Phase coexistence implies nondifferentiability of the pressure

If multiple Gibbs phases exist at the same parameters with different order-parameter expectations, the thermodynamic pressure is not differentiable in the conjugate field.
Phase coexistence implies nondifferentiability of the pressure

Consider a lattice system in finite volume Λ\Lambda with an external field hh coupled linearly to an extensive order parameter AΛA_\Lambda: HΛ,h=HΛ,0hAΛH_{\Lambda,h}=H_{\Lambda,0}-h\,A_\Lambda. Let ZΛ(β,h)Z_\Lambda(\beta,h) be the and pΛ(β,h)=1ΛlogZΛ(β,h)p_\Lambda(\beta,h)=\frac{1}{|\Lambda|}\log Z_\Lambda(\beta,h) the finite-volume .

Assume the thermodynamic limit pressure exists:

p(β,h)=limΛZdpΛ(β,h), p(\beta,h)=\lim_{\Lambda\uparrow\mathbb{Z}^d} p_\Lambda(\beta,h),

with the limit taken along a standard van Hove sequence.

Statement

The function hp(β,h)h\mapsto p(\beta,h) is convex. Moreover:

  • If p(β,h)p(\beta,h) is differentiable at a given hh, then every μ\mu at parameters (β,h)(\beta,h) has the same order-parameter density

    a(μ)=limΛZd1ΛEμ[AΛ], a(\mu)=\lim_{\Lambda\uparrow\mathbb{Z}^d}\frac{1}{|\Lambda|}\,\mathbb{E}_\mu[A_\Lambda],

    and it is fixed by the derivative:

    a(μ)=1βhp(β,h). a(\mu)=\frac{1}{\beta}\,\partial_h p(\beta,h).
  • Conversely, if there exist two Gibbs measures μ1,μ2\mu_1,\mu_2 at the same (β,h)(\beta,h) with

    a(μ1)a(μ2), a(\mu_1)\neq a(\mu_2),

    then p(β,h)p(\beta,h) is not differentiable at hh; equivalently, the left and right derivatives satisfy

    hp(β,h)<h+p(β,h). \partial_h^- p(\beta,h) < \partial_h^+ p(\beta,h).

    This is a first-order transition / phase coexistence signature in the sense of .

In the important special case AΛ=MΛA_\Lambda=M_\Lambda (magnetization), this connects coexistence of distinct magnetized phases to a cusp in hp(β,h)h\mapsto p(\beta,h).

Key hypotheses

  • Linear field coupling hAΛ-hA_\Lambda.
  • Existence of the thermodynamic limit pressure p(β,h)p(\beta,h).
  • Existence of at least two infinite-volume Gibbs measures at the same (β,h)(\beta,h) with different a(μ)a(\mu) (for the “coexistence \Rightarrow nondifferentiability” direction).

Conclusions

  • Differentiability of p(β,h)p(\beta,h) at hh rules out coexistence of Gibbs states with different densities of the conjugate order parameter.
  • Coexistence forces a non-single-valued “slope” at hh (a nontrivial subgradient), hence nondifferentiability.
  • In convex-analysis language (see ), multiple coexisting values of a(μ)a(\mu) correspond to a nontrivial subdifferential of p(β,)p(\beta,\cdot) at hh.