The generalized Langevin equations are presented by considering such microscopic motions of molecules described by the microscopic Hamiltonian whose potential function is quadratic and internal degree of freedom is multidimensional. Considering the long time behavior of the reactive mode, the Grote-
The stochastic theory and the transition-state theory
โ Scribed by S.G. Christov
- Publisher
- Elsevier Science
- Year
- 1992
- Tongue
- English
- Weight
- 291 KB
- Volume
- 188
- Category
- Article
- ISSN
- 0009-2614
No coin nor oath required. For personal study only.
โฆ Synopsis
The relations between the stochastic and transition-state theories are reconsidered on the basis of a harmonic oscillator model. It is shown from the physical point of view that both theories are not equivalent.
๐ SIMILAR VOLUMES
For thermal reactants, it is shown that classical transition state theory and collision theory yield the very same explicit expression for the steric factor in terms of the 3N-7 internal coordinates dependence of the barrier to reaction. Various special cases are worked out for an atom-diatom exchan
A modified transition state theory, appropriate for direct reactions, which incorporates dynamic constraints and can account for popuhtion inversion, is presented. it is shown that the distribution of vibntionni states can be czaracterized by ;i lagrangian parameter that can be interpreted ns tempem
A nonseparable semiclassical transition state approximation for reactions involving more than one eiectronic surface is rugestcd. The single surface formulation in terms of quasiprobabi!ity distributions used by Miller is discussed along with 3 sepxable semiclassical approximation for the nonadhbati