Reactive quantum Boltzmann equations: A derivation from an arrangement channel space representation and BBGKY hierarchy

Journal Article · Tue Mar 01 04:00:00 EST 1983 · J. Chem. Phys.; (United States)

DOI:https://doi.org/10.1063/1.445026· OSTI ID:6337254

Evans, J W; Hoffman, D K; Kouri, D J

A rigorous derivation of the reactive quantum Boltzmann equations is presented for systems where breakup and recombination are excluded. The use of an arrangement channel space representation allows an exact decomposition of the N particle density matrix into components for different chemical compositions and an exact definition of reduced species density matrices (as opposed, e.g., to standard projection operator techniques). This necessitates the use of the combinatorially complex arrangement channel BBGKY hierarchy which, however, avoids the need for the usual heuristic specification of collision terms. Another advantage is that scattering equations generated for the reactive and nonreactive many body T matrices appearing in the Boltzmann equations have ''well-behaved'' kernels (unlike the corresponding Lippmann--Schwinger equations). From the derived equations we readily obtain, e.g., reaction-diffusion equations and nonequilibrium expressions for the chemical reaction rates.

• Research Organization: Ames Laboratory and Department of Chemistry, Iowa State University, Ames, Iowa 50011
• OSTI ID: 6337254
• Journal Information: J. Chem. Phys.; (United States), Journal Name: J. Chem. Phys.; (United States) Vol. 78:5; ISSN JCPSA
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400201* -- Chemical & Physicochemical Properties
BOLTZMANN EQUATION
CHEMICAL REACTION KINETICS
CHEMICAL REACTIONS
DECOMPOSITION
DENSITY MATRIX
DIFFERENTIAL EQUATIONS
DIFFUSION
EQUATIONS
KINETICS
MATRICES
PARTIAL DIFFERENTIAL EQUATIONS
REACTION KINETICS
TRANSPORT THEORY