Reference-Measure Freedom of the Effective Hamiltonian: From Stochastic Thermodynamics to the Macroscopic Limit

Abstract

The effective Hamiltonian (EH), also referred to as the potential of mean force or free-energy landscape, is widely used to describe equilibrium properties and slow dynamics in chemical and softmatter systems. However, the conventional EH has been argued to be ill-defined because it does not transform as a scalar under a change of coordinates. Here, we show that this apparent problem originates from an implicit change of the reference measure (gauge) with respect to which the equilibrium probability density is defined. We formulate the equilibrium measure and the Fokker--Planck equation (FPE) intrinsically on the manifold of slow variables and show that an EH is a scalar function defined with respect to a chosen gauge. Different EHs, including the conventional EH and the diffusion-dependent EH recently proposed in a Riemannian formulation, thus provide different gauge representations of the same intrinsic equilibrium measure and stochastic dynamics. We further show that the gauge choice has an operational meaning: different restraint protocols for the slow variables select different reference measures. Finally, when the equilibrium measure obeys a large-deviation principle in a macroscopic limit, differences among EHs associated with subleading gauges become subleading relative to the large-deviation speed. The leading part of the EH is then determined by the gauge-independent large-deviation rate function, and the corresponding deterministic dynamics is likewise gauge independent.