution

Macroscopic mechanical properties of polymers are determined by their microscopic molecular chain distribution. Due to randomness of these molecular chains, probability theory has been used to find their micro-states and energy distribution. In this paper, aided by central limit theorem and mixed Bayes rule, we showed that entropy elasticity based on Gaussian distribution is questionable. By releasing freely jointed chain assumption, we found that there is energy redistribution when each bond of a molecular chain changes its length. Therefore, we have to change Gaussian distribution used in polymer elasticity to Maxwell-Boltzmann distribution. Since Maxwell-Boltzmann distribution is only a good energy description for gas molecules, we found a mathematical path to change Maxwell-Boltzmann distribution to Fermi-Dirac distribution based on molecular chain structures. Because a molecular chain can be viewed as many monomers glued by covalent electrons, Fermi-Dirac distribution describes the probability of covalent electron occupancy in micro-states for solids such as polymers. Mathematical form of Fermi-Dirac distribution is logistic function. Mathematical simplicity and beauty of Fermi-Dirac distribution make many hard mechanics problems easy to understand. Generalized logistic function or Fermi-Dirac distribution function was able to understand many polymer mechanics problems such as viscoelasticity [1], viscoplasticity [2], shear band and necking [3], and ultrasonic bonding [4].