Dynamical properties of colloidal systems: III. Collective and self-diffusion of interacting charged particles

The formalism, developed in two earlier papers, for the dynamics of interacting Brownian particles is applied to a system of charged spherical particles in solution. Memory-type transport equations are derived for the propagators of collective and self-diffusion. The memory function for collective diffusion can be related, in the hydrodynamic limit, to the viscosity of the “fluid” of Brownian particles. The memory functions are calculated for a Debye-Hückel system, from an experimentally determined static structure factor S(k), and for an overdamped one-component plasma (OCP). In the two latter cases satisfactory agreement is found with dynamical light scattering results on solutions of polystyrene spheres; in particular, the deviation of the dynamical structure factor from a simple exponential decay can be related to memory effects. With regard to self-diffusion the velocity autocorrelation function, the mean square displacement of one particle and from it the self-diffusion coefficient D_s are calculated. Using S(k) for an actual system, $\text{D}{}_{\mathrm{s}}\text{≈}\text{1}\text{3}\text{D}{}_0$ is obtained, where D₀ is the free diffusion constant. The calculations on the basis of the overdamped OCP-model show that the dynamical properties of the experimentally investigated systems of charged polystyrene spheres can be described by this model for a wide range of scattering angles.     

Ab initio calculations on the structure of the cyclopropenyl anion

Calculations at the SCF level and with inclusion of correlation were carried out on a portion of the potential ¹A′ state of the cyclopropenyl anion which was found to be nonplanar in its most stable geometry.     

Dynamical properties of colloidal systems: II. Correlation- and response functions

For systems of interacting Brownian particles a Fokker-Planck equation is derived for the probability distribution function of the concentration fluctuations, using assumption of a Gaussian static distribution function. The drift- and the diffusion term are determined by static correlation functions. By this approach specific properties of different systems as e.g., suspensions of charged spherical particles or chain polymers are taken into account. Although the diffusion term is fluctuation dependent the properties of detailed balance and both fluctuation dissipation theorems are satisfied. Using the formalism of Martin, Siggia and Rose, Dyson- and vertex-equations for the two-particle correlation functions are derived. An explicit calculation of these functions, together with related quantities as the dynamic structure factor, and of the diffusion coefficients, is given in a mean-field approximation. The results are compared with several earlier theories, which were developed for specific systems.     

Theory of light scattering from a system of interacting Brownian particles

Starting from a N-particle diffusion equation for a system of N interacting spherical Brownian particles, a non-linear transport equation for concentration fluctuations δc(r, t) of the particles is derived. This dynamic equation is transformed into a hierarchy of equations for retarded propagators of increasing numbers of concentration fluctuations. A cluster expansion to lowest order in the average concentration results in a set of two coupled equations. The spectrum of light scattered by the interacting particles is in general not a Lorentzian, due to the non-linear term in the transport equation. For small scattering wave vectors k the width is D(ω)k², where ω is the transferred frequency. It is shown that D(0) = D_e, the effective diffusion coefficient. For a hardcore interaction potential the spectrum is Lorentzian and it is found that D_e = D₀(1 + φ), where D₀ is the diffusion constant for independent particles and φ the volume concentration of Brownian particles.     

Charged particle emission following the absorption of stopped π− in 12C, 59Co and 197Au

Energy spectra of charged particles (p, d, t, ³He, α) emitted following the absorption of stopped π^? in ¹²C, ⁵⁹Co and ¹⁹⁷Au have been measured. The results are compared with results from neutron spectroscopy and discussed in the context of the quasi-deuteron model of π^? absorption.     

Deformation potentials of bulk semiconductors

A theory of deformation potential electron-phonon scattering coefficients is presented for elemental and compound semiconductors. Expressions for the acoustical deformation potential constants at symmetry points are obtained in closed form for direct-gap bulk semiconductors. The deformation potential vs k is predicted for GaAs.