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Pressure and its physical terms. Solving the molar Van der Waals equation for pressure givesThe excluded-volume parameter $b$ reduces the volume available for translational motion, raising the kinetic pressure relative to $RT/V$. The attraction parameter $a$ lowers the pressure because attractive interactions reduce the momentum transferred to the boundary. This mean-field model treats $a,b$ as temperature-independent material constants. For one mole, $V$ is the sample volume with the molar amount already fixed; $b$ has units of that volume and $a$ of pressure times volume squared.

volume dependence of entropy. The Helmholtz free energy has differential $dF=-SdT-PdV$. Equality of mixed derivatives yields the Maxwell relationFor $a=0$ this derivative is $R/(V-b)$, givingEquivalently, $S=R\ln (V-b)+f(T)$ with a common reference volume understood inside the logarithm. The equation of state fixes this volume dependence, not the otherwise unspecified function of temperature.

Excess entropy at fixed volume and temperature. The ideal gas has $(\partial S_{\mathrm{id}}/\partial V{)}_T=R/V$. ThereforeIntegrate from infinite volume, where the entropy difference is specified to vanish:It is negative because excluding configurations reduces the accessible state count. It tends to zero as $V\to \infty$ and has leading dilute limit $-Rb/V$. This is the entropy excess of a van der Waals gas.

Effect of attraction. Restoring a temperature-independent $a$ changes the pressure by $-a/V^2$, but not its derivative with respect to temperature. With the same infinite-volume entropy reference, it therefore does not change $\Delta S^{\mathrm{ex}}$ at fixed $V,T$. This can also be seen fromThe attraction affects internal energy and the equilibrium volume, so it can affect entropy indirectly when different state points are compared. If $a$ were temperature dependent, its derivative would contribute directly to the entropy; that is outside the stipulated constant-parameter model.

Coexistence isotherm. Below the Van der Waals critical point, the formal homogeneous isotherm has a local minimum and maximum. Its middle branch has $\partial P/\partial V>0$, hence negative isothermal compressibility, and is mechanically unstable. Portions of the negative-slope branches can be metastable rather than globally stable. The equilibrium isotherm replaces the loop between liquid volume $V_l$ and vapour volume $V_g$ by a constant saturation pressure $P_s$. The two volume are fixed byThe Maxwell equal-area construction expresses equality of the two phases' chemical potentials. Intermediate total volume are mixtures: changing the vapour fraction changes total volume at the same pressure, rather than following the unstable homogeneous curve. The spinodals are the turning points of the formal isotherm; they are distinct from the coexistence endpoints.

Dense-phase volume at low temperature. At a general subcritical temperature, the two coexistence equations above must be solved together. For this equation of state the area condition is explicitlyThis supplies an exact implicit determination of the liquid volume even when a simple closed form is unavailable.

For the asymptotically low-temperature limit, put $\tau =RTb/a\ll 1$. The liquid is dense, $V_l\simeq b$, while the vapour is dilute, $P_s{V}_g\simeq RT$ and $V_g\gg V_l$. The area condition then givesThus the vapour volume grows exponentially in $1/\tau$, and the saturation pressure is exponentially small. It is consequently consistent to neglect $P_s$ in the liquid equation to algebraic order in $\tau$:Choose the root near $b$, not the large-volume zero-pressure root:Expanding gives the leading requested dense-phase behavior,This is the low-temperature liquid volume of a van der Waals gas. Setting $P_s=0$ is an asymptotic approximation, not an exact coexistence condition at every temperature below $T_c$. The figure illustrates generic subcritical coexistence; its finite-temperature liquid volume is determined by the full equal-area equations. The van der Waals liquid also ceases to be a realistic description at sufficiently low physical temperature, where other phases or quantum effects can matter.

First solve the equation of state for the volume:The Gibbs free energy has differential $dG=-SdT+Vdp+\mu dN$. At fixed temperature and particle number, integrate $dG=Vdp$ between the two pressures:ConsequentlyUse $S=-(\partial G/\partial T{)}_{p,N}$, keeping both endpoint pressures fixed while differentiating the difference:Equivalently, the Maxwell relation $(\partial S/\partial p{)}_{T,N}=-(\partial V/\partial T{)}_{p,N}$ gives $-N{k}_B/p+N{A}^{\prime }(T)$, 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 $p_0,p_1>0$ and positive volume throughout. The correction $A(T)$ has units of volume per particle, so each term in $\Delta G$ is an energy and each term in $\Delta S$ has units of energy per kelvin.

Particles within each species are indistinguishable, while the two species are physically distinguishable and their numbers are fixed. Independence makes the canonical partition function factor by species:Since $Z_1\propto T^{3/2}$ at fixed volume, $U=-{\partial }_{\beta }\ln Z=3N{k}_{B}T/2$. The canonical entropy is thereforeFor large species populations, Stirling's approximation gives the equivalent Sackur-Tetrode equation formFor structureless particles with the same translational partition function, $Z_1=V/{\lambda }^3$, where $\lambda$ is their common thermal de Broglie wavelength. More generally the supplied common constant factor in $Z_1$ should be retained in the entropy.

Writing $x_i=N_i/N$ separates the total-number contribution from the composition term:The last term is the entropy of mixing relative to separated ideal components at the same temperature and pressure. This is the entropy of a two-species classical ideal gas. Artificially labeling otherwise identical chemical atoms would not justify dividing by separate factorials or adding a mixing entropy. The pure-species limit is obtained by $x\ln x\to 0$.

Fermion occupation and ordinary metallic heat capacity. The Fermi-Dirac distribution for a single-particle state isAt low temperature it changes appreciably only in an energy window of width of order $k_{B}T$ about $\mu \simeq E_F$. If the full density of states $D(E)$ is smooth and nonzero there, only about $D(E_F)k_{B}T$ states change population. Each excited particle or hole carries energy of order $k_{B}T$ relative to the Fermi surface, so $U(T)-U(0)$ is of order $D(E_F)(k_{B}T{)}^2$. Differentiation therefore gives $C_{\mathrm{el}}\propto T$.

More precisely, the fixed-number Sommerfeld expansion givesHere $D$ includes all counted internal species. This argument requires $k_{B}T\ll E_F$ 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 $g$ count identical positive-energy branches, keeping the state-counting convention explicit. The number of wavevector states in a ring of radius $k$ is $gA(2\pi kdk)/(2\pi {)}^2$. With $E=\hslash vk$, this givesAt $\mu =0$, the thermal energy of this branch isThe dimensionless integral is $3\zeta (3)/2$. Differentiating givesThis 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 $C_{+}$ for the same cone count. The $T^2$ scaling is unchanged. For a positive-energy-only gas, holding $\mu =0$ 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 isThe thermal window then lies far from the cone tip. Since $D(E)\propto E$, its fractional change across that window is only of order $k_{B}T/\mu$. Treating it as locally constant restores the Sommerfeld result $C_{\mathrm{el}}\propto D(\mu )T\propto \mu T$. When $k_{B}T$ is comparable to or larger than $\mu$, the window probes the vanishing density of states near the tip and crosses toward the neutral $T^2$ 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 ${\omega }^2$. Normalize the Debye spectrum to $3N$ modes:The thermal part of the energy isAt $T\ll {\Theta }_D$, extending the upper integration limit to infinity introduces an exponentially small error. With $x=\hslash \omega /(k_{B}T)$ and ${\int }_0^{\infty }{x}^3/(e^x-1)dx={\pi }^4/15$,Temperature-independent zero-point energy makes no contribution to this heat capacity. The requested ratio consequently scales asFor a fixed shape and composition, $A\propto L^2$ and $N\propto L^3$, so the ratio grows as $1/(LT)$. 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 $\hslash v/L$. The phonon continuum has its own finite-size cutoff. Therefore dominance obtained by formally taking $T\to 0$ 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 $3N$-mode Debye normalization gives ratio prefactor $15g\zeta (3)/(16{\pi }^5)$; including electron holes doubles it. For $g=1$, this is approximately $0.00368$ before that doubling, rather than the supplied $5/(12{\pi }^2)\simeq 0.0422$. 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 $1\mathrm{m}{\mathrm{m}}^3$ has side $L=10^{-3}\mathrm{m}$. Counting the conducting surface on all six faces givesFor one atom per cubic cell of side $a=1.5\times 10^{-9}\mathrm{m}$,Use $k_B=1.380649\times 10^{-23}\mathrm{J}{\mathrm{K}}^{-1}$ and $\hslash =1.05457\times 10^{-34}\mathrm{J}\mathrm{s}$. Inserting the stated $v=5\times 10^5\mathrm{m}{\mathrm{s}}^{-1}$, ${\Theta }_D=500\mathrm{K}$ and $T=1\mathrm{K}$ into the paper's supplied prefactor givesThus bulk phonons dominate at this temperature in this estimate. If only one face contributes, the ratio is $1.22\times 10^{-6}$; if there are $\nu$ chemical atoms per unit cell, divide the corresponding estimate by $\nu$. These geometrical and crystallographic factors are not supplied explicitly.

With the same prefactor and geometry, extrapolating $1/T$ would suggest equality near $7.3\mu \mathrm{K}$. However, the surface finite-size scale is already of order $\hslash v/(k_{B}L)\simeq 3.8\mathrm{mK}$ 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.

Order parameter and the free-energy landscape. In Landau theory, take a scalar magnetization component at fixed volume and composition. It is an order parameter: its nonzero spontaneous value distinguishes an ordered phase with ferromagnetism from the symmetric high-temperature phase. One first constructs a constrained order-parameter free energy at specified magnetization by summing over microscopic states compatible with it. An external magnetic field is an independent control, so it can also appear in that constrained function. For a total magnetic moment the conjugate term is $-BM$; if $M$ is a magnetization density, the total-energy term is $-VBM$, or $-BM$ in free-energy density. Minimizing over $M$ then yields the equilibrium thermodynamic potential as a function of the imposed field.

Thus treating both $M$ and $B$ as arguments of a Landau function does not treat them as independent natural variables of the already-minimized equilibrium free energy. The first is the fluctuating or constrained order parameter, and the second its conjugate field.

At zero field, reversal symmetry requires $F(M)=F(-M)$, excluding odd powers. Near a continuous transition, assume the homogeneous constrained free energy is analytic for small $M$, that the quadratic coefficient crosses zero linearly, and that the quartic coefficient is positive. ThenThe temperature $T_c$ is where the zero-field quadratic coefficient vanishes and spontaneous ordering begins in this approximation. Higher powers are negligible sufficiently close to it; spatial fluctuations are neglected in this mean-field treatment.

Stationarity gives $2M[b(T-T_c)+2d{M}^2]=0$. Above $T_c$, the only minimum is at zero. Below it, zero becomes a maximum and two minima appear:The two signs describe spontaneous symmetry breaking: they are the average magnetizations in the symmetry-broken pure phases. A strictly finite system at exactly zero field samples the two wells symmetrically and has ensemble average $⟨M⟩=0$. A spontaneous pure-phase value is defined by selecting a phase, for example taking the thermodynamic limit before removing a small field. This qualification distinguishes a minimum's location from the average over a symmetric two-well distribution.

Minimum free energy and the heat-capacity jump. At a nonzero minimum, $M^2=-b(T-T_c)/(2d)$. Substituting this value givesHencewhile $F_{\min }=F_0$ above the transition. Take the temperature derivatives only after minimizing, so the equilibrium order parameter is allowed to change with temperature. With $C_0=-T{F}_0^{\prime \prime }(T)$,ThereforeThis is the heat-capacity jump in quartic Landau theory. The entropy is continuous at $T_c$, so there is no latent heat. If $F$ denotes free-energy density rather than total free energy, these expressions denote heat capacity per unit volume with the same normalization.

Stabilizing a tricritical expansion. At a tricritical point, the quartic coefficient is tuned to zero at the same point where the quadratic coefficient changes sign. Reversal symmetry still excludes odd powers. The next available stabilizing term is thereforeA negative or vanishing leading sextic coefficient would not stabilize this truncation for large $|M|$; a higher positive term would then be needed and the present tricritical form would be insufficient. The ordinary quartic theory has a continuous transition for $d>0$, while a stabilized theory with $d<0$ can have a first-order transition. Their meeting at zero field is what makes the simultaneous tuning tricritical.

The tricritical minimum. At zero field and $T<T_c$, stationarity givesThe nonzero solutions are minima: their curvature is $2b(T-T_c)+30d^{\prime }{M}^4=8b(T_c-T)>0$. Put $t=T_c-T>0$. Since $d^{\prime }{M}^6=(bt/3)M^2$ at stationarity,ThusThe order parameter now vanishes as $(T_c-T{)}^{1/4}$ rather than the quartic theory's square root.

Heat-capacity singularity. Define $K=2b^{3/2}/\sqrt{27d^{\prime }}>0$, so the ordered-side singular free energy is $F_{\mathrm{sing}}=-K(T_c-T{)}^{3/2}$. Its derivatives areConsequentlyThis is the tricritical heat-capacity amplitude in a sextic Landau expansion. It is positive on the ordered side and diverges as $T\to T_c^{-}$, rather than remaining a finite jump. This value of the heat-capacity critical exponent is the mean-field result along the path keeping the quartic term zero; a detuning to $d>0$ ultimately restores ordinary quartic behavior. Fluctuation corrections to the mean-field theory are not included in the stipulated polynomial minimization.

Use the Gibbs-Duhem equation for a homogeneous, extensive, single-component thermodynamic phase:At fixed temperature, this becomes $dp=nd\mu$, with number density $n=N/V$. Separately, at fixed particle number,The chain rule along the same isothermal process in the equation of state now givesConsequentlyThis 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 $\mathrm{P}{\mathrm{a}}^{-1}$, as required. The derivation assumes a smooth bulk equation of state; changing the fractions of coexisting thermodynamic phases at fixed pressure needs separate treatment.

Measure single-particle energy from the lowest state and write ${\epsilon }_k=c{k}^{\alpha }$, with $c>0$. In a homogeneous system, the number of wavevector states in a thin spherical shell is proportional to $k^{d-1}dk$. Changing variables from $k$ to $\epsilon$ gives the density of states per unit spatial volume,where $S_{d-1}$ is the area of the unit sphere in $d$ dimensions; an additional internal state degeneracy would multiply this expression by a constant.

The Bose-Einstein distribution has $\mu \le 0$. At saturation, $\mu \to 0^{-}$, the maximum excited-state number density isOnly the lower endpoint can cause divergence. There the integrand is proportional toThe improper integral converges precisely when its power exceeds $-1$. ThusWhen $d=\alpha$, the divergence is logarithmic; when $d<\alpha$, it is a power divergence. In either case the excited states can accommodate any fixed finite density at every positive temperature, so there is no bulk Bose-Einstein condensation at nonzero temperature.

For completeness, putting $s=d/\alpha >1$ and using the Gamma function and Riemann zeta function givesAt fixed density $n$, the right-hand side reaches $n$ at $T_c$; below it the excess particles occupy the lowest state, with condensate fraction $1-(T/T_c{)}^s$. This is Bose condensation with power-law dispersion in the homogeneous thermodynamic limit. A finite vessel or a trapping potential changes the low-energy state count and must not be silently substituted for that setting.

Use the classical dilute-gas conventionso the second virial coefficient has units of volume. The Mayer f-function formula for an isotropic pair potential isOnly separations smaller than $a$ contribute. Define $x=\beta \epsilon >0$ and substitute $t=r^3/a^3$, so $r^{2}dr=(a^3/3)dt$:This is the second virial coefficient of a bounded cubic repulsion. For every finite positive $T$, $1-e^{-x}<x$, so $B_2(T)>0$. There is no finite positive Boyle temperature. At high temperature, expanding the exponential givesThus the intended limiting statement isAt the other extreme the classical expression tends to $2\pi a^3/3$, the hard-exclusion value for separation $a$. This is a check on the integral, not a claim that a real molecular gas stays classical at arbitrarily low temperature. A molar virial expansion would instead use $B_{2,\mathrm{m}}=N_A{B}_2$.

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 $E_{\mathrm{tot}}$, the probability of a particular system microstate $i$ is proportional to the reservoir multiplicity at $E_{\mathrm{tot}}-E_i$. Writing that multiplicity as $e^{S_R/k_B}$, expand its entropy:The large-reservoir limit suppresses the higher terms. Normalization therefore givesThe sum counts individual microstates; when grouping them by energy, their state degeneracies must be included. This $Z$ 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 $d\Omega =\sin \theta d\theta d\phi$. With $x=\beta mB$, the angular partition function isChoosing a normalized angular measure would remove $4\pi$, with no effect on the energy derivatives. Differentiating at fixed $B$,The angular average $⟨\cos \theta ⟩=\coth x-1/x$ is the Langevin function. Since $dx/dT=-x/T$,This is the heat capacity of a classical magnetic dipole, in $\mathrm{J}{\mathrm{K}}^{-1}$ for one magnetic moment. The word specific here refers to that single moment; $N$ independent magnetic moments have $N$ times this heat capacity. At $B=0$ the energy is independent of orientation and $C_B=0$, obtained by the continuous $x\to 0$ limit. At fixed nonzero $B$, the classical low-temperature limit instead gives $C_B\to k_B$.

Equipartition and its proof. The equipartition theorem states that an independent quadratic term $a{q}^2/2$ in a classical Hamiltonian, with $a>0$, contributes $k_{B}T/2$ to its mean energy. One needs a canonical measure that factors as $dq$ 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 $H=a{q}^2/2+H_0$, integration by parts givesIntegrate over all other variables and divide by $Z$. It follows thatThe 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 $x\gg 1$, the moment is concentrated near alignment. Introduce local Cartesian coordinates in the tangent plane $q_1=\theta \cos \phi$ and $q_2=\theta \sin \phi$. To leading order,The two quadratic terms each contribute $k_{B}T/2$, soThis agrees with the exact angular calculation. Treating $\theta$ alone as one Cartesian quadratic variable would miss the $\sin \theta$ 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 $m_s=-1,0,1$, with $S_z=\hslash m_s$. Put $\Delta =\hslash |\gamma |B>0$, where $\gamma$ is the gyromagnetic ratio. The three energies are $-\Delta ,0,+\Delta$, irrespective of the sign of $\gamma$. Relative to the ground state they are $0,\Delta ,2\Delta$. Thus, with $q=e^{-\beta \Delta }$,Differentiation, or the canonical energy fluctuation identity $C_B=k_B{\beta }^2\mathrm{Var}(E)$, givesIn 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 $k_{B}T\ll \Delta$. 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 $d{U}_R=-dU$ and $d{V}_R=-dV$. Its particle number and the system's particle number are fixed. The reservoir's first law of thermodynamics therefore givesAdd the system's entropy change. Because $T_R,p_R$ are constant,Thus define the availabilityAn additive constant in $A$ is immaterial; its value above the equilibrium reference is the exergy. The Second law of thermodynamics gives $\Delta S_{\mathrm{tot}}\ge 0$, hence $\Delta A\le 0$. A stable equilibrium maximizes total entropy over the allowed variations and therefore minimizes $A$. The environmental $T_R,p_R$ 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 $x$, let $S(x)$ count the compatible system microstates. The product of the system and reservoir multiplicities isAll factors independent of $x$ enter a normalization constant, givingHere $A(x)$ 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, $A^{\prime }(x_0)=0$ and $A^{\prime \prime }(x_0)>0$. Its Taylor expansion givesKeeping 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 $A(x)$. Higher terms can shift the mean away from its most probable value $x_0$.

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 $\Gamma$, this contribution is $\Gamma \Omega =\Gamma \alpha V^{2/3}$, with no surface entropy under the stated approximation. Its differential isHenceIndependent thermal and volume variations give $T=T_R$ andThe air pressure is evaluated at $V_0$; 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, $\alpha =(36\pi {)}^{1/3}$, $\Omega =4\pi R^2$, and the pressure jump becomes $2\Gamma /R$, 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 $T_R$, eliminate its entropy in favor of its Helmholtz free energy:The identity $(\partial F_{\mathrm{air}}/\partial V{)}_{T,N}=-p_{\mathrm{air}}$ givesUsing 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 $V^{2/3}$; gas compression supplies the positive restoring curvature. For ideal air, ${\kappa }_T^{-1}=p_{\mathrm{air}}$, and mechanical equilibrium reduces the denominator toThe units are consistent: $D$ is pressure, so $k_B{T}_R{V}_0/D$ has units ${\mathrm{m}}^6$, the units of a volume variance. Holding $p_{\mathrm{air}}$ externally fixed while varying $V$ 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 $\alpha =4.84$, $\Gamma =0.072\mathrm{N}{\mathrm{m}}^{-1}$ and $p_R=10^5\mathrm{Pa}$. ThenWith the Boltzmann constant $k_B=1.380649\times 10^{-23}\mathrm{J}{\mathrm{K}}^{-1}$,Thus the fractional root mean square fluctuation and fractional variance are respectivelyThe absolute root mean square fluctuation is $2.01\times 10^{-19}{\mathrm{m}}^3$. 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.