Interpretation of Diffusing Wave Spectra in Nontrivial Systems

TL;DR

This paper applies advanced mathematical methods to interpret diffusing wave spectroscopy spectra, revealing their dependence on multiple moments of particle displacements and highlighting limitations of simplified models in complex systems.

Contribution

It extends previous mathematical approaches to relate DWS spectra to higher moments of particle displacements, addressing complexities in polydisperse and interacting systems.

Findings

DWS spectra depend on higher moments of particle displacements.

Simplified exponential models are inaccurate for complex fluids.

Multiple scattering fluctuations significantly influence DWS spectra.

Abstract

Mathematical methods previously used (Phillies, J. Chem. Phys., 122 224905 (2005)) to interpret quasielastic light scattering spectroscopy (QELSS) spectra are here applied to relate diffusing wave spectroscopy (DWS) spectra to the moments \bar{X^{2n}} of particle displacements in the solution under study. DWS spectra of optical probes are like QELSS spectra in that in general they are not determined solely by the second moment \bar{X^{2}}. In each case, the relationship between the spectrum and the particle motions arises from the field correlation function g^{(1)}_{s}(t) for a single quasi-elastic scattering event. In most physically interesting cases, g^{(1)}_{s}(t) receives except at the shortest times large contributions from higher moments \bar{X(t)^{2n}}, n >1. As has long been known, the idealized form g^{(1)}_{s}(t) =\exp(-2 q^{2} \bar{X(t)^{2}}), sometimes invoked to interpret DWS and QELSS spectra, only refers to (adequately) monodisperse, noninteracting, probes in purely Newtonian liquids and is erroneous for polydisperse particles, interacting particles, or particles in viscoelastic complex fluids. Furthermore, in DWS experiments fluctuations (for multiple scattering paths of fixed length) in the number of scattering events and the total-square scattering vector significantly modify the spectrum.