Here we continue our investigation aimed at the derivation of the Boltzmann equation from the first principles of quantum mechanics. The key difficulty that we overcome in this manuscript is the incompatibility between traditional methods employed in the derivation of classical mechanics from quantum mechanics and methods used to describe transitions between quantum states due to interaction. Here we use a novel technique that is similar to the wavelet transform method that originally appeared in the context of signal processing. With this method, we can simultaneously work with slowly varying potentials that give rise to classical-like wave-function behaviour, motion along a prescribed trajectory, and sharp potentials that lead to behaviour that is best understood in terms of quantum transitions. Working with smooth potentials in this framework, we derive the Liouville equation from the Schrödinger equation. When using this method for sharp potentials, we naturally obtain the description of system dynamics in terms of a transition-rate matrix. The transition rates between system states, which characterize the process, are determined by Fermi's golden rule. We observe that, through the Liouville equation, we can deduce the non-collision part of the Boltzmann equation, and that, through the transition-rate matrix, we can deduce the collision integral. We combine the results to derive the Boltzmann equation, the main formula of physical kinetics.
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.