transition state
In theories describing @E02035@ it is usually assumed that there is a transition state of more positive molar Gibbs energy between the reactants and the products through which an assembly of atoms (initially composing the @M03986@ of the reactants) must pass on going from reactants to products in either direction. In the formalism of '@T06470@' the transition state of an @E02035@ is that set of states (each characterized by its own geometry and energy) in which an assembly of atoms, when randomly placed there, would have an equal @P04855@ of forming the reactants or of forming the products of that @E02035@. The transition state is characterized by one and only one imaginary frequency. The assembly of atoms at the transition state has been called an @A00092@. (It is not a @C01203@ according to the definition in this Compendium.) It may be noted that the calculations of reaction rates by the transition state method and based on calculated @P04780@ refer to the potential energy maximum at the @C01145@, as this is the only point for which the requisite separability of transition state coordinates may be assumed. The ratio of the number of assemblies of atoms that pass through to the products to the number of those that reach the @C01145@ from the reactants can be less than unity, and this fraction is the '@T06479@' \(\kappa \). (There are also reactions, such as the gas-phase @C01153@ of simple @R05066@, that do not require '@A00093@' and which therefore do not involve a transition state.)
See also:
Gibbs energy of activation
Hammond principle
potential energy profile
transition structure
activated complex
PAC, 1994, 66, 1077. (Glossary of terms used in physical organic chemistry (IUPAC Recommendations 1994)) on page 1174 [Terms] [Paper]