Lecture

Rate Theory: Transition States and Dynamics

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Description

This lecture covers the fundamentals of rate theory in chemical reactions, including classical and quantum transition-state theories, tunneling effects, and the use of ring-polymer molecular dynamics. It discusses the concepts of flux-side correlation functions, recrossing, and the Bennett-Chandler approach, emphasizing the importance of optimal dividing surfaces and asymmetric barriers. The lecture also explores the implications of symmetric and asymmetric barriers on reaction rates, as well as the crossover temperature in deep-tunneling regimes.

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Related concepts (27)

Transition state theory

In chemistry, transition state theory (TST) explains the reaction rates of elementary chemical reactions. The theory assumes a special type of chemical equilibrium (quasi-equilibrium) between reactants and activated transition state complexes. TST is used primarily to understand qualitatively how chemical reactions take place.

Chemical reaction

A chemical reaction is a process that leads to the chemical transformation of one set of chemical substances to another. Classically, chemical reactions encompass changes that only involve the positions of electrons in the forming and breaking of chemical bonds between atoms, with no change to the nuclei (no change to the elements present), and can often be described by a chemical equation. Nuclear chemistry is a sub-discipline of chemistry that involves the chemical reactions of unstable and radioactive elements where both electronic and nuclear changes can occur.

Reaction rate

The reaction rate or rate of reaction is the speed at which a chemical reaction takes place, defined as proportional to the increase in the concentration of a product per unit time and to the decrease in the concentration of a reactant per unit time. Reaction rates can vary dramatically. For example, the oxidative rusting of iron under Earth's atmosphere is a slow reaction that can take many years, but the combustion of cellulose in a fire is a reaction that takes place in fractions of a second.

Reaction rate constant

In chemical kinetics, a reaction rate constant or reaction rate coefficient (k) is a proportionality constant which quantifies the rate and direction of a chemical reaction by relating it with the concentration of reactants. For a reaction between reactants A and B to form a product C, where A and B are reactants C is a product a, b, and c are stoichiometric coefficients, the reaction rate is often found to have the form: Here k is the reaction rate constant that depends on temperature, and [A] and [B] are the molar concentrations of substances A and B in moles per unit volume of solution, assuming the reaction is taking place throughout the volume of the solution.

Reaction mechanism

In chemistry, a reaction mechanism is the step by step sequence of elementary reactions by which overall chemical reaction occurs. A chemical mechanism is a theoretical conjecture that tries to describe in detail what takes place at each stage of an overall chemical reaction. The detailed steps of a reaction are not observable in most cases. The conjectured mechanism is chosen because it is thermodynamically feasible and has experimental support in isolated intermediates (see next section) or other quantitative and qualitative characteristics of the reaction.

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