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Confined coupled quadratic canonical systems
Finite classical continuous canonical model with positive diagonal mass matrix, strictly positive stiffness matrix, fixed positive action reference and beta>0; the Lebesgue product calculations assume ACω; no unpinned zero mode or empirical equilibration claim.
Statement
Assume as defined in The Axiom of Countable Choice () for the Euclidean Lebesgue product measure used below. Let , let with in kg, and let be a real symmetric positive-definite stiffness matrix with entries in J m. For displacement in metres and momentum in kg m s, define Adopt the canonical probability density proportional to relative to , where has units J and the fixed action reference has units J s. Under the preparation of Declared example preparations and thermodynamic interpretation, the dimensionless partition function and moments are The model mean energy is . With in J K and in K from Declared example preparations and thermodynamic interpretation, so that , define the fixed-parameter heat-capacity response by It has units J K. This model has no volume variable, so is not a fixed-volume derivative.
Facts & Assumptions
Given: , , positive diagonal, symmetric positive definite, , fixed , and the displayed continuous-coordinate canonical model.
Declared example preparations and thermodynamic interpretation: in each named model with finite positive , the canonical probability is relative to the specified reference; and the fixed-reference thermodynamic interpretation is adopted separately from the probability preparation.
Gaussian covariance for positive quadratic forms and a boundary counterexample: assuming , for a symmetric positive-definite quadratic form on , the normalized Gaussian integral is , with mean zero and covariance .
Under , Euclidean phase-space Lebesgue measure is the product of the and Lebesgue measures; Tonelli factors nonnegative densities and Fubini factors their integrable moments (On Borel subsets of R^{m+n}, the product lambda_m times lambda_n agrees with lambda_{m+n}, Tonelli's theorem for nonnegative measurable functions on a sigma-finite product, Fubini's theorem for L^1 functions on a sigma-finite product).
The canonical density is a model preparation, not a claim that an isolated trajectory equilibrates or that a laboratory realizes this law.
Proof
By [F1], the phase-space weight factors as . The product-measure identity and Tonelli [F3] justify multiplying the two nonnegative Lebesgue integrals. Applying [F2] to the factor gives normalization and covariance .
The momentum quadratic form has symmetric positive-definite matrix . Applying [F2] with gives its integral and covariance of equal to .
Multiplying the two integrals from steps 1.1–1.2 and dividing by the reference factor gives . The phase-space Lebesgue measure is the product of its and factors by [F3]; the normalized canonical density therefore factors into independent and laws. Each factor is even, so its mean is zero, and its covariance is the one computed in steps 1.1–1.2.
By [F1], taking the expectation of and summing the diagonal traces of the two covariance identities gives The adopted relation makes . Holding the model parameters fixed therefore gives , with units J K.
Remarks
Positive definiteness is a confinement condition. If has a translation zero mode, the full-space configurational integral diverges and this normalized ensemble does not exist without an additional constraint or confinement.
Depends on
The Axiom of Countable Choice ()
Declared example preparations and thermodynamic interpretation
Gaussian covariance for positive quadratic forms and a boundary counterexample
On Borel subsets of R^{m+n}, the product lambda_m times lambda_n agrees with lambda_{m+n}
Tonelli's theorem for nonnegative measurable functions on a sigma-finite product
Fubini's theorem for L^1 functions on a sigma-finite product