Počet záznamů: 1
Towards a Unified Formulation of Dynamics and Thermodynamics I. From Microscopic to Macroscopic Time Scales
0358304 - UFCH-W 2012 RIV US eng J - Článek v odborném periodiku
Durand, P. - Paidarová, Ivana
Towards a Unified Formulation of Dynamics and Thermodynamics I. From Microscopic to Macroscopic Time Scales.
International Journal of Quantum Chemistry. Roč. 111, č. 2 (2011), s. 225-236 ISSN 0020-7608
Grant CEP: GA AV ČR IAA100400501; GA AV ČR IAA401870702
Výzkumný záměr: CEZ:AV0Z40400503
Klíčová slova: Liouville equation * time scales * chemical kinetics and dynamics
Kód oboru RIV: CF - Fyzikální chemie a teoretická chemie
Impakt faktor: 1.357, rok: 2011
We go a step further on the path opened in the mid-1950s by Prigogine and his collaborators towards a unified description of dynamics and thermodynamics of irreversible processes. Here, the theory is developed from concepts and methods originating in the quantum theory of resonances. The Liouville-von Neumann equation is solved by means of effective Liouvillians, which are similar to the effective Hamiltonians used in quantum mechanics. Hierarchies of effective Liouvillians allow us to determine the long macroscopic time scales from short microscopic characteristic times. For that purpose, standard perturbation theory is used in the complex plane. Damped and oscillating irreversible decays of a fluctuation are described by means of a two-dimensional matrix representation of the Liouvillian. Finally, we derive a kinetic equation for a simple model of a chemical reaction proceeding towards equilibrium. The model implies a transition state assimilated to a short-lived resonance.
Trvalý link: http://hdl.handle.net/11104/0196391