Ionic fluctuations in finite volumes: fractional noise and hyperuniformity

Noether invariance in statistical mechanics provides fundamental connections between the symmetries of a physical system and its conservation laws and sum rules. The latter are exact identities that involve statistically averaged forces and force correlations and they are derived from statistical mechanical functionals. However, the implications for more general observables and order parameters are unclear. Here, we demonstrate that thermally averaged classical phase space functions are associated with exact hyperforce sum rules that follow from translational Noether invariance. Both global and locally resolved identities hold and they relate the mean gradient of a phase-space function to its negative mean product with the total force. Similar to Hirschfelder’s hypervirial theorem, the hyperforce sum rules apply to arbitrary observables in equilibrium. Exact hierarchies of higher-order sum rules follow iteratively. As applications we investigate via computer simulations the emerging one-body force fluctuation profiles in confined liquids. These local correlators quantify spatially inhomogeneous self-organization and their measurement allows for the development of stringent convergence tests and enhanced sampling schemes in complex systems.

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Ionic fluctuations in finite volumes: fractional noise and hyperuniformity

Abstract: Observing finite regions of a bigger system is a common experience, from microscopy to molecular simulations. In the latter especially, there is ongoing interest in predicting thermodynamic properties from tracking...

Cited by 4 publications

References 111 publications

The known-unknowns of anomalous underscreening in concentrated electrolytes

The known-unknowns of anomalous underscreening in concentrated electrolytes

Towards local tracking of solvated metal ions at solid-liquid interfaces

Hyperforce balance via thermal Noether invariance of any observable

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