Kramers theory extension

A relatively unexplored extension of the Kramers theory is the escape of a Brownian particle out of a potential well in the presence of an external periodic force. Processes such as multiphoton dissociation and isomerization of molecules in high-pressure gas or in condensed phases/ laser-assisted desorption/ and transitions in current-driven Josephson junctions under the influence of microwaves " may be described with such a model, where the pieriodic force results from the radiation field. 

The Kramers theory and its extensions have found many applications since the original work by Kramers. Recent application of the non-Markovian theory in the low-friction limit to thermal desorption was described by Nitzan and Carmeli. Another novel application of the Markovian theory is to transition from a nonequilibrium state of a Josephson junction. In what follows we shall briefly review the recent application of the generalized Kramers theory to chemical rate processes. More detailed reviews of the exjjerimental and theoretical status of this field may be found in Hynes. ... 

Figure 9.1 Generic barrier for the transition dynamics in a more extensive part of the state in a chemical reaction. In classical TST, barrier region the area between the reactant the transition state, indicated by j , is located surface S and product surface Sp, which at the top of the barrier. Once the parti- plays a dominant role in Kramers theory and...

Kinetics is concerned with many-particle systems which require movements in space and time of individual particles. The first observations on the kinetic effect of individual molecular movements were reported by R. Brown in 1828. He observed the outward manifestation of molecular motion, now referred to as Brownian motion. The corresponding theory was first proposed in a satisfactory form in 1905 by A. Einstein. At the same time, the Polish physicist and physical chemist M. v. Smolu-chowski worked on problems of diffusion, Brownian motion (and coagulation of colloid particles) [M. v. Smoluchowski (1916)]. He is praised by later leaders in this field [S. Chandrasekhar (1943)] as a scientist whose theory of density fluctuations represents one of the most outstanding achievements in molecular physical chemistry. Further important contributions are due to Fokker, Planck, Burger, Furth, Ornstein, Uhlenbeck, Chandrasekhar, Kramers, among others. An extensive list of references can be found in [G.E. Uhlenbeck, L.S. Ornstein (1930) M.C. Wang, G.E. Uhlenbeck (1945)]. A survey of the field is found in [N. Wax, ed. (1954)]. 

Our approach to the study of the departure from equilibrium in chemical reactions and of the "microscopic theory of chemical kinetics is a discrete quantum-mechanical analog of the Kramers-Brownian-motion model. It is most specifically applicable to a study of the energy-level distribution function and of the rate of activation in unimolecular (dissociation Reactions. Our model is an extension of one which we used in a discussion of the relaxation of vibrational nonequilibrium distributions.14 18 20... 

Kramers approach to rate theory in the underdamped and spatial-diffusion-limited regimes spurred extensions which were applicable to the much more complex STGLE. Grote and Hynes (23) used a parabolic barrier approximation to derive the rate expression for the GLE in the spatial diffusion limit. Carmeli and Nitzan derived expressions for the rate of the GLE (24) and the STGLE (25) in the underdamped limit. The overdamped limit for the rate in the presence of delta correlated friction was solved using the mean first passage time expression (26,27). A turnover theory, valid for space- and time-dependent friction, has only been recently presented by Haynes, Voth, and Poliak... 

Because of the technological importance of ions as active elements in solid-state lasers, optical spectra of lanthanides in sites of low symmetry have been studied extensively. For these sites, the constraints imposed by group theory are weak, and selection rules are often nonexistent (such is the case with Kramers ions in C2 symmetry, for example). Thus, it becomes difficult to unravel the optical spectrum unambiguously. Even if this has been done, it is not straightforward to fit the data with a crystal-field Hamiltonian. The parameter space is large (14 crystal-field parameters in C2 symmetry) and several minima may exist that are indistinguishable from one another insofar as the quality of the fit is concerned. 

Abstract. The key concepts from H.A. Kramers influential work on noise-assisted escape of a particle bound in a potential well are summarized, as is the extensive impact that these ideas have had on the development of condensed-phase reaction-rate theories in the twentieth century. 

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