An efficient implementation of the quantum mechanical transition state theory recently proposed by Hansen and Andersen @J. Chem. Phys. 101, 6032 ~1994!; J. Phys. Chem. 100, 1137 ~1996!# is presented. Their method approximates the flux–flux autocorrelation function by using short-time information to fit an assumed functional form ~with physically correct properties!. The approach described here ...

The results of transition state theory are derived rigorously in the general context of ergodic dynamical systems defined by a vector field on a Riemannian manifold. A new perspective on how to compute the dynamical corrections to the TST transition frequency is given. Hamiltonian dynamical systems are considered as a special case and the so-called Marcus formula for the rate constant is re-der...

A program can be considered as a device that generates discrete time signals, where a signal is an execution. Shannon information rate, or bit rate, of the signals may not be uniformly distributed. When the program is specified by a finite state transition system, algorithms are provided in identifying information-rich components. For a black-box program that has a partial specification or does...

Pavel F. Bessarab,1,2 Valery M. Uzdin,2,3 and Hannes Jónsson1 1Science Institute and Faculty of Science, VR-III, University of Iceland, 107 Reykjavı́k, Iceland 2Department of Physics, St. Petersburg State University, St. Petersburg, 198504, Russia 3St. Petersburg State University of Information Technologies, Mechanics and Optics, St. Petersburg, 197101, Russia (Received 14 November 2011; revised...

The success of Transition State Theory (TST) in describing the rates of chemical reactions has been less-than-perfect in solution (and sometimes even in the gas phase) because conventional dividing surfaces are only approximately free of recrossings between reactants and products. Recent advances in dynamical systems theory have helped to identify the interconnected manifolds —“superhighways”— ...

A theory for calculating rates of transitions in quantum systems is presented and applied to desorption of H from a 2 Ž . Cu 110 surface. The quantum transition state is defined as a conical dividing surface in the space of closed Feynman paths and a ‘reaction coordinate’ in this extended space is used to parametrize a reversible work evaluation of the free energy barrier. In a low temperature,...

Clogging is one of the main failure mechanisms encountered in industrial processes such as membrane filtration. Our understanding of the factors that govern the build-up of fouling layers and the emergence of clogs is largely incomplete, so that prevention of clogging remains an immense and costly challenge. In this paper we use a microfluidic model combined with quantitative real-time imaging ...

F. Revuelta, Thomas Bartsch, R. M. Benito, and F. Borondo Grupo de Sistemas Complejos, and Dep. de F́ısica y Mecánica, Escuela Técnica Superior de Ingenieros Agrónomos, Universidad Politécnica de Madrid, 28040 Madrid, Spain Department of Mathematical Sciences, Loughborough University, Loughborough LE11 3TU, United Kingdom Departamento de Qúımica, and Instituto de Ciencias Matemáticas CSIC-UAM-UC...

the sorption isotherm and state diagram of sundried, golden and sultana raisins were constructed for investigation and comparison of the product stability. the isotherms were measured at 15, 25 and 35 °c using an isopiestic method and the data were modeled with gab model. glass transition temperatures of the products were measured by differential scanning calorimetery (dsc) and fitted to gordon...

We analyze thermal rate constants as computed with surface hopping dynamics and resolve certain inconsistencies that have permeated the literature. On one hand, according to Landry and Subotnik (J. Chem. Phys. 2012, 137, 22A513), without decoherence, direct dynamics with surface hopping overestimates the rate of relaxation for the spin-boson Hamiltonian. On the other hand, according to Jain and...