Maxwell-Boltzmann distribution equation method

The basic principles are described in many textbooks [24, 26]. They are thus only sketchily presented here. In a conventional classical molecular dynamics calculation, a system of particles is placed within a cell of fixed volume, most frequently cubic in size. A set of velocities is also assigned, usually drawn from a Maxwell-Boltzmann distribution appropriate to the temperature of interest and selected in a way so as to make the net linear momentum zero. The subsequent trajectories of the particles are then calculated using the Newton equations of motion. Employing the finite difference method, this set of differential equations is transformed into a set of algebraic equations, which are solved by computer. The particles are assumed to interact through some prescribed force law. The dispersion, dipole-dipole, and polarization forces are typically included whenever possible, they are taken from the literature. 

At this point, it is worthwhile to return on the theoretical basis of the kinetic method, and make some considerations on the assumptions made, in order to better investigate the validity of the information provided by the method. In particular some words have to been spent on the effective temperamre The use of effective parameters is common in chemistry. This usually implies that one wishes to use the form of an established equation under conditions when it is not strictly valid. The effective parameter is always an empirical value, closely related to and defined by the equation one wishes to approximate. Clearly, is not a thermodynamic quantity reflecting a Maxwell-Boltzmann distribution of energies. Rather, represents only a small fraction of the complexes generated that happen to dissociate during the instrumental time window (which can vary from apparatus to apparatus). 

All chemical process involves the motion of atoms within a molecule. Molecular dynamics (MD), in the broadest sense, is concerned with molecules in motion. It combines the energy calculations from molecular mechanics with equations of motion. Generally, an appropriate starting structure is selected (normally an energy minimized structure). Each atom in the system is then assigned a random velocity that is consistent with the Maxwell-Boltzmann distribution for the temperature of interest. The MM formalism is used to calculate the forces on all the atoms. Once the atom positions are known, the forces, velocities at time t, and the position of the atoms at some new time t + 5t can be predicted. More details about the method can be found in Ref.. ... 

More quantitative results have been obtained by Prigogine16 and co-workers, who adopted a kinetic method of approach and who treated this problem by the modern methods of the kinetic theory of gases. The integro-differential Maxwell-Boltzmann equation was extended to the case of inelastic collisions to get the velocity distribution functions /y, in terms of which the reaction rate may be written... 

We give below a simple method to derive an approximate solution to the hnear-ized Poisson-Boltzmann equation (1.9) for the potential distribution i/ (r) around a nearly spherical spheroidal particle immersed in an electrolyte solution [12]. This method is based on Maxwell s method [13] to derive an approximate solution to the Laplace equation for the potential distribution around a nearly spherical particle. 

Integral methods include all those which attempt solution of the moment equation (Maxwell s equation of transfer) of the Boltzmann equation. The well known integral methods which have been applied include Mott-Smith s bimodal distribution [2.100], Grad s 13 moment equations [2.101], Lees two-stream Maxwellian [2.102], and Waldmann s higher-order hydrodynamics and boundary conditions [2.103]. 

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