Physlib.StatisticalMechanics.CanonicalEnsemble.Finite
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Finiteness of Canonical Ensembles is Preserved under Addition
#instIsFiniteProdHAddLet and be canonical ensembles. If both and satisfy the finiteness condition `IsFinite` (which implies that their respective spaces of microstates are finite and their associated measures are counting measures), then their additive composition also satisfies the `IsFinite` condition.
Finiteness of Canonical Ensembles is Preserved under Measurable Equivalence
#instIsFiniteCongrLet be a canonical ensemble. If satisfies the finiteness condition `IsFinite` (which implies that its microstate space is a finite type and its associated measure is the counting measure), then for any measurable equivalence , the ensemble (the ensemble re-indexed over the state space via ) also satisfies the `IsFinite` condition.
Finiteness of Canonical Ensembles is Preserved under Scalar Multiplication by a Natural Number
#instIsFiniteForallFinNsmulLet be a canonical ensemble. If satisfies the finiteness condition `IsFinite` (which implies that its microstate space is finite and its associated measure is the counting measure), then for any natural number , the -fold composition of the ensemble (denoted by `nsmul n 𝓒`) also satisfies the `IsFinite` condition.
A finite canonical ensemble has a finite measure
#instIsFiniteMeasureμOfIsFiniteIn a canonical ensemble that satisfies the finiteness condition `IsFinite` (which implies the microstate space is finite and the measure is the counting measure), the associated measure is a finite measure.
Non-emptiness of implies for finite canonical ensembles
#instNeZeroMeasureμOfIsFiniteOfNonemptyIn a canonical ensemble where the microstate space is finite and the measure is the counting measure (as specified by the `IsFinite` condition), if is non-empty, then the measure is non-zero ().
Shannon entropy
#shannonEntropyFor a canonical ensemble with a finite set of microstates, the Shannon entropy at a given temperature is defined by the formula \[ S = -k_B \sum_{i} p_i \ln p_i \] where is the Boltzmann constant and is the probability of the system being in microstate at temperature .
Mathematical Partition Function as a Finite Sum of Boltzmann Factors
#mathematicalPartitionFunction_of_fintypeFor a canonical ensemble with a finite set of microstates , the mathematical partition function at temperature is equal to the sum of the Boltzmann factors over all microstates: \[ Z(T) = \sum_{i \in \iota} e^{-\beta E_i} \] where is the energy of microstate and is the inverse temperature.
Partition Function for Finite Systems
#partitionFunction_of_fintypeFor a canonical ensemble with a finite set of microstates , the partition function at temperature is given by the sum of the Boltzmann factors over all microstates: \[ Z(T) = \sum_{i \in \iota} e^{-\beta E_i} \] where is the energy of microstate and is the inverse temperature.
The unnormalized Boltzmann measure of a microstate is in a finite system
#μBolt_of_fintypeFor a finite canonical ensemble at temperature , the unnormalized Boltzmann measure of a microstate is given by , where is the inverse temperature and is the energy associated with the state .
The Boltzmann Measure of a Finite Canonical Ensemble is Finite
#instIsFiniteMeasureμBoltOfIsFiniteConsider a canonical ensemble with a finite number of microstates. For any temperature , the Boltzmann measure (the measure where the weight of a state is given by , with ) is a finite measure.
The probability measure of a microstate equals in finite systems
#μProd_of_fintypeFor a finite canonical ensemble at temperature , the value of the normalized probability measure for a single microstate is equal to the probability of the system being in that state.
Mean energy formula for finite canonical ensembles
#meanEnergy_of_fintypeFor a canonical ensemble with a finite number of microstates at temperature , the mean energy is equal to the sum over all microstates of the energy of the microstate multiplied by its probability of occurrence: \[ \langle E \rangle(T) = \sum_{i} E_i p_i(T) \]
Shannon entropy for finite canonical ensembles
#entropy_of_fintypeFor a canonical ensemble with a finite set of microstates at temperature , the Shannon entropy is given by \[ S(T) = -k_B \sum_{i} p_i \ln p_i \] where is the Boltzmann constant and is the probability of the system being in microstate at temperature .
The probability of a microstate in a finite canonical ensemble is at most 1 ()
#probability_le_oneFor a canonical ensemble with a finite and non-empty set of microstates , the probability of the system being in microstate at temperature is less than or equal to 1.
Strict Positivity of the Mathematical Partition Function for Finite Ensembles
#mathematicalPartitionFunction_pos_finiteFor a canonical ensemble where the set of microstates is finite and non-empty, the mathematical partition function is strictly positive for any temperature . That is, \[ Z_{\text{math}}(T) > 0. \] The mathematical partition function corresponds to the integral of the Boltzmann factor over the microstate space, which reduces to the sum in the finite case.
Strict Positivity of the Partition Function for Finite Ensembles
#partitionFunction_pos_finiteFor a canonical ensemble where the set of microstates is finite and non-empty, the physical partition function is strictly positive for any temperature . That is, \[ Z(T) > 0. \] In this finite discrete case, the partition function reduces to the sum of Boltzmann factors , where . Since each exponential term is positive and the set of microstates is non-empty, the sum is strictly positive.
for Finite Canonical Ensembles
#probability_nonneg_finiteFor a canonical ensemble where the set of microstates is finite and non-empty, the probability of the system being in a microstate at temperature is non-negative. That is, \[ P(i; T) \ge 0. \] In this finite context, the probability is given by the Boltzmann distribution , where is the energy of the state, is the inverse temperature, and is the partition function.
The sum of probabilities in a finite canonical ensemble equals 1
#sum_probability_eq_oneFor a canonical ensemble with a finite and non-empty set of microstates , the sum of the probabilities of all microstates at a given temperature is equal to 1: \[ \sum_{i \in \iota} P(i; T) = 1 \] where denotes the probability of the system being in microstate at temperature .
Shannon Entropy is Non-negative
#entropy_nonnegFor a canonical ensemble where the set of microstates is finite and non-empty, the Shannon entropy at temperature is non-negative. That is, \[ S \ge 0, \] where the Shannon entropy is defined as , is the Boltzmann constant, and is the probability of the system being in microstate .
Shannon Entropy Equals Differential Entropy in Finite Canonical Ensembles
#shannonEntropy_eq_differentialEntropyFor a finite canonical ensemble at temperature with a discrete set of microstates , the Shannon entropy , defined by \[ S_{\text{Shannon}}(T) = -k_B \sum_{i \in \iota} p_i \ln p_i \] (where is the Boltzmann constant and is the probability of the system being in microstate ), is equal to the differential entropy of the system.
for Finite Canonical Ensembles
#thermodynamicEntropy_eq_shannonEntropyFor a canonical ensemble with a finite set of microstates (satisfying the `IsFinite` condition), the thermodynamic entropy at temperature is equal to the discrete Shannon entropy : \[ S_{\text{thermo}}(T) = S_{\text{Shannon}}(T) \] where the Shannon entropy is defined as , is the Boltzmann constant, and is the probability of the system being in microstate at temperature . In this finite case, all semi-classical correction factors vanish because the degrees of freedom and the phase space unit is .
Mean Square Energy for Finite Systems:
#meanSquareEnergy_of_fintypeFor a canonical ensemble with a finite set of microstates at temperature , the mean square energy is equal to the sum over all microstates of the squared energy of each state weighted by its probability: \[ \langle E^2 \rangle = \sum_{i \in \iota} E_i^2 p_i(T) \] where is the energy of microstate and is the probability of the system being in that state.
Energy Variance for Finite Systems:
#energyVariance_of_fintypeFor a canonical ensemble with a finite and non-empty set of microstates at temperature , the energy variance is equal to the mean of the squared energies weighted by their probabilities minus the square of the mean energy: \[ \text{Var}(E) = \left( \sum_{i \in \iota} E_i^2 p_i(T) \right) - \langle E \rangle^2 \] where represents the energy of microstate , is the probability of the system being in state at temperature , and is the mean energy of the system.
Partition function for finite systems
#mathematicalPartitionFunctionBetaRealFor a canonical ensemble with a finite set of microstates , the partition function is defined as a function of the inverse temperature by the sum: \[ Z(\beta) = \sum_{i \in \iota} e^{-\beta E_i} \] where represents the energy of microstate .
The partition function is strictly positive () for finite non-empty systems
#mathematicalPartitionFunctionBetaReal_posFor a finite canonical ensemble where the set of microstates is non-empty, the partition function is strictly positive for any inverse temperature parameter .
Boltzmann probability
#probabilityBetaRealFor a canonical ensemble with a finite set of microstates , the Boltzmann probability of a microstate at inverse temperature is defined as the ratio: \[ p_i(\beta) = \frac{e^{-\beta E_i}}{Z(\beta)} \] where represents the energy of microstate and is the partition function of the system.
Mean energy in a finite canonical ensemble
#meanEnergyBetaRealFor a canonical ensemble with a finite set of microstates , the mean energy as a function of the inverse temperature parameter is defined as the expected value of the energy over all microstates: \[ U(\beta) = \sum_{i \in \iota} E_i p_i(\beta) \] where is the energy of microstate , and is the Boltzmann probability of microstate , given by: \[ p_i(\beta) = \frac{e^{-\beta E_i}}{Z(\beta)} \] where is the partition function of the system.
General Mean Energy equals Finite Sum Mean Energy
#meanEnergy_Beta_eq_finiteFor a canonical ensemble with a finite set of microstates , the general measure-theoretic mean energy at a positive inverse temperature is equal to the finite sum definition of mean energy , which is given by the expected value: \[ U(\beta) = \sum_{i \in \iota} E_i p_i(\beta) \] where is the energy of microstate and is the Boltzmann probability of that microstate.
Mean Energy is Differentiable for Finite Systems
#differentiable_meanEnergyBetaRealFor a canonical ensemble with a finite and non-empty set of microstates , the mean energy is a differentiable function of the inverse temperature parameter . The mean energy is defined as: \[ U(\beta) = \sum_{i \in \iota} E_i p_i(\beta) \] where is the energy of microstate , and is the Boltzmann probability of that state.
is Differentiable
#differentiable_mathematicalPartitionFunctionBetaRealFor a finite canonical ensemble , the partition function is differentiable with respect to the inverse temperature parameter .
Numerator of the mean energy
#meanEnergyNumeratorFor a finite canonical ensemble with microstates indexed by and corresponding energies , this function maps the inverse temperature parameter to the sum . This sum represents the numerator used in the definition of the mean energy , where is the partition function.
The mean energy numerator is differentiable
#differentiable_meanEnergyNumeratorFor a finite canonical ensemble with microstates indexed by and corresponding energies , the numerator of the mean energy, defined as the function for , is differentiable with respect to .
For a finite canonical ensemble with microstates indexed by and corresponding energies , let be the partition function and be the mean energy numerator. For any inverse temperature , the derivative of the partition function with respect to is equal to the negative of the mean energy numerator:
Derivative of the Mean Energy Numerator
#deriv_meanEnergyNumeratorFor a finite canonical ensemble with microstates indexed by and corresponding energies , let denote the mean energy numerator. For any inverse temperature , the derivative of this numerator with respect to is given by
Derivative of Mean Energy
#deriv_meanEnergyBetaRealFor a finite canonical ensemble with microstates indexed by and corresponding energies , let be the mean energy and be the Boltzmann probability of microstate at inverse temperature . The derivative of the mean energy with respect to is given by the expression: where is the square of the mean energy and the sum represents the expected value of the squared energy .
for Finite Canonical Ensembles
#derivWithin_meanEnergy_Beta_eq_neg_varianceFor a canonical ensemble with a finite set of microstates , let be the mean energy as a function of the inverse temperature . For any positive temperature with corresponding inverse temperature , the derivative of the mean energy with respect to is equal to the negative of the energy variance at that temperature: where the energy variance is defined as .
Fluctuation-Dissipation Theorem for Finite Systems:
#fluctuation_dissipation_theorem_finiteFor a canonical ensemble with a finite set of microstates , let be a strictly positive temperature. The heat capacity of the system is related to the variance of the energy fluctuations by the expression: where is the Boltzmann constant and .
