Roy Podgaetsky | Searcharxiv

arXiv2026

Time-delayed feedback turns Arrhenius escape logarithmic

Thermal escape is governed by the Arrhenius law, where the mean escape time scales exponentially with the barrier height. We show that the non-Markovianity induced by time-delayed feedback in the confining force removes this exponential scaling. Beyond a threshold set by the curvature of the minimum, the delay destabilizes the well, and the thermal noise seeds an instability that is subsequently amplified deterministically to the boundary leading to \textit{slingshot} escape trajectories. The escape time becomes logarithmic in the barrier, its fluctuations follow a Gumbel law, and an optimal delay enables escape faster than free diffusion. Our results propose time delay as a tunable and experimentally feasible control parameter for accelerating activated processes.

cond-mat.stat-mech↗

arXiv2022

Collective Variables for Conformational Polymorphism in Molecular Crystals

Controlling polymorphism in molecular crystals is crucial in the pharmaceutical, dye, and pesticide industries. However, its theoretical description is extremely challenging, due to the associated long timescales ($ > 1 \, \mu s$). We present an efficient procedure for identifying collective variables that promote transitions between conformational polymorphs in molecular dynamics simulations. It involves applying a simple dimensionality reduction algorithm to data from short ($\sim ps$) simulations of the isolated conformers that correspond to each polymorph. We demonstrate the utility of our method in the challenging case of the important energetic material, CL-20, which has three anhydrous conformational polymorphs at ambient pressure. Using these collective variables in Metadynamics simulations, we observe transitions between all solid polymorphs in the biased trajectories. We reconstruct the free energy surface and identify previously unknown defect and intermediate forms in the transition from one known polymorph to another. Our method provides insights into complex conformational polymorphic transitions of flexible molecular crystals.

physics.chem-ph↗