相关论文: First Principles Reactive Flux Theory for Surface …
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.…
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 describe a first-principles statistical mechanics approach enabling us to simulate the steady-state situation of heterogeneous catalysis. In a first step density-functional theory together with transition-state theory is employed to…
We present a first-principles based multiscale modeling approach to heterogeneous catalysis that integrates first-principles kinetic Monte Carlo simulations of the surface reaction chemistry into a fluid dynamical treatment of the…
We assess heat and mass transfer limitations in in situ studies of model catalysts with a first-principles based multiscale modeling approach that integrates a detailed description of the surface reaction chemistry and the macro-scale flow…
A general formalism is presented to describe the turnover frequency (TOF) during heterogeneous catalysis beyond a mean field treatment. For every elementary reaction we define its multiplicity as the number of times the reaction can be…
The turn-over frequency of the catalytic oxidation of CO at RuO2(110) was calculated as function of temperature and partial pressures using ab initio statistical mechanics. The underlying energetics of the gas-phase molecules, dissociation,…
Understanding of the complex behavior of particles at surfaces requires detailed knowledge of both macroscopic and microscopic processes that take place; also certain processes depend critically on temperature and gas pressure. To link…
HCN is a key ingredient for synthesizing biomolecules such as nucleobases and amino acids. We calculate 42 reaction rate coefficients directly involved with or in competition with the production of HCN in the early Earth or Titan…
Finding representative reaction pathways is necessary for understanding mechanisms of molecular processes, but is considered to be extremely challenging. We propose a new method to construct reaction paths based on mean first-passage times.…
Lying-standing transitions in the first molecular monolayer at organic-inorganic interfaces strongly influence interface dipoles, energy-level alignment, and growth modes, yet their collective kinetics remain difficult to predict. Here, we…
The accuracy of rate constants calculated using transition state theory depends crucially on the correct identification of a recrossing--free dividing surface. We show here that it is possible to define such optimal dividing surface in…
Surfaces serve as highly efficient catalysts for a vast variety of chemical reactions. Typically, such surface reactions involve billions of molecules which diffuse and react over macroscopic areas. Therefore, stochastic fluctuations are…
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…
Dynamics between reactants and products are often mediated by a rate-determining barrier and an associated dividing surface leading to the transition state theory rate. This framework is challenged when the barrier is time-dependent because…
A practical method for finding free energy barriers for transitions in high-dimensional classical and quantum systems is presented and used to calculate the dissociative sticking probability of H2 on a metal surface within transition state…
Understanding the set of elementary steps and kinetics in each reaction is extremely valuable to make informed decisions about creating the next generation of catalytic materials. With physical and mechanistic complexity of industrial…
Resonantly-forced oscillatory reaction-diffusion systems can exhibit fronts with complicated interfacial structure separating phase-locked homogeneous states. For values of the forcing amplitude below a critical value the front "explodes"…
We consider the governing equations for the motion of the viscous fluids in two moving domains and an evolving surface from both energetic and thermodynamic points of view. We make mathematical models for multiphase flow with surface flow…
The framework of transition state theory (TST) provides a powerful way for analyzing the dynamics of physical and chemical reactions. While TST has already been successfully used to obtain reaction rates for systems with a single…