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Register a new userReaction dynamics through kinetic transition states
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The transformation of a system from one state to another is often mediated by a bottleneck in the systems phase space. In chemistry these bottlenecks are known as emph{transition states} through which the system has to pass in order to evolve from reactants to products. The chemical reactions are usually associated with configurational changes where the reactants and products states correspond, e.g., to two different isomers or the undissociated and dissociated state of a molecule or cluster. In this letter we report on a new type of bottleneck which mediates emph{kinetic} rather than configurational changes. The phase space structures associated with such emph{kinetic transition states} and their dynamical implications are discussed for the rotational vibrational motion of a triatomic molecule. An outline of more general related phase space structures with important dynamical implications is given.
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Recently the phase space structures governing reaction dynamics in Hamiltonian systems have been identified and algorithms for their explicit construction have been developed. These phase space structures are induced by saddle type equilibrium points which are characteristic for reaction type dynamics. Their construction is based on a Poincar{e}-Birkhoff normal form. Using tools from the geometric theory of Hamiltonian systems and their reduction we show in this paper how the construction of these phase space structures can be generalized to the case of the relative equilibria of a rotational symmetry reduced $N$-body system. As rotations almost always play an important role in the reaction dynamics of molecules the approach presented in this paper is of great relevance for applications.
Motivated by a phenomenon of phase transition in a model of alignment of self-propelled particles, we obtain a kinetic mean-field equation which is nothing else than the Doi equation (also called Smoluchowski equation) with dipolar potential. In a self-contained article, using only basic tools, we analyze the dynamics of this equation in any dimension. We first prove global well-posedness of this equation, starting with an initial condition in any Sobolev space. We then compute all possible steady-states. There is a threshold for the noise parameter: over this threshold, the only equilibrium is the uniform distribution, and under this threshold, there is also a family of non-isotropic equilibria. We give a rigorous prove of convergence of the solution to a steady-state as time goes to infinity. In particular we show that in the supercritical case, the only initial conditions leading to the uniform distribution in large time are those with vanishing momentum. For any positive value of the noise parameter, and any initial condition, we give rates of convergence towards equilibrium, exponentially for both supercritical and subcritical cases and algebraically for the critical case.
We review the construction of the supersymmetric sigma model for unitary maps, using the color- flavor transformation. We then illustrate applications by three case studies in quantum chaos. In two of these cases, general Floquet maps and quantum graphs, we show that universal spectral fluctuations arise provided the pertinent classical dynamics are fully chaotic (ergodic and with decay rates sufficiently gapped away from zero). In the third case, the kicked rotor, we show how the existence of arbitrarily long-lived modes of excitation (diffusion) precludes universal fluctuations and entails quantum localization.
Transition State Theory forms the basis of computing reaction rates in chemical and other systems. Recently it has been shown how transition state theory can rigorously be realized in phase space using an explicit algorithm. The quantization has been demonstrated to lead to an efficient procedure to compute cumulative reaction probabilities and the associated Gamov-Siegert resonances. In this letter these results are used to express the cumulative reaction probability as an absolutely convergent sum over periodic orbits contained in the transition state.
We investigate analytically and numerically the spatial structure of the non-equilibrium stationary states (NESS) of a point particle moving in a two dimensional periodic Lorentz gas (Sinai Billiard). The particle is subject to a constant external electric field E as well as a Gaussian thermostat which keeps the speed |v| constant. We show that despite the singular nature of the SRB measure its projections on the space coordinates are absolutely continuous. We further show that these projections satisfy linear response laws for small E. Some of them are computed numerically. We compare these results with those obtained from simple models in which the collisions with the obstacles are replaced by random collisions.Similarities and differences are noted.
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