Generalized Transition State Theory
Any form of TST, such as microcanonical variational TST, canonical variational TST, and improved canonical variational TST, in which the transition state is not necessarily located at the saddle point, is referred to as generalized transition state theory.
Microcanonical Variational TST
A development of transition state theory in which the dividing surface is varied so as to minimize the rate calculated for a fixed energy. The rate expressions obtained in a microcanonical treatment can be integrated over the energy, taking into account the statistical distribution over energy states, so as to give the canonical, or thermal rates.
Canonical Variational TST
A development of transition state theory in which the position of the dividing surface is varied so as to minimize the rate constant at a given temperature.
Improved Canonical Variational TST
A modification of canonical variational transition state theory in which, for energies below the threshold energy, the position of the dividing surface is taken to be that of the microcanonical threshold energy. This forces the contributions to rate constants to be zero if they are below the threshold energy. A compromise dividing surface is then chosen so as to minimize the contributions to the rate constant made by reactants having higher energies.
Read more about this topic: Transition State Theory
Famous quotes containing the words generalized, transition, state and/or theory:
“One is conscious of no brave and noble earnestness in it, of no generalized passion for intellectual and spiritual adventure, of no organized determination to think things out. What is there is a highly self-conscious and insipid correctness, a bloodless respectability submergence of matter in manner—in brief, what is there is the feeble, uninspiring quality of German painting and English music.”
—H.L. (Henry Lewis)
“The god or hero of the sculptor is always represented in a transition from that which is representable to the senses, to that which is not.”
—Ralph Waldo Emerson (1803–1882)
“A perfect personality ... is only possible in a state of society where man is free to choose the mode of work, the conditions of work, and the freedom to work. One to whom the making of a table, the building of a house, or the tilling of the soil, is what the painting is to the artist and the discovery to the scientist,—the result of inspiration, of intense longing, and deep interest in work as a creative force.”
—Emma Goldman (1869–1940)
“The great tragedy of science—the slaying of a beautiful theory by an ugly fact.”
—Thomas Henry Huxley (1825–1895)