In the grand canonical ensemble, the system exchanges both energy and particles with a reservoir at fixed temperature and chemical potential . The probability of a particular many-body microstate , with energy and particle number , is its Boltzmann weight divided by the grand canonical partition function , where . The denominator normalizes ; a degeneracy is accounted for by counting distinct microstates, rather than changing an individual state's probability.
For noninteracting particles, specify a microstate by the occupation numbers of one-particle levels of energy . Then , so the Gibbs probability factorizes between levels. Put .
For fermions, the Pauli exclusion principle permits in each complete one-particle state, giving . Its mean occupancy is
the Fermi-Dirac distribution.
For bosons, , so the geometric sum is when . Differentiating that sum gives
the Bose-Einstein distribution. Finite-system convergence requires ; condensation is the limiting approach to the lowest energy with macroscopic ground-state occupation. Both quantum distributions reduce to when occupation is small. The quantities derived here are mean occupancies of states, rather than normalized probabilities over the set of one-particle energies.
Component chemical potentials. Define the per-spin quantum concentration . For a classical component with one-particle potential energy , the local Helmholtz free energy density is . Its derivative with respect to number density gives the full local chemical potential, including the magnetic energy. With the up state defined as the lower level,
The Bohr magneton is a magnetic moment; is an energy. The factor two for the two spin states is not already included in .
Total equilibrium chemical potential. If spin conversion is allowed, a particle can be added in either spin state at the same equilibrium free-energy cost. Thus
not their sum or zero. The total particle number, or a reservoir, fixes this common value; the supplied information does not specify a numerical chemical potential. A useful local expression is , with , whose density dependence is found below.
Why it is uniform and common. Moving a small number of one species from to changes the free energy by . If this difference were nonzero, a transfer could lower the free energy. Equilibrium under diffusion therefore requires each full chemical potential to be spatially constant. A spin flip transferring from down to up similarly changes free energy by , proving equality when spin relaxation is permitted. This is chemical equilibrium of a classical spin gas. Mere thermal contact at fixed separate spin populations would not enforce the latter equality; full spin equilibrium is the necessary assumption. A spatially varying magnetic field is balanced by a spatially varying density, not by a varying full chemical potential.
Magnetization. Invert the component equations at the common :
The two levels have moments and along the field. The magnetization, magnetic moment per unit volume, is therefore
Its SI units are . This expression neglects interactions and magnetic feedback of the gas on the specified external field.
High-temperature response. For , and , yielding
At fixed number density, this is the Curie law: the susceptibility with respect to is . The conventional dimensionless susceptibility with respect to is approximately when . At fixed , however, changes with temperature, so itself need not scale simply as . The moment per particle has the Curie behaviour; the density constraint must be stated.
Total density. Adding the two populations gives
For a finite container and fixed , normalization gives . In a weak field the leading density is uniform, with changes only of order . Particles preferentially occupy regions where the magnitude of the field lowers one of the spin energies, even though the common chemical potential remains uniform.
First solve the equation of state for the volume:
The Gibbs free energy has differential . At fixed temperature and particle number, integrate between the two pressures:
Consequently
Use , keeping both endpoint pressures fixed while differentiating the difference:
Equivalently, the Maxwell relation gives , whose pressure integral is the same result. These are the Gibbs free-energy change for a pressure-linear gas correction identities. The physical path requires and positive volume throughout. The correction has units of volume per particle, so each term in is an energy and each term in has units of energy per kelvin.
Fermion occupation and ordinary metallic heat capacity. The Fermi-Dirac distribution for a single-particle state is
At low temperature it changes appreciably only in an energy window of width of order about . If the full density of states is smooth and nonzero there, only about states change population. Each excited particle or hole carries energy of order relative to the Fermi surface, so is of order . Differentiation therefore gives .
More precisely, the fixed-number Sommerfeld expansion gives
Here includes all counted internal species. This argument requires and a density of states varying slowly across the thermal window; a band edge or vanishing density of states can change the power law.
Two-dimensional linear dispersion at zero chemical potential. Let count identical positive-energy branches, keeping the state-counting convention explicit. The number of wavevector states in a ring of radius is . With , this gives
At , the thermal energy of this branch is
The dimensionless integral is . Differentiating gives
This is the heat capacity for a two-dimensional linear fermion dispersion. A physical neutral particle–hole-symmetric Dirac cone also has electron holes in its filled negative-energy band. Their excitation energy gives an equal contribution, doubling for the same cone count. The scaling is unchanged. For a positive-energy-only gas, holding allows its mean particle number to vary; a neutral two-band surface instead maintains zero net excess charge as electron–hole pairs are thermally excited. These conventions should not be conflated when specifying an exact coefficient.
Nonzero chemical potential. The ordinary metallic regime is
The thermal window then lies far from the cone tip. Since , its fractional change across that window is only of order . Treating it as locally constant restores the Sommerfeld result . When is comparable to or larger than , the window probes the vanishing density of states near the tip and crosses toward the neutral behavior, provided the linear dispersion remains valid.
Bulk phonons and the surface-to-bulk comparison. For the topological insulator model, assume bulk electronic excitations are frozen out while the conducting surface remains active. In three dimensions, acoustic phonons have a density of modes proportional to . Normalize the Debye spectrum to modes:
The thermal part of the energy is
At , extending the upper integration limit to infinity introduces an exponentially small error. With and ,
Temperature-independent zero-point energy makes no contribution to this heat capacity. The requested ratio consequently scales as
For a fixed shape and composition, and , so the ratio grows as . Smaller samples and lower temperatures favor the surface contribution. It dominates if the dimensionless right-hand side, including its state-counting prefactor, exceeds unity. This is the surface-electron and bulk-phonon heat-capacity crossover.
The continuum electronic law also requires a thermal energy larger than the surface finite-size level spacing, of order . The phonon continuum has its own finite-size cutoff. Therefore dominance obtained by formally taking cannot always be inferred from the two continuum power laws alone.
There is a numerical-normalization qualification in the paper. Combining the explicit one-positive-branch result above with the conventional -mode Debye normalization gives ratio prefactor ; including electron holes doubles it. For , this is approximately before that doubling, rather than the supplied . The problem specifies neither a cone/spin multiplicity that equates these nor another mode normalization. Its supplied prefactor is therefore used as the stipulated approximation for the requested numerical estimate, rather than claimed as an exact consequence of the single-branch count.
Numerical estimate. A cubic sample of volume has side . Counting the conducting surface on all six faces gives
For one atom per cubic cell of side ,
Use and . Inserting the stated , and into the paper's supplied prefactor gives
Thus bulk phonons dominate at this temperature in this estimate. If only one face contributes, the ratio is ; if there are chemical atoms per unit cell, divide the corresponding estimate by . These geometrical and crystallographic factors are not supplied explicitly.
With the same prefactor and geometry, extrapolating would suggest equality near . However, the surface finite-size scale is already of order for this specimen. That extrapolated crossover lies outside the continuum electronic regime, so it is not a reliable prediction of the sample's ultimate lowest-temperature heat capacity.
Use the Gibbs-Duhem equation for a homogeneous, extensive, single-component thermodynamic phase:
At fixed temperature, this becomes , with number density . Separately, at fixed particle number,
The chain rule along the same isothermal process in the equation of state now gives
Consequently
This is isothermal compressibility from chemical-potential response. Since chemical potential has units of energy per particle, the right-hand side has units of volume per energy, or , as required. The derivation assumes a smooth bulk equation of state; changing the fractions of coexisting thermodynamic phases at fixed pressure needs separate treatment.
Canonical probabilities. A canonical ensemble describes a system of fixed particle number and fixed external parameters such as volume, weakly coupled to a much larger thermal reservoir. They exchange energy and reach thermal equilibrium, while the reservoir's temperature stays effectively constant. The interaction energy is negligible in the state counting. The combined isolated system is described by equal probabilities for its accessible microstates.
If its total energy is , the probability of a particular system microstate is proportional to the reservoir multiplicity at . Writing that multiplicity as , expand its entropy:
The large-reservoir limit suppresses the higher terms. Normalization therefore gives
The sum counts individual microstates; when grouping them by energy, their state degeneracies must be included. This is the canonical partition function.
Classical orientational heat capacity. Hold the magnetic field fixed. Orientations of the magnetic dipole moment have the solid angle measure . With , the angular partition function is
Choosing a normalized angular measure would remove , with no effect on the energy derivatives. Differentiating at fixed ,
The angular average is the Langevin function. Since ,
This is the heat capacity of a classical magnetic dipole, in for one magnetic moment. The word specific here refers to that single moment; independent magnetic moments have times this heat capacity. At the energy is independent of orientation and , obtained by the continuous limit. At fixed nonzero , the classical low-temperature limit instead gives .
Equipartition and its proof. The equipartition theorem states that an independent quadratic term in a classical Hamiltonian, with , contributes to its mean energy. One needs a canonical measure that factors as times the measure of the remaining variables, convergence of the integrals, and vanishing boundary terms. The coordinate must not be restricted by a thermally important hard boundary or a coupled constraint.
For , integration by parts gives
Integrate over all other variables and divide by . It follows that
The same reasoning applies to quadratic momenta among the canonical variables. It is the number of quadratic energy contributions that is counted, not an unrestricted count of coordinate labels.
Two soft orientational directions. When , the moment is concentrated near alignment. Introduce local Cartesian coordinates in the tangent plane and . To leading order,
The two quadratic terms each contribute , so
This agrees with the exact angular calculation. Treating alone as one Cartesian quadratic variable would miss the measure and the second tangent direction. There are no extra rotational kinetic terms in the stipulated Hamiltonian; adding such terms would be a different model.
Quantum spin one. The spin projections are , with . Put , where is the gyromagnetic ratio. The three energies are , irrespective of the sign of . Relative to the ground state they are . Thus, with ,
Differentiation, or the canonical energy fluctuation identity , gives
In the requested limit,
This spin-1 paramagnet has a nondegenerate ground state and a finite spectral gap. Excitations are exponentially rare, so its heat capacity tends to zero. Classical orientational equipartition assumed a continuum of arbitrarily small excitation energies; that assumption fails when . This is a change in the accessible state spectrum, not a violation of the equipartition theorem within its classical domain.
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.
Quantum ideal-gas statistics Created 2026-09-24 Updated 2026-11-05
Quantum ideal-gas statistics describes noninteracting identical particles while retaining the exchange rules of bosons or fermions. In thermal equilibrium, a one-particle state of energy has mean occupation
The minus sign is the Bose-Einstein distribution; the plus sign is the Fermi-Dirac distribution. A bosonic state permits arbitrary occupation, whereas Pauli exclusion principle restricts each fermionic state to zero or one particle. [ref]
The mean particle number and internal energy follow by summing and . When every occupation is small, both denominators reduce to the same exponential and reproduce Maxwell–Boltzmann statistics. Thus absence of interactions does not make a gas classical.
At fixed particle number and volume, a classical monatomic ideal gas has and . The canonical energy fluctuation identity therefore gives . Absolute fluctuations grow as , while relative fluctuations decrease as . A particle reservoir changes the fluctuation problem because energy and particle-number fluctuations are then correlated.
With the ground-state energy set to zero, the chemical potential of an ideal Bose gas cannot exceed zero. The limiting population of excited states as it approaches zero is the saturation particle number, provided the integral converges. Additional particles occupy the ground state macroscopically. For a three-dimensional uniform box, with thermal wavelength .
Two localized orbitals coupled by quantum tunnelling and on-site interactions give the smallest Bose-Hubbard model. A symmetric double-well potential with lowest one-particle energies has and common diagonal energy . At fixed total particle number, that common diagonal term is constant. A fixed-number two-mode condensate gives a simple variational method for this model, while stronger interactions can require occupation-correlated trial quantum states.
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.