Premium
Hamiltonian formulations of chemical kinetics
Author(s) -
Georgian T.,
Findley G. L.
Publication year - 2009
Publication title -
international journal of quantum chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.484
H-Index - 105
eISSN - 1097-461X
pISSN - 0020-7608
DOI - 10.1002/qua.560240732
Subject(s) - legendre transformation , hamiltonian (control theory) , chemical reaction , reaction coordinate , chemical kinetics , kinetics , hamiltonian mechanics , variational principle , euler's formula , euler–lagrange equation , lagrangian , thermodynamics , chemistry , physics , classical mechanics , computational chemistry , mathematics , mathematical physics , mathematical analysis , phase space , mathematical optimization , organic chemistry
We present a Hamiltonian approach to phenomenological chemical kinetics. The genesis of this approach resides in the definition of an intrinsic reaction coordinate space in which each distinct reaction coordinate corresponds to a distinct chemical reaction. The Gibbs function is then used to generate a variational principle which, in turn, leads to a set of Euler‐Lagrange equations. The form of the Euler‐Lagrange equations in reaction coordinate space permits the identification of the Gibbs function as a Langrangian, and a Legendre transformation of the Gibbs function results in a reaction Hamiltonian. Hamiltonians for two simple chemical reactions are presented, and the results of the present approach are shown to be consistent with phenomenological chemical kinetics.