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Maxwell relations turn pressure, volume and temperature measurements into information about entropy. For example, the pressure rise when heating a rigid sealed vessel determines the entropy change when expanding the same sample isothermally:The quantities on the two sides describe different experiments, yet both are mixed partial derivatives of one Helmholtz free energy. This is the useful surprise: a mechanical measurement can reveal a thermal property. Similarly, the coefficient of thermal expansion gives $(\partial S/\partial P{)}_{T,N}=-\alpha V$. ^[ref]

For a simple compressible system, hold particle number $N$ and composition fixed, and allow only pressure-volume work. Write $U$ for internal energy, $H=U+PV$ for enthalpy, $F=U-TS$ for Helmholtz free energy, and $G=H-TS$ for Gibbs free energy. Their natural-variable differentials areThus the first partial derivatives, with the subscript recording the variables kept fixed, areThe symmetry of second derivatives produces all four standard Maxwell relations, including their signs:For a brief derivation of the $F$ relation, differentiate $F_T=-S$ with respect to $V$ and $F_V=-P$ with respect to $T$: $-S_V=F_{TV}=F_{VT}=-P_T$. Each other row follows in the same way. Assume continuous second partial derivatives of the relevant thermodynamic potential in the region considered. At a phase transition, the equilibrium potential may lose this smoothness; apply the identities within each smooth thermodynamic phase, and handle latent heat and phase coexistence separately. If particle numbers vary, the potential differentials acquire chemical potential terms, so the fixed-$N$ constraints must remain explicit. ^[ref]

For an ideal gas with fixed $N$, the ideal gas law gives $P=N{k}_{B}T/V$. At fixed volume, heating changes the pressure at rate $N{k}_B/V$. Consequently an isothermal expansion at positive temperature hasFor one mole with $R=8.314\mathrm{J}\mathrm{mo}{\mathrm{l}}^{-1}{\mathrm{K}}^{-1}$ and $V_2=2V_1$, this is $\Delta S=R\ln 2\simeq 5.763\mathrm{J}{\mathrm{K}}^{-1}$. At $300\mathrm{K}$, a reversible isothermal expansion absorbs $Q=T\Delta S\simeq 1728.85\mathrm{J}$ and performs equal work, since its internal energy is unchanged. The entropy difference is a state function difference: the same equilibrium endpoints give the same $\Delta S$ in an insulated free expansion, although there $Q=0$ and the process is irreversible.

The same Maxwell relations let thermal measurements determine the difference between constant-pressure and constant-volume heat capacities. In a smooth single thermodynamic phase,using heat capacity at constant volume, heat capacity at constant pressure, coefficient of thermal expansion and isothermal compressibility. Along fixed pressure, $dV=\alpha VdT$, soThus measured expansion and compression responses determine a heat capacity difference without measuring both heat capacities separately. They do not determine the absolute heat capacities or absolute entropy by themselves; an independent thermal measurement supplies that missing information. For an ideal gas, $\alpha =1/T$ and ${\kappa }_T=1/P$ reduce the result to $C_P-C_V=PV/T=N{k}_B$, which is Mayer's relation.

When the necessary higher partial derivatives exist and commute, differentiating the Maxwell relations once more also givesIntegrating these slopes determines how a heat capacity changes with volume or pressure at fixed temperature. For an ideal gas, both right-hand sides vanish because the ideal gas law is linear in temperature at either fixed volume or fixed pressure. Consequently $C_V$ and $C_P$ depend only on temperature at fixed $N$, although they need not be constant in temperature. ^[ref]

Historically, James Clerk Maxwell's Theory of Heat, first published in 1871, presents these connections using the geometry of isothermal processes and reversible adiabatic processes. His fourth edition, page 167, explicitly relates expansion on heating at fixed pressure to heat emitted during an isothermal compression: the modern $G$ relation gives $\delta Q_{\mathrm{rev}}=TdS=-T\alpha VdP$. This explains why a substance with positive coefficient of thermal expansion emits heat when compressed isothermally, whereas one with negative coefficient absorbs it. ^{[ref] [ref]}

For a mechanical coordinate $x$ at fixed temperature, total volume and particle numbers, the relevant thermodynamic potential is the Helmholtz free energy $F(x)$. Its generalized force is $f=-F^{\prime }(x)$. At mechanical equilibrium, $f(x_{\ast })=0$, and a linearly restoring force has $f^{\prime }(x_{\ast })<0$, equivalently $F^{\prime \prime }(x_{\ast })>0$. A Taylor expansion then proves a strict local free-energy minimum. If $F$ is a strictly convex function throughout the accessible domain, the stationary state is the unique global minimum.

For the same atoms in a three-dimensional volume $V$, the one-atom translational partition function is $q_{\mathrm{trans}}^{(3)}=V/{\Lambda }^3$. Comparing the same $N$ atoms at the same temperature cancels the common $N!$ in their canonical partition functions. Therefore the molar adsorption confinement free energy, with the sign defined as adsorbed minus free, isThe logarithm is dimensionless: $V/\sigma$ and $\Lambda$ are both lengths. For a macroscopic gas depth $V/\sigma \gg \Lambda$, confinement raises the translational Helmholtz free energy. Equivalently, the translational state count is reduced by a factor $\sigma \Lambda /V$ per atom. The question supplies neither a volume nor an adsorption binding energy, so this answer is symbolic and describes the confinement cost, not a numerical net adsorption free energy.

For example, a binding energy $D>0$ per atom would supply a separate $-N_{\mathrm{A}}D$ to $\Delta F_m$, together with any normal-motion internal contribution retained by a more detailed model. Adsorption can then be favourable despite the loss of free translational phase space. Merely calling the change a loss must not reverse the sign of the explicitly defined $F_{\mathrm{ads}}-F_{\mathrm{gas}}$.

For the adsorbed lattice gas, the Helmholtz free energy isUse Stirling's approximation with $M,N,M-N$ large, then differentiate at fixed $M,T,B$. Writing surface coverage as $\theta =N/M$ gives the adsorption chemical potentialThe occupation ratio comes from site-mixing entropy; it is essential near saturation.

Let $N_g$ be the number of free atoms and $n_g=N_g/V$. In the field-free gas, both spin states have zero energy, so the one-atom partition function is $q_g=2V/{\Lambda }^3$, where $\Lambda$ is the thermal de Broglie wavelength. For a dilute ideal gas,ThereforeThe last equality uses $p=n_g{k}_{\mathrm{B}}T$. The bulk spin degeneracy is two even though the bulk magnetic field vanishes: degeneracy is not the absence of spin states.

Assume a dilute classical ideal gas of $N$ indistinguishable, noninteracting particles, with translational states dense enough to replace their sum by a continuum integral. Separate translation from all internal degrees of freedom. ThenUsing Stirling's approximation in the Helmholtz free energy,Differentiate at fixed $N,V$. Since ${\Lambda }^{-3}\propto T^{3/2}$,Only after this derivative set $N=N_A$ and $V=RT/p^{\circ }$ for one mole at standard pressure:This is the translational Sackur-Tetrode equation. The $N!$ factor is essential for the correct extensive entropy; replacing $V$ by a temperature-dependent standard molar volume before taking the fixed-volume derivative would give the wrong constant term.

Let ${\epsilon }_s$ be the energy of one adsorbed atom, using the same energy reference as the gas-phase value ${\epsilon }_0$. For equivalent, noninteracting adsorption sites, choosing the occupied positions givesEvery configuration has energy $N_1{\epsilon }_s$, so the canonical lattice-gas partition function isThere is no further $1/N_1!$ factor: the combinatorial choice already counts indistinguishable adsorbates correctly. The Helmholtz free energy, using Stirling's approximation for a macroscopic number of occupied and empty sites, isHence the adsorbed-phase chemical potential at fixed $T,M$ isThe logarithm comes from configurational entropy: adding an atom is less favorable when vacancies are scarce. In the gas, the stipulated expression can be writtenwhere $\Lambda$ is the thermal de Broglie wavelength. Equality of chemical potentials at chemical equilibrium givesThereforeThe binding energy $E_b={\epsilon }_0-{\epsilon }_s$ is positive for favorable binding. The units of $b$ are inverse pressure, making $bp$ dimensionless. Choosing the adsorbed energy as zero simply sets ${\epsilon }_s=0$ and leaves the same physics; it must not remove the relative binding energy. This is the Langmuir isotherm, with low-pressure linear uptake and high-pressure monolayer saturation.

For an ideal mixture, the Helmholtz free energy is a sum over species. At fixed $T,V$ and all other populations, the molecular partition function $q_i$ does not depend on $N_i$. Differentiating the contribution written using each species' own energy reference givesThe desired additive energy term requires a consistent energy reference in molecular partition functions. Let ${\epsilon }^{0,i}$ be the energy per molecule of species $i$ in its reference state, measured relative to a common chemical energy zero, and let $q_i$ sum excitations above that reference. ThenThereforeOne convenient choice is each species' rovibrational ground state, so the molecular reference includes its zero-point energy. A different consistent reference is possible, but the corresponding partition function must change. The offset cannot arise from differentiation of a formula that has already omitted it, and it must not be counted twice. These chemical potentials are per particle; molar expressions instead use the molar gas constant.

Treat each species as a dilute classical ideal gas: molecules of the same species are indistinguishable, while different species are distinguishable. Let $N_i$ be the number of molecules of species $i$, $q_i(T,V)$ its molecular partition function with energies measured from a chosen internal reference, and ${\epsilon }^{0,i}$ that reference energy per molecule relative to a common chemical energy convention. Then the mixture's canonical partition function factorizes:The $N_i!$ corrects the overcounting of indistinguishable particles. The exponential restores the species-dependent reference energies that matter for reactions. Thus the Helmholtz free energy isUsing Stirling's approximation, $\ln (N_i!)\simeq N_i\ln N_i-N_i$, and differentiating at fixed $T,V,N_{j\ne i}$ yieldsThe ideal-gas $q_i$ does not depend on the number of molecules, so no additional $\partial q_i/\partial N_i$ term appears. These are chemical potentials per molecule; multiply by the Avogadro constant for a molar chemical potential. The result assumes the thermodynamic, nondegenerate-gas limit.

Following the restricted model in the preceding part, its electronic factor for $N$ independent magnetic molecules is $Q_{\mathrm{mag}}=(2\cosh x{)}^N$. Its field-dependent Helmholtz free energy is thereforewhere $A_{\mathrm{ind}}$ denotes terms independent of the field. Equivalently, the change from zero field is $A(B)-A(0)=-N{k}_{\mathrm{B}}T\ln \cosh x$. Retaining the excited-state offset simply adds $N\Delta$ to the restricted free energy.

If $N$ instead counts all molecules in thermal equilibrium, the correct electronic expression isThe ordinary translational indistinguishability factor is field independent and does not alter either magnetic derivative.

For identical, non-interacting molecules, the translational canonical partition function is $Q_N=q_{\mathrm{trans}}^N/N!$. Stirling's approximation gives the Helmholtz free energyAt fixed $V$, $q_{\mathrm{trans}}\propto T^{3/2}$, so differentiation gives $S=Nk[\log (q_{\mathrm{trans}}/N)+5/2]$. For one mole at the standard-state molar volume,Here the quoted molar translational quantity is per mole, and its ratio to $N_A$ is dimensionless. The derivative defining entropy is taken at fixed volume before inserting the standard-state volume; differentiating along a constant-pressure path would give the wrong additive constant.

For a homogeneous polymer solution, examine the curvature of the mixing Helmholtz free energy with respect to composition. A composition fluctuation into equal volumes at $\varphi \pm \delta \varphi$ changes the average free energy byThus $f^{\prime \prime }>0$ locally resists fluctuations and $f^{\prime \prime }<0$ amplifies them, leading to spinodal decomposition. The spinodal curve is the locus $f^{\prime \prime }=0$, separating locally stable or metastable homogeneous compositions from locally unstable ones. The coexistence binodal instead follows a common tangent to the free energy. Between the binodal and spinodal, separation needs nucleation.

In Flory–Huggins solution theory, $\varphi$ is the volume fraction, $N$ is the number of equal-sized lattice segments per chain, $T$ is temperature, $k_{\mathrm{B}}$ is the Boltzmann constant, and $\chi$ is the dimensionless Flory interaction parameter. The stated $f$ is the mixing Helmholtz free energy per lattice site. The first two terms describe mixing entropy; the last describes the contact-energy contribution.

At fixed $T$ and composition-independent $\chi$,Hence the spinodal isThe homogeneous state is locally unstable when $\chi >{\chi }_s(\varphi )$. The minimum gives the critical point of a Flory–Huggins polymer solution:If $\chi$ depends on temperature, the equation $\chi (T)={\chi }_s(\varphi )$ converts this result into a temperature–composition boundary.

In the Asakura-Oosawa model, nonadsorbing polymers are treated as ideal, mutually penetrable particles, but their centers cannot enter a layer around a hard colloid. The polymer osmotic pressure is $\Pi =\rho k_{\mathrm{B}}T$ in the ideal dilute limit, with the appropriate number density in the space dimension considered.

For fixed polymer number, reducing the inaccessible volume increases the available volume and lowers the polymer Helmholtz free energy. Equivalently, at fixed polymer chemical potential, the polymer contribution to the effective colloid potential isWhen the excluded layers overlap, their union occupies less space than two separate layers. More polymer configurations become available, so the resulting depletion force attracts the colloids. It is an entropy-driven effective interaction, even though each microscopic colloid–polymer interaction is purely repulsive.

At fixed volume and temperature, equilibrium minimizes the Helmholtz free energy $F=U-TS$. Mixing increases translational entropy, whereas favourable contacts between chromatin segments can lower the interaction contribution to internal energy. At low enough temperature, favourable contacts can compensate the entropy lost on concentrating the arrays; at higher temperature, the mixing contribution can dominate. This gives the upper-critical dome assumed in (a).

A simple illustrative Flory–Huggins solution theory writes the dimensionless mixing free energy per site asHere $N$ is an effective polymer size, not automatically the number 12, and $A>0$ represents an effective energetic incompatibility of polymer and solvent. The common-tangent construction determines coexisting compositions. Solving $g^{\prime \prime }=g^{(3)}=0$ givesSince $\chi$ decreases on heating, the coexistence interval narrows and closes at $T_c=A/{\chi }_c$. For fixed pressure the corresponding potential is Gibbs free energy, with the enthalpic term in $G=H-TS$; enthalpy and internal energy should not be interchanged without stating the mechanical constraint. Hydration, ion release or temperature-dependent effective interactions can change this simple temperature trend.

Write ${\beta }_T=(k_{B}T{)}^{-1}$ to distinguish inverse temperature from an order-parameter critical exponent. For the Ising model, define the full two-point correlation function $G(r)=⟨{\sigma }_0{\sigma }_r⟩$ and its connected correlation function $G_c(r)=G(r)-M^2$ in a translation-invariant phase. Away from a thermodynamic critical point, the large-distance envelope decays exponentially, possibly multiplied by a power of distance:This defines the correlation length in physical distance units when the limit exists. At a continuous phase transition, $\xi \to \infty$ and the critical connected correlation function typically has algebraic decay $G_c(r)\sim |r{|}^{-(D-2+\eta )}$, where $\eta$ is the anomalous dimension. Below the transition the full $G(r)$ tends to $M^2$, so the decay definition must use $G_c$.

Let $S={\sum }_r{\sigma }_r$ and $F=-{\beta }_T^{-1}\log Z$ be the extensive Helmholtz free energy. Holding the field-independent constant $C$ and other physical couplings fixed,Because the Hamiltonian contains $-hS$, ${\partial }_h\log Z={\beta }_T⟨S⟩$ and ${\partial }_h^2\log Z={\beta }_T^2(⟨S^2⟩-⟨S{⟩}^2)$. Translation invariance then proves the correlation-function susceptibility sum rule:In the ordered zero-field phase these statements refer to a selected pure thermodynamic phase; averaging equally over opposite magnetizations introduces the separate spin-mixture contribution to zero-field susceptibility.

A normalized blocking kernel $K_b({\sigma }^{\prime },\sigma )\ge 0$ satisfies ${\sum }_{{\sigma }^{\prime }}{K}_b({\sigma }^{\prime },\sigma )=1$. For example, assign one block spin to each block of $b^D$ microscopic spins using majority sign, with equal probabilities for a tie. Define the blocked Hamiltonian, retaining the entire generated operator space, byThe field-independent contribution $N{g}_E$ belongs to the identity operator. With $N^{\prime }=N{b}^{-D}$ andsumming over ${\sigma }^{\prime }$ proves $Z(u,C,N)=Z(u^{\prime },C^{\prime },N^{\prime })$ exactly. Iterating gives $N_p=N{b}^{-pD}$ and the same partition function with $(u_p,C_p,N_p)$. Observables at large scales are reproduced by appropriately blocked observables and sources. Truncating the generated interactions makes this an approximation; dropping the additive constant already destroys the equality of free energies even when normalized spin expectations remain correct.

The extensive Helmholtz free energy is unchanged: $F(u_0,C_0,N)=F(u_p,C_p,N_p)$. In contrast, its value per site changes because the number of sites changes. Define the reduced zero-constant free-energy density $f_0(u)={\beta }_{T}F(u,0,N)/N$ in the thermodynamic limit. The preceding equality yieldsand iteration proves the additive free-energy recursion under blocking:Equivalently $C_p=b^{pD}[C_0+{\sum }_{j=0}^{p-1}{b}^{-jD}{g}_E(u_j)]$. Thus the inhomogeneous source records the identity-operator contribution to renormalization-group free energy from eliminated short-distance degrees of freedom.

To express this recursion for the singular part, write $f_0=a+f_s$, where $a$ is the regular analytic background. Then the same displayed recursion holds with $f_s$ andThis is the analytic subtraction of an inhomogeneous renormalization recursion. A purely analytic source can often be absorbed into $a$, after which it does not control the leading singular powers. It is not legitimate simply to discard an analytic source in the full free energy, where it can dominate the regular background. Moreover an analytic monomial $c{t}^m{h}^n$ contributesIf $m{l}_t+n{l}_h=D$, the sum is $p$ and hence generates a logarithm when $p\sim -\log |t|/(l_t\log b)$: a renormalization-group free-energy resonance. Such a term cannot be discarded when describing that logarithmic singularity. Neglect of the inhomogeneous term in the leading power-law scaling therefore assumes that its regular part has been subtracted, that any remaining source only changes finite scaling amplitudes, and that there are no relevant resonances or marginal logarithms. Omitting an irrelevant operator further requires absence of a dangerously irrelevant coupling, whose vanishing limit can make a scaling function singular.

A renormalization-group fixed point obeys $R_b{u}_{\ast }=u_{\ast }$. Linearization gives $\delta u^{\prime }=A\delta u$; in eigenvector coordinates $w_i^{\prime }=b^{l_i}{w}_i$. Positive $l_i$ label relevant operators, negative $l_i$ label irrelevant operators, and zero $l_i$ labels a marginal operator requiring nonlinear analysis. The critical surface is the stable manifold obtained by tuning all relevant scaling fields to zero. A repulsive renormalization-group trajectory leaves the fixed point along a relevant direction as the observation length increases. Locally a typical zero-field section has $dw/d\ell =-\omega w$, $dt/d\ell =l_{t}t$, $\ell =\log b$, so the critical surface $t=0$ attracts along $w$, while trajectories with either sign of $t$ depart from it. A magnetic scaling field adds another relevant direction.

Under the stated homogeneous-scaling assumptions and after fixing irrelevant fields at their limiting values, two relevant scaling fields obey $t^{\prime }=b^{l_t}t$, $h^{\prime }=b^{l_h}h$. These fields are analytic coordinates near the renormalization-group fixed point, proportional to the physical reduced temperature and conjugate field to leading order. The singular free-energy density consequently obeysHere $F_s$ denotes the singular free energy per original site or unit volume, with regular dimensional factors absorbed; the extensive singular part is $N{F}_s$. Iterate and choose $b^p=|t{|}^{-1/l_t}$ to obtain the scaling hypothesis for critical phenomena:The sign labels the two sides of the transition: $f_{+}$ describes $t>0$, the disordered side, while $f_{-}$ describes $t<0$, the ordered side. The two functions need not coincide; $f_{-}$ has the zero-field one-sided derivative appropriate to spontaneous magnetization. The numbers $l_t,l_h$ are scaling eigenvalues in logarithmic form: the corresponding discrete RG multipliers are $b^{l_t},b^{l_h}$.

The correlation length obeys $\xi (t,h)=b\xi (b^{l_t}t,b^{l_h}h)$. The same scale choice gives $\nu =1/l_t$. Differentiating $F_s$ once and twice with respect to the conjugate field, and twice with respect to temperature, givesAt $t=0$, instead choose the scale $b^p=|h{|}^{-1/l_h}$. Then $F_s(0,h)\sim |h{|}^{D/l_h}$ and $M\sim \mathrm{sgn}(h)|h{|}^{D/l_h-1}$, so $\delta =l_h/(D-l_h)$. Thus differentiation and scale matching establishThe first is the Widom scaling relation and the second the hyperscaling relation. The hyperscaling relation requires precisely the regular homogeneous scaling used here. Above the ordinary upper critical dimension, the quartic coupling is dangerously irrelevant in the ordered phase and this derivation cannot discard it: the mean-field critical exponents $\nu =1/2$, $\alpha =0$ do not obey $\alpha =2-D\nu$ for $D>4$. At marginal dimensions logarithmic factors likewise require care beyond the displayed pure powers.

Use ${\beta }_{\mathrm{th}}=1/(k_{B}T)$ for inverse temperature to distinguish it from the order-parameter exponent. The decaying two-point correlation function needed for the response identity is connected:Away from the critical point in a short-range Ising model pure phase, the correlation length controls the exponential long-distance falloff, $G(r)\sim A(r)e^{-|r|/\xi }$ with a possible algebraic prefactor. The full two-spin expectation below the transition instead tends to $M^2$. The spin-mixture contribution to zero-field susceptibility explains why a symmetric mixture is unsuitable for defining a finite connected correlation length in the ordered phase.

Let $F=-{\beta }_{\mathrm{th}}^{-1}\log Z$ be the total Helmholtz free energy. Take magnetization and susceptibility per site, soDifferentiating the Boltzmann weights at fixed temperature givesTranslation invariance then yields the correlation-function susceptibility sum ruleTotal magnetization and total susceptibility multiply these expressions by $N$; per physical volume they have an additional factor $a^{-D}$ relative to the per-site convention. These normalizations do not change the critical powers.

For the subsequent scaling requests, let $F_s$ denote singular free energy per site; the fixed extensive normalization is suppressed. The labels $+$ and $-$ denote $t>0$ and $t<0$, with distinct scaling functions and amplitudes on the two sides. Below the transition a one-sided derivative at $h=0$ selects a spontaneous-magnetization branch. Writing $x=h/|t{|}^{\Delta }$, differentiation of the scaling hypothesis for critical phenomena givesThe field-independent $I_{\pm }$ makes no contribution to these field derivatives, although it can change heat-capacity amplitudes. Assuming nonzero leading amplitudes and the indicated pure-phase limits, comparison with the exponent definitions givesThis is the Rushbrooke scaling relation. A temperature-independent critical isotherm requires the large-$|x|$ magnetization scaling function to grow as $\mathrm{sgn}(x)|x{|}^{\beta /\Delta }$: otherwise $M_s=|t{|}^{\beta }{\mathcal{M}}_{\pm }(x)$ would retain a temperature power as $t\to 0$ at fixed small $h$. Therefore $1/\delta =\beta /\Delta$. Since the preceding two equalities also give $\Delta =\beta +\gamma$, the Widom scaling relation follows:For the hyperscaling relation, additionally assume that one correlation volume supplies an order-one singular free-energy contribution and that there is a single isotropic correlation length, with no dangerously irrelevant coupling spoiling this argument. Then $F_s\sim {\xi }^{-D}\sim |t{|}^{D\nu }$. Two temperature derivatives give the singular heat capacity, soHyperscaling is an additional physical assumption, not a consequence of the two-variable equation alone, and generally fails above the upper critical dimension.

Finally the correlation scaling function $f_G(x)$ falls exponentially, up to algebraic factors, for $x\to \infty$ in a massive short-range pure phase. At $x\to 0$ it approaches a finite nonzero value in the scaling regime. Approximating the lattice sum at distances much larger than $a$, and denoting the area of the unit sphere by $S_{D-1}$, givesIf $\eta <2$ and the integral has a finite nonzero limiting value, microscopic distances contribute only a regular background and the leading divergence is ${\xi }^{2-\eta }$. Thus the Fisher scaling relation isThese statements concern leading singular powers; logarithmic corrections and cancellations of amplitudes require separate treatment.

The partition function sums the Boltzmann weights of all statistical configurations. For discrete states $s$ of energy $E_s$, $Z={\sum }_s{e}^{-{\beta }_{\mathrm{th}}{E}_s}$; for a regulated scalar field it is a functional integral, $Z=\int \mathcal{D}\varphi e^{-{\beta }_{\mathrm{th}}H[\varphi ]}$. It normalizes probabilities and generates thermodynamic averages. Its Helmholtz free energy isA quantum version uses $Z=\mathrm{Tr}{e}^{-{\beta }_{\mathrm{th}}\hat{H}}$. In the following identification, $F(M)$ is a constrained free-energy density, so its units match those of a Hamiltonian density rather than a total extensive energy.

Fix a microscopic cutoff ${\Lambda }_0$. Split the field into retained modes ${\varphi }_{<}$ with momenta below $\Lambda$ and eliminated modes ${\varphi }_{>}$ between $\Lambda$ and ${\Lambda }_0$. Define the Wilsonian coarse-grained statistical Hamiltonian exactly byIts coefficients and additive constant depend on $\Lambda$ so that integrating the retained modes gives precisely the original $Z$. With sources and observables carried along, the same construction preserves long-wavelength responses. Thus changing this intermediate ultraviolet cutoff is a change of description, not a change of the physical system. It is advantageous because one can integrate out fluctuations irrelevant to the observable length scale, organize a local gradient expansion, and use renormalization-group flow toward simpler universal fixed-point descriptions. Exact invariance retains all generated operators; truncating them is an approximation.

The quadratic gradient coefficient generally becomes $K_{\Lambda }$, not a constant. Field renormalization sets a chosen kinetic normalization, for example ${\varphi }_R=\sqrt{K_{\Lambda }}\varphi$ when this makes the gradient coefficient one in the energy convention. Sources and observables must be transformed inversely so that their physical meaning is preserved. Under rescaled coordinates $x^{\prime }=x/b$, the critical field scaling isIts anomalous part is the anomalous dimension; it gives $G(r)\sim r^{-2x_{\varphi }}$ and the conjugate-field exponent $y_h=D-x_{\varphi }$. Different conventions for the wave-function factor require corresponding changes in its logarithmic derivative. A fixed physical magnetization must not be confused with a cutoff-dependent dimensionless renormalized field.

To justify the zero-cutoff identification of constrained free energy, work first in a finite periodic volume $V$. Define the physical spatial mean $M=V^{-1}\int \varphi (x)d^{D}x$ and constrain that mean in the microscopic integral:Retain the constant mode $M$ while eliminating every nonzero mode. When $\Lambda$ is below the smallest nonzero box momentum, the remaining energy is $H_{\Lambda }[M]=V{U}_{\Lambda }(M)$. Consequently $e^{-{\beta }_{\mathrm{th}}V{U}_{\Lambda }(M)}=Z_M$ with a consistently fixed, possibly field-independent measure normalization. This provesFor a uniform field, $U_{\Lambda }(M)$ is the Hamiltonian density $\mathcal{H}(\Lambda ,M)$ in the question. The statement assumes that the physical zero mode is retained, all other modes are integrated exactly, field-rescaling factors are undone, and density and additive-normalization conventions agree. Taking the cutoff limit in the finite box before its thermodynamic limit makes this derivation unambiguous. With an applied uniform source, $Z(h)=\int dM{e}^{-{\beta }_{\mathrm{th}}V[F_c(M)-hM]}$ up to the same measure convention; its large-volume saddle minimizes $F_c(M)-hM$.

The Landau approximation further assumes that this potential can be approximated by a regular local polynomial on the homogeneous branches, and that the remaining fluctuations are negligible for the observables sought. It is not an assertion that an exact zero-cutoff free energy is the bare polynomial. In a coexistence region the exact constrained density can be convexified by domains, while a nonconvex Landau branch potential describes local phases and their metastability.

For the breakdown criterion use a short-range scalar theory with positive quadratic gradient stiffness. At the Gaussian fixed point, invariance of $\int (\nabla \varphi {)}^2{d}^{D}x$ gives field dimension $(D-2)/2$. A coupling $g_{2n}$ multiplying ${\varphi }^{2n}$ therefore has engineering scaling exponentIt is irrelevant only above its upper critical dimension. For the ordinary critical point the leading stabilizing interaction is quartic, while at a tricritical point the renormalized quartic term is tuned away and the leading interaction is sextic. ThereforeOne can also see the failure through the Ginzburg criterion. Long-wavelength fluctuations averaged over a correlation volume obey $⟨(\delta M{)}^2{⟩}_{\xi }\sim {\xi }^{2-D}$, up to temperature and stiffness factors. The quartic saddle has $M^2\sim {\xi }^{-2}$, giving a fluctuation/mean-square ratio proportional to ${\xi }^{4-D}$. The tricritical sextic saddle has $M^2\sim {\xi }^{-1}$, giving a ratio proportional to ${\xi }^{3-D}$. Both ratios grow without bound below their respective critical dimension, invalidating the fluctuation-free Landau exponents sufficiently close to a transition.