Interpretation of Light Scattering Spectra in Terms of Particle Displacements

TL;DR

This paper clarifies how light scattering spectra relate to particle displacements, emphasizing that the spectrum's form indicates whether mean-square displacements can be directly inferred, especially highlighting the limitations of assuming exponential decay.

Contribution

It derives a general form for the light scattering correlation function that accounts for higher-order displacement moments, correcting the common exponential approximation.

Findings

The correlation function reflects all displacement moments, not just the mean-square.

Exponential decay of the correlation function indicates direct measurement of mean-square displacements.

The paper provides a diagnostic to determine when the spectrum accurately reveals particle displacements.

Abstract

Quasi-elastic light scattering spectroscopy of dilute solutions of diffusing mesoscopic probe particles is regularly used to examine the dynamics of the fluid through which the probe particles are moving. For probes in a simple liquid, the light scattering spectrum is a simple exponential; the field correlation function $g^{(1)}_{P}(q,\tau)$ of the scattering particles is related to their mean-square displacements $\bar{X^{2}} \equiv < (\Delta x(\tau))^{2}>$ during $\tau$ via $g^{(1)}(q,\tau) = \exp(- {1/2} q^{2} \bar{X^{2}})$. However, historical demonstrations of this expression refer only to ideal Brownian particles in simple liquids, and show that if the form is correct then it is also true that $g^{(1)}(q,\tau) = \exp(- \Gamma \tau)$, a pure exponential in $\tau$. In general, $g^{(1)}_{P}(q,\tau)$ is not a single exponential in time. $g^{(1)}_{P}(q,\tau)$ reflects not only the mean-square particle displacements but also all higher-order mean displacement moments $\bar{X^{2n}}$. A correct general form for $g^{(1)}(q,\tau)$, replacing the generally-incorrect $\exp(- {1/2} q^{2} \bar{X^{2}})$, is obtained. A simple experimental diagnostic determining when the field correlation function gives the mean-square displacements is identified, namely $g^{(1)}(q,\tau)$ reveals $\bar{X^{2}}$ if $g^{(1)}(q,\tau)$ is exponential in $\tau$.