Diffusion coefficients from signal fluctuations: Influence of molecular shape and rotational diffusion

Abstract: Analysis of signal fluctuations of a locally fixed probe, caused by molecules diffusing under the probe, can be used to determine diffusion coefficients. Theoretical treatments so far have been limited to point-like particles or to molecules with circle-like shapes. Here we extend these treatments to molecules with rectangle-like shapes, for which also rotational diffusion needs to be taken into account. Focusing on the distribution of peak widths in the signal, we show how translational as well as rotational diffusion coefficients can be determined. We address also the question, how the distribution of interpeak time intervals and autocorrelation function can be employed for determining diffusion coefficients. Our approach is validated against kinetic Monte Carlo simulations.