4.8 Article

Solvation in Space-time: Pretransition Effects in Trajectory Space

期刊

PHYSICAL REVIEW LETTERS
卷 120, 期 26, 页码 -

出版社

AMER PHYSICAL SOC
DOI: 10.1103/PhysRevLett.120.260602

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资金

  1. National Science Foundation [1507642]
  2. Department of Energy [DE-AC02-05CH11231]
  3. Department of Energy (FWP) [CHPHYS02]
  4. EPSRC [EP/M014266/1]
  5. EPSRC [EP/M014266/1] Funding Source: UKRI
  6. Direct For Mathematical & Physical Scien [1507642] Funding Source: National Science Foundation
  7. Division Of Chemistry [1507642] Funding Source: National Science Foundation

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We demonstrate pretransition effects in space-time in trajectories of systems in which the dynamics displays a first-order phase transition between distinct dynamical phases. These effects are analogous to those observed for thermodynamic first-order phase transitions, most notably the hydrophobic effect in water. Considering the (infinite temperature) East model as an elementary example, we study the properties of space-time solvation by examining trajectories where finite space-time regions are conditioned to be inactive in an otherwise active phase. We find that solvating an inactive region of space-time within an active trajectory shows two regimes in the dynamical equivalent of solvation free energy: an entropic small solute regime in which uncorrelated fluctuations are sufficient to evacuate activity from the solute, and an energetic large solute regime which involves the formation of a solute-induced inactive domain with an associated active-inactive interface bearing a dynamical interfacial tension. We also show that as a result of this dynamical interfacial tension there is a dynamical analog of the hydrophobic collapse that drives the assembly of large hydrophobes in water. We discuss the general relevance of these results to the properties of dynamical fluctuations in systems with slow collective relaxation such as glass formers.

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