Observation-time-induced crossover from fluctuating diffusivity

Abstract

A sharp change in apparent mobility at a characteristic temperature that depends on the observation time has been reported in experiments and simulations of hydrated proteins. Such behavior is often discussed in the context of the protein dynamical transition, yet its general physical origin remains unclear. Here, we show that fluctuating diffusivity within a Langevin framework naturally gives rise to an observation-time-induced crossover in translational diffusion: the effective diffusion coefficient exhibits a temperature-dependent change whose crossover point systematically shifts with the observation time. Through analytical and numerical analyses, we elucidate the mechanism of this crossover and identify the minimal conditions required for its emergence. Our results establish observation-time-induced crossover as a generic non-equilibrium phenomenon in systems with slowly relaxing mobility fluctuations. While distinct from internal dynamical transitions probed in neutron scattering, this framework provides a unified perspective that encompasses related finite-time crossover phenomena observed in hydrated proteins and other complex soft-matter systems.

Graphical abstract: Observation-time-induced crossover from fluctuating diffusivity

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Article information

Article type
Paper
Submitted
23 Dec 2025
Accepted
04 Mar 2026
First published
20 Mar 2026
This article is Open Access
Creative Commons BY license

Phys. Chem. Chem. Phys., 2026, Advance Article

Observation-time-induced crossover from fluctuating diffusivity

M. Shirataki and T. Akimoto, Phys. Chem. Chem. Phys., 2026, Advance Article , DOI: 10.1039/D5CP04999G

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