Availability and total entropy. The reservoir changes by and . Its particle number and the system's particle number are fixed. The reservoir's first law of thermodynamics therefore gives
Add the system's entropy change. Because are constant,
Thus define the availability
An additive constant in is immaterial; its value above the equilibrium reference is the exergy. The Second law of thermodynamics gives , hence . A stable equilibrium maximizes total entropy over the allowed variations and therefore minimizes . The environmental enter this definition even when the system has not yet reached their values. Because both thermal and mechanical exchanges are allowed, equilibrium here includes mechanical balance; equality of temperatures alone does not ensure the minimum.
Probability and curvature. For a fixed value of a macroscopic coordinate , let count the compatible system microstates. The product of the system and reservoir multiplicities is
All factors independent of enter a normalization constant, giving
Here is the constrained or effective availability for this coordinate, including the multiplicity of any eliminated variables. A nonuniform coordinate measure must likewise be retained or incorporated in that effective availability.
At a stable interior minimum, and . Its Taylor expansion gives
Keeping the quadratic term yields a normal distribution,
This is availability curvature and equilibrium fluctuations. The quoted fluctuation formula holds at quadratic order in the Gaussian fluctuation approximation; it is not an exact identity for an arbitrary nonlinear . Higher terms can shift the mean away from its most probable value .
Bubble equilibrium. Keep the number of air molecules fixed and include the surface energy in the system's total internal energy. For constant surface tension , this contribution is , with no surface entropy under the stated approximation. Its differential is
Hence
Independent thermal and volume variations give and
The air pressure is evaluated at ; since the bubble is closed it generally depends on volume, so this equation is implicit until an air equation of state is supplied. For a sphere, , , and the pressure jump becomes , the Young–Laplace equation for a single gas–liquid interface. There is no second surface as in a thin soap film.
Isothermal volume fluctuations. With the air maintained at , eliminate its entropy in favor of its Helmholtz free energy:
The identity gives
Using the curvature result,
These are the volume fluctuations of a closed gas bubble. Stability requires the denominator to be positive. The negative surface contribution reflects the concavity of ; gas compression supplies the positive restoring curvature. For ideal air, , and mechanical equilibrium reduces the denominator to
The units are consistent: is pressure, so has units , the units of a volume variance. Holding externally fixed while varying would remove the gas-compression term and change this stability problem; that is not the fixed-particle-number situation here.
Numerical size of the fluctuations. The volume conversion is important:
Use the specified , and . Then
With the Boltzmann constant ,
Thus the fractional root mean square fluctuation and fractional variance are respectively
The absolute root mean square fluctuation is . The very small fractional value supports the local Gaussian fluctuation approximation. This estimate neglects exchange of dissolved air, variations of surface tension, shape fluctuations and temperature fluctuations, consistently with the prescribed fixed-number, isothermal bubble model.
Occupation and the two-dimensional Fermi energy. For an independent single-particle state, the Fermi-Dirac distribution is
The chemical potential enforces the chosen mean particle number through , including spin states in the sum. It is common to all states in particle-exchange equilibrium and must generally change with temperature or field when the total mean number is held fixed. At zero temperature, the distribution becomes a Heaviside step function at the Fermi energy.
Let the sample area be and let be its internal spin spin degeneracy. In the continuum limit, filling the disk gives
Therefore
For spin-half fermions with both spin states available, and ; for a spin-polarized gas . The question does not specify the area or spin degeneracy, so these conventions must be stated rather than extracting an energy from alone. Although the original text calls momentum, the supplied dispersion makes it a wave vector; physical momentum is . The result agrees with the constant two-dimensional free-electron density of states. Discrete level spacings in a finite sample would require a specified boundary spectrum.
One level occupied on average. Write and . The two mean spin occupations are
Imposing gives , hence . Thus, for every positive temperature,
The total magnetic moment is . Consequently
This is the grand-canonical spin susceptibility of a half-filled single level. Empty, singly occupied and doubly occupied orbital states are allowed in the grand canonical ensemble. At zero field, the singly occupied configurations together have probability , explaining the factor of two relative to one permanent spin-half moment. If exactly one Electron were required at all times, a canonical two-state partition function would instead give and . That different answer does not implement the stated average-number constraint.
Density-of-states formula for the susceptibility. Here is the zero-field single-spin density of states. Regard its argument as the full spin-shifted energy. The shifted functions are , so
The total number is even in ; thus at fixed total number on a smooth branch. More directly, terms from cancel in the spin difference because the two densities coincide at zero field. To first order,
It follows that
For a physical energy band, take to vanish below its lower edge. Provided the endpoint term vanishes, integration by parts also gives
This form displays the positive response and the narrow thermal window around . A sharp band edge is included by the corresponding distributional derivative in the first expression. The susceptibility defined here is the derivative of total magnetic moment with respect to , with units ; it is not automatically a dimensionless SI volume susceptibility. A density-of-states convention per unit volume likewise gives a response per unit volume. These are the field conventions for magnetic susceptibility.
Chemical potential at fixed number. Define the integrated single-spin state count
The probability kernel has unit integral, mean , and variance . Using integration by parts,
Expand about . The linear term integrates to zero, while gives
This is the number form of the Sommerfeld expansion. Since at zero temperature, set with :
Therefore
The coefficient can be obtained directly. With ,
For example, the sum follows by expanding on , using the evenness of the kernel and integrating each exponential. Thus . A density of states increasing with energy gives a downward quadratic chemical-potential shift. For the constant two-dimensional density of states that shift vanishes to this order; a finite lower band edge still allows exponentially small corrections.
Low-temperature susceptibility at fixed number. Apply the same kernel expansion to itself:
The shift of must be retained in the first term. Writing and similarly for its derivatives,
Consequently
This is the fixed-number low-temperature Pauli susceptibility. The contribution is thermal broadening at fixed chemical potential; the contribution enforces fixed total number. Both are needed. If the density of states were instead defined with both spin directions included, the prefactor would be absorbed into that definition. Only the spin response has been calculated; no orbital magnetic response is included.
The expansion assumes , sufficient smoothness near the Fermi energy, and a temperature small compared with the energy scale over which changes or encounters a band edge. It does not apply unmodified at a singular density of states. For the ideal two-dimensional parabolic band, , so the leading Pauli response is temperature independent, consistently with the earlier state count.
For fixed particle number and temperature, a bubble with surface tension and area has effective availability . Its stationary condition is . Its curvature is . Positive curvature is required for stable Gaussian fluctuation approximation. The variance follows from availability curvature and equilibrium fluctuations. For an ideal gas, the restoring denominator becomes for positive . Treating the internal pressure as externally fixed instead of fixing the gas particle number changes the stability problem.