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Grand responses in beta and chemical potential

Physical scope

Grand preparation on a countable disjoint union with local uniform exponential-moment envelopes for energy and particle number; all derivatives are finite-model derivatives.

Statement

For the grand preparation Grand canonical particle-exchange preparation, write let G and mphys be its disjoint-union state space and reference, define H(N,z):=HN(z) on sector ΓN, and define the particle-number statistic N(N,z):=N. Write mN for mNphys in the sector sum, so Ξ(β,μ)=∑N∫e−βHN+βμN dmN. Here β>0 and μ has units J per particle. Let SH:={(N,z)∈G:HN(z)<∞}, restrict mphys to this measurable set, and compute energy moments there; the grand weight is zero outside it and the restricted measure is sigma-finite. Assume the local envelopes of Dominated exponential normalization and covariance hold uniformly on this restricted space for its finite-valued sufficient statistics H and N; expectations written ⟨N⟩ refer to N. Then ∂ηlog⁡Ξ=⟨N⟩,∂η2log⁡Ξ=Var⁡(N),η=βμ, and, at fixed μ, −∂βlog⁡Ξ=⟨H−μN⟩,∂μ⟨N⟩=βVar⁡(N),∂β⟨N⟩∣μ=−Cov⁡(N,H−μN). The covariance is computed in the full number-exchanging state. No fixed-N derivative or thermodynamic-limit identification is implied.

Facts & Assumptions

Given: A finite positive grand normalizer and uniform local exponential moment bounds for the joint energy and number variables.

[A1]

The adopted grand density is Ξ−1e−β(H−μN) with positive finite normalizer (Grand canonical particle-exchange preparation). In addition, assume the local common exponential-moment envelopes on SH stated above; these are hypotheses of this theorem, not consequences of the preparation postulate.

[A2]

β=(kBT)−1>0 and μ is held fixed in the β response (SI quantities and unit conventions).

[F1]

Under common envelopes, logarithmic derivatives are means and covariances (Dominated exponential normalization and covariance).

Proof

Given: [A1]–[A2] and the grand-law and exponential-differentiation interfaces [F1].

1.1A1F1algebra

Set θ=(−β,η) and X=(H∣SH,N) in [F1] on the restricted reference space. Its first and second derivatives give ∂ηlog⁡Ξ=⟨N⟩, ∂η2log⁡Ξ=Var⁡(N), and ∂βlog⁡Ξ∣η=−⟨H⟩. At fixed μ, the coordinate relation η=βμ makes the derivative direction (−1,μ) in (θH,θN) coordinates, so ∂βlog⁡Ξ∣μ=−⟨H−μN⟩.

2.1A1A2F1step 1.1algebra∎

At fixed β, ∂μ=β∂η, so ∂μ⟨N⟩=β∂η2log⁡Ξ=βVar⁡(N). At fixed μ, differentiating the first mean along direction (−1,μ) gives ∂β⟨N⟩∣μ=−Cov⁡(N,H)+μVar⁡(N)=−Cov⁡(N,H−μN). All terms are finite by [A1], proving the responses.

Depends on

Dependency tree · 2 levels

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