Predicting Ion Sequestration in Charged Polymers with the Steepest-Entropy-Ascent Quantum Thermodynamic Framework

Abstract: The steepest-entropy-ascent quantum thermodynamic framework is used to investigate the effectiveness of multi-chain polyethyleneimine-methylenephosphonic acid in sequestering rare-earth ions (Eu$^{+3}$) from aqueous solutions. The framework applies a thermodynamic equation of motion to a discrete energy eigenstructure to model the binding kinetics of europium ions to reactive sites of the polymer chains. The energy eigenstructure is generated using a non-Markovian Monte Carlo model that estimates energy level degeneracies. The equation of motion is used to determine the occupation probability of each energy level, describing the unique path through thermodynamic state space by which the polymer system sequesters rare-earth ions from solution. A second Monte Carlo simulation is conducted to relate the kinetic path in state space to physical descriptors associated with the polymer, including the radius of gyration, tortuosity, and Eu-neighbor distribution functions. These descriptors are used to visualize the evolution of the polymer during the sequestration process. The fraction of sequestered Eu$^{+3}$ ions depends upon the total energy of the system, with lower energy resulting in higher sequestration. The kinetics of the overall sequestration are dependent on the steepest-entropy-ascent principle used by the equation of motion to generate a unique kinetic path from an initial non-equilibrium state.