Related papers: Microscopic derivation of transition-state theory …
A model is proposed for studying the reaction dynamics in complex quantum systems in which the complete mixing of states is hindered by an internal barrier. Such systems are often treated by the transition-state theory, also known in…
To model a complex system intrinsically separated by a barrier, we use two random Hamiltonians, coupled to each other either by a tunneling matrix element or by an intermediate transition state. We study that model in the universal limit of…
Two quantum systems, each described as a random-matrix ensemble. are coupled to each other via a number of transition states. Each system is strongly coupled to a large number of channels. The average transmission probability is the product…
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…
We study the decay of general initial states out of a metastable potential well in quantum mechanics. We provide a closed-form expression for the probability current that tunnels through the barrier in terms of the resonant states into…
Transition State Theory is a central cornerstone in reaction dynamics. Its key step is the identification of a dividing surface that is crossed only once by all reactive trajectories. This assumption is often badly violated, especially when…
We consider the general scenario of an excited level |i> of a quantum system that can decay via two channels: (i) via a single-quantum jump to an intermediate, resonant level |bar m>, followed by a second single-quantum jump to a final…
We construct and explore a family of states for quantum systems in contact with two or more heath reservoirs. The reservoirs are described by equilibrium distributions. The interaction of each reservoir with the bulk of the system is…
Chemical reactions subjected to time-varying external forces cannot generally be described through a fixed bottleneck near the transition state barrier or dividing surface. A naive dividing surface attached to the instantaneous, but moving,…
The description of an open quantum system's decay almost always requires several approximations as to remain tractable. Here, we first revisit the meaning, domain and seeming contradictions of a few of the most widely used of such…
A quantum version of a recent formulation of transition state theory in {\em phase space} is presented. The theory developed provides an algorithm to compute quantum reaction rates and the associated Gamov-Siegert resonances with very high…
The Gaussian Orthogonal Ensemble (GOE) of random matrices has been widely employed to describe diverse phenomena in strongly coupled quantum systems. An important prediction is that the decay rates of the GOE eigenstates fluctuate according…
We develop a resonance theory to describe the evolution of open systems with time-dependent dynamics. Our approach is based on piecewise constant Hamiltonians: we represent the evolution on each constant bit using a recently developed…
Based on the general form of the master equation for open quantum systems the tunneling is considered. Using the path integral technique a simple closed form expression for the tunneling rate through a parabolic barrier is obtained. The…
This dissertation unifies one of the central methods of classical rate calculation, `Transition-State Theory' (TST), with quantum mechanics, thereby deriving a rigorous `Quantum Transition-State Theory' (QTST). The resulting QTST is…
Transition State Theory overestimates reaction rates in solution because conventional dividing surfaces between reagents and products are crossed many times by the same reactive trajectory. We describe a recipe for constructing a…
A quantum-mechanical framework is set up to describe the full counting statistics of particles flowing between reservoirs in an open system under time-dependent driving. A symmetry relation is obtained which is the consequence of…
When driven by a potential bias between two finite reservoirs, the particle current across a quantum system evolves from an initial loading through a coherent, followed by a metastable phase, and ultimately fades away upon equilibration. We…
We present the results of studying the influence of different environmental states on the coherence of quantum processes. We choose to discuss a simple model which describe two electronic reservoirs connected through tunneling via a…
The rate of escape of an ideal bead-spring polymer in a symmetric double-well potential is calculated using transition state theory (TST) and the results compared with direct dynamical simulations. The minimum energy path of the transitions…