Quantum reaction rates and sampling of quantum equilibrium structure
Quantum reaction rates and sampling of quantum equilibrium structure
Publication Type:
Journal ArticleSource:
Journal of Chemical Physics, Volume 127, Number 22 (2007)URL:
https://www.scopus.com/inward/record.uri?eid=2-s2.0-37149005211&doi=10.1063%2f1.2805071&partnerID=40&md5=6ecdc755fc69a80cb08458df0e42575fKeywords:
Correlation functions, Kubo transform, Linear response theory, Quantum equilibrium structure, Quantum Theory, Reaction coordinates, Reaction rates, Regression analysis, Spectral densityAbstract:
The quantum reaction rates and sampling of quantum equilibrium structure is discussed. Quantum time correlation functions, which are obtained from the linear response theory, are defined as a scalar product including the Kubo transform. This form of the scalar product also insures that the nonequilibrium average of the random force fluctuations corresponding to an observable vanish so that the macroscopic law is obtained on long distance and time scales and the Onsager regression hypothesis is satisfied. The time-dependent rate coefficient may be calculated using the three spectral density functions. All three predict the same rate constant, despite different time dependence of these estimates. The real and symmetric density function may be more suitable for simple model systems, while the simpler density function may be more useful for complicated systems involving reaction coordinates.
