Time evolution of a small reactive system

Badiali
2013 Condensed Matter Physics  
We investigate the irreversible evolution of a small system in which a chemical reaction takes place. We have two main goals: the first requires to find an equation to produce a time-irreversible behavior,the second consists in introducing a simple exactly solvable model in order to understand basic facts in chemical kinetics. Our basic tool is the transition function counting the number of paths joining two points in the reactive coordinates system. An exact quantum Smoluchowski equation is
more » ... wski equation is derived for the reactive system in vacuum, in the presence of a solvent in equilibrium at any time with the reactive system a new Smoluchowski equation is obtained. The transition from a quantum regime to a classical one is discussed. The case of a reactive system not in equilibrium with its neighborhood is investigated in terms of path integral and via a partial differential function. Memory effects and closure assumptions are discussed. Using a simple potential model, the chemical rate constant is exactly calculated and questions such as the meaning of the activation energy or the physical content of the so-called prefactor are investigated.
doi:10.5488/cmp.16.43003 fatcat:7xjeltmatbeqhdpifbc27sv5iq