相关论文: Eyring equation and the second order rate law: Ove…
Elementary gas-phase reactions of the bimolecular type A + B -> Products are characterized by the second order kinetic law -d[A]/dt=k[A][B], where [A] and [B] are the concentrations of A and B species, t is time and k is the rate constant,…
Transition state theory (TST) is generalized for the nonequilibrium system with power-law distributions. The stochastic dynamics that gives rise to the power-law distributions for the reaction coordinate and momentum is modeled by the…
The power-law TST reaction rate coefficient for an elementary bimolecular reaction is studied when the reaction takes place in a nonequilibrium system with power-law distributions. We derive a generalized TST rate coefficient, which not…
Classical transition state theory (TST) is the cornerstone of reaction rate theory. It postulates a partition of phase space into reactant and product regions, which are separated by a dividing surface that reactive trajectories must cross.…
The classical approaches to the derivation of the (generalized) Mass Action Law (MAL) assume that the intermediate transition state (i) has short life time and (ii) is in partial equilibrium with the initial reagents of the elementary…
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…
Recently, Gorban (2021) analysed some kinetic paradoxes of the transition state theory and proposed its revision that gave the "entangled mass action law", in which new reactions were generated as an addition to the reaction mechanism under…
Second law of thermodynamics is applied to a few electronic processes. It is seen that the second law of thermodynamics holds good for all except one mentioned here. The classical approach, based on exact equivalence of emission and…
Reaction rate theory in solids is modified taking into account intrinsic localized modes or discrete breathers (DBs) that can appear in crystals with sufficient anharmonicity resulting in violation of Arrhenius law. Large amplitude…
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…
The rates of chemical reactions are not absolute but their magnitude depends upon the relative speeds of the moving observers. This has been proved by unifying theories of chemical kinetics, which are transition state theory, collision…
Development of thermodynamic induction up to second order gives a dynamical bifurcation for thermodynamic variables and allows for the prediction and detailed explanation of nonequilibrium phase transitions with associated spontaneous…
Stochastic dynamics of chemical reactions in a mutually repressing two-gene circuit is numerically simulated. The circuit has a rich variety of different states when the kinetic change of DNA status is slow. The stochastic switching…
We apply quantum rate theory to calculate the transition rates as hydrogen or deuterium atoms escape from a vacancy trap in iron into a neighbouring metastable site. We determine transition rates and corresponding activation energies over a…
We show that the system entropy change for the transitions between non-equilibrium steady states arbitrarily far from equilibrium for any constituting process is given by the relative entropy of the distributions of these steady states.…
We study the TST reaction rate for the systems with power-law distributions. We derive the expressions of the reaction rate coefficient with tunneling correction, which strongly depends on the power-law parameter. The numerical results show…
In the development of equations of state for polyatomic molecules, thermodynamic perturbation theory (TPT) is widely used to calculate the change in free energy due to chain formation. TPT is a simplification of a more general and exact…
When traversing a symmetry breaking second order phase transition at a finite rate, topological defects form whose number dependence on the quench rate is given by simple power laws. We propose a general approach for the derivation of such…
Standard order-disorder phase transition in the Ising model is described in terms of rates of processes of spin flips. This formulation allows to extend numerous results on phase transition for sciences other than physics of magnetism. We…
Instanton theory is an established method to calculate rate constants of chemical reactions including atom tunneling. Technical and methodological improvements increased its applicability. Still, a large number of energy and gradient…