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Along an isolated two-phase coexistence line, two distinct stable minima have equal free energy. If this line ends at an ordinary interior endpoint without encountering another phase, the distinction between the two phases must disappear: their minima and the intervening barrier merge. For separated nondegenerate minima, their stationary values are smooth functions of the controls. The difference $\Delta V=V(m_1)-V(m_2)$ has ${\partial }_h\Delta V=-m_1+m_2\ne 0$. The implicit function theorem therefore continues the equation $\Delta V=0$ as a local coexistence curve. It cannot end while those distinct stable minima persist.

At the merger the potential satisfiesThe third-derivative condition is essential: a stationary zero-curvature point with nonzero third derivative is an inflection, not a stable equilibrium. Shifting to $\psi =m-m_c$ gives an ordinary quartic Landau free energy with two independent control directions, temperature-like and field-like. The curvature and the order-parameter discontinuity vanish, the magnetic susceptibility diverges, and the correlation length diverges. The endpoint is therefore associated with a continuous transition. This is the critical endpoint of a quartic Landau free energy mechanism.

In the symmetric quartic example, the coexistence line is $h=0,r<0$. Its jump $2\sqrt{-r/u}$ vanishes at $(r,h)=(0,0)$, where $V=u{m}^4/4$. This supplies a concrete realization. The word “must” requires the stated ordinary-endpoint assumptions: a first-order line can instead meet a third phase, a multicritical point, a boundary of parameter space, or continue without a finite endpoint. A spinodal point alone is not an equilibrium critical endpoint.

A first-order phase transition has a discontinuity in a first derivative of the equilibrium free energy, such as the entropy or order parameter. It can have latent heat when the entropy jumps. A continuous phase transition has a continuously vanishing order parameter and no latent heat, with singular higher derivatives and a diverging correlation length. The LG theory compares global minima, not merely the points where a local minimum loses stability.

For the uniform quartic Landau free energythe equation of state is $rm+u{m}^3=h$. At zero field the stable minimum is $m=0$ for $r>0$, and $m=\pm \sqrt{-r/u}$ for $r<0$. Thus tuning $r$ through zero gives a continuous transition. For a fixed $r<0$, varying $h$ through zero instead switches between the two ordered minima and makes $m$ jump, giving a first-order phase transition in the conjugate field.

A temperature-like first-order transition can occur at zero field when $u<0$ and a positive sextic term $v{m}^6/6$ stabilizes the potential. Write $q=m^2$. Stationarity of a nonzero phase gives $r+uq+v{q}^2=0$, while equality with $V(0)=0$ gives $rq/2+u{q}^2/4+v{q}^3/6=0$. Solving these two conditions yieldsThe order parameter jumps from zero to $\pm \sqrt{q_{\mathrm{coex}}}$. At this pointso the competing stationary points are genuinely global minima. This phase coexistence condition differs from the spinodal points $r=0$ and $r=u^2/(4v)$, which mark loss or creation of local stability, not equilibrium coexistence.

If the symmetry permits a cubic term $w{m}^3/3$, a positive quartic coefficient does not preclude a first-order transition. For $V=r{m}^2/2+w{m}^3/3+u{m}^4/4$ with $w\ne 0,u>0$, stationarity and coexistence give $m=-2w/(3u)$ and $r=2w^2/(9u)$. This is the first-order transition in a cubic-quartic Landau potential; the symmetry restriction on the expansion is therefore part of the prediction.

The proposed Landau free energy has stationary equation $m[a(T-T_c)+b{m}^2]=0$. For $T>T_c$ its minimum is $m=0$. For $T<T_c$ the minima are $\boxed{m=\pm \sqrt{a(T_c-T)/b}}$, while zero becomes a maximum; at $T_c$ the positive quartic term keeps the free energy bounded below. Thus the two symmetry-related states, continuous transition and square-root onset agree with the mean-field approximation.

More explicitly the mean-field entropy expansion gives $F=F_0+N[k_B(T-T_c)m^2/2+k_{B}T{m}^4/12+O(m^6)]$ at zero field. Near $T_c$, replacing $T$ by $T_c$ in the quartic coefficient gives the positive constants $a=N{k}_B$ and $b=N{k}_B{T}_c/3$, and reproduces the preceding square-root amplitude. The polynomial is a local expansion near the transition, not a global expression at every temperature.

Assume the scalar order parameter can take either sign. The cubic term breaks $m\mapsto -m$ symmetry, and a positive quartic coefficient bounds the Landau free energy below. Stationary points satisfyso, besides the disordered point $m=0$, the possible ordered points areThe disordered point has curvature $A^{\prime \prime }(0)=A_2$ and is locally stable when $A_2>0$. Nonzero stationary points first appear whenThat condition alone does not make them the equilibrium phase: one must compare their free energies.

At a nonzero stationary point, substitute $A_2=-A_{3}m-A_4{m}^2$ to obtainFor an ordered state to coexist with $A(0)=0$, this requiresBoth curvatures at phase coexistence are positive and equal to $2A_3^2/(9A_4)$. The barrier is at $m=-A_3/(3A_4)$. In fact the potential at phase coexistence factorizes:The two distinct minima are therefore explicit, with a finite jump in the order parameter whenever $A_3\ne 0$.

To state the equilibrium inequalities for either sign of $A_3$, put $m=-\mathrm{sgn}(A_3)\rho$ with $\rho \ge 0$. This sign always has lower energy than the opposite sign of equal magnitude. ThenThe bracket's minimum is $A_2/2-A_3^2/(9A_4)$. It follows thatThe favored ordered minimum, when it exists, isThus a first-order phase transition is possible and occurs when the coefficients cross the coexistence relation. There is no continuous transition between $m=0$ and the equilibrium ordered state while $A_3$ remains nonzero and $A_4$ remains finite and positive. The ordered state becomes globally favorable while $A_2$ is still positive, before the disordered curvature can vanish. Although a stationary solution tends to zero at $A_2=0$, it is not the global transition branch. A continuous transition would require eliminating the cubic term, outside the stated $A_3\ne 0$ condition.

The spinodal points clarify the metastable region: for $2A_3^2/(9A_4)<A_2<A_3^2/(4A_4)$ the ordered minimum is metastable; for $0<A_2<2A_3^2/(9A_4)$ the disordered minimum is metastable. At $A_2=0$ the disordered state loses local stability. These local-stability limits should not be mistaken for the first-order transition in a cubic-quartic Landau potential.

In the Landau theory approximation, choose the global minimum of the Landau free energy as a function of the magnetization. Since ${\mathcal{A}}_6>0$, the polynomial is a coercive function and a global minimum exists. The candidates are stationary points satisfyingCheck their values of the free-energy density; a stationary point or a metastable local minimum alone need not be the equilibrium state. Positive curvature ${\mathcal{A}}_2+3{\mathcal{A}}_4{m}^2+5{\mathcal{A}}_6{m}^4$ ensures local stability; when it vanishes, higher terms must be checked. The selected global minimum is the equilibrium magnetization within this approximation.

At zero magnetic field, equal opposite minima describe distinct phases exhibiting spontaneous symmetry breaking. A spontaneous magnetization is obtained by taking the thermodynamic limit before $h\to 0^{+}$ or $h\to 0^{-}$. A symmetric finite-volume average can instead have zero expectation even when the minima are nonzero. Thus one must specify the phase when interpreting the minimizer as the equilibrium expectation.

These are mean-field critical exponents at a tricritical point. Hold the other control at its tricritical value and take the coefficients to be real analytic functions of temperature along a thermal approach with ${\mathcal{A}}_2=a(T-T_c)+o(T-T_c)$, $a>0$, ${\mathcal{A}}_6\to s>0$, and ${\mathcal{A}}_4=0$ or ${\mathcal{A}}_4=o(|{\mathcal{A}}_2{|}^{1/2})$. At fixed tricritical $g$, a generic real analytic temperature path with nonzero thermal slope has ${\mathcal{A}}_4=O(T-T_c)$ and meets the last condition. Paths tangent to a scaling direction can have different apparent temperature powers.

At zero field on the ordered side with ${\mathcal{A}}_4=0$, stationarity gives $m^4=-{\mathcal{A}}_2/s$; under the more general approach ${\mathcal{A}}_4=o(|{\mathcal{A}}_2{|}^{1/2})$, this relation holds to leading order. Thus the order-parameter critical exponent isFor the zero-quartic representative, putting this minimum into the Landau free energy gives the singular order-parameter contribution (and the leading asymptotic contribution under the stated negligible-quartic approach)Using $C_{\mathrm{s}}=-T{\partial }_T^2{f}_{\mathrm{s}}$ at fixed other control yields $C_{\mathrm{s}}\sim (T_c-T{)}^{-1/2}$, specifically $T{a}^{3/2}/(4\sqrt{s(T_c-T)})$ to leading order. HenceThis heat-capacity critical exponent refers to the nonzero ordered-side singular amplitude; in this mean-field approximation to Landau theory, the disordered global minimum contributes zero singular free energy, while any regular background remains. Fluctuation corrections lie outside the present approximation.

In the disordered phase, differentiating the equation of state at $m=h=0$ gives the magnetic susceptibility $\chi =1/{\mathcal{A}}_2$. On the ordered branch its curvature is ${\mathcal{A}}_2+5s{m}^4=4|{\mathcal{A}}_2|$, so $\chi =1/(4|{\mathcal{A}}_2|)$. Both give the magnetic-susceptibility critical exponentAt the tricritical temperature with both lower coefficients zero, $h=s{m}^5$, so $m=\mathrm{sgn}(h)(|h|/s{)}^{1/5}$ and the critical-isotherm exponent isThe Widom scaling relation $\gamma =\beta (\delta -1)$ and Rushbrooke scaling relation $\alpha +2\beta +\gamma =2$ both check these powers. Their validity here is a mean-field conclusion, not a claim that fluctuations in every spatial dimension preserve them.

The field $\varphi$ is a compositional order parameter in a binary fluid mixture. Its spatial integral is conserved in a closed sample, so advection and diffusion enter a continuity equation; the material derivative follows the incompressible fluid. The diffusive current $\mathbf{J}=-M\nabla \mu$, with positive order-parameter mobility $M$, moves material down the chemical potential gradient. The chemical potential of a composition field is the functional derivative of the symmetric quartic Landau free energyso $\mu =a\varphi +b{\varphi }^3-\kappa {\nabla }^2\varphi$. Positive $b,\kappa$ stabilize large amplitudes and penalize sharp interfaces; $a<0$ permits phase separation.

The momentum equation is the Navier-Stokes equation with dynamic viscosity $\eta$, constant mass density $\rho$, and the Korteweg force $-\varphi \nabla \mu$ arising from composition stresses. The pressure enforces incompressible flow, $\nabla \cdot \mathbf{v}=0$, and can absorb pure gradient contributions to that thermodynamic force. For example, $-\varphi \nabla \mu =\mu \nabla \varphi -\nabla (\varphi \mu )$ gives an equivalent force after redefining the pressure. These equations constitute deterministic Model H dynamics.

Their dissipative signs can be checked by the energy dissipation identity for Model H. Under periodic or no-flux, no-work boundary conditions, composition advection and capillary work cancel between $F$ and the kinetic energy, givingThus diffusion and viscosity dissipate energy, while the reversible advective coupling transfers it between composition and motion. Thermal noises are omitted at this deterministic hydrodynamic level.

Use the usual homogeneous, local, analytic Landau-Ginzburg theory; rotational symmetry and Z2 symmetry alone do not specify locality, analyticity, or the signs of the coefficients. The local derivative expansion contains every rotational scalar with an even total number of fields:The omitted terms include all allowed higher field powers and contracted spatial derivatives. Terms differing by a total derivative are equivalent for bulk behavior with suitable boundary conditions. The displayed gradient energy assumes spatial homogeneity. If only rotations about an origin are imposed, rotationally invariant position-dependent coefficients are also possible.

In the mean-field approximation, take a spatially uniform order parameter and minimize its Landau free energy. For $\gamma >0$, $u>0$ and $r=a(T-T_c)$ with $a>0$, keeping the quadratic and quartic terms givesThe single minimum splits into two minima as the temperature passes below the critical temperature. Choosing one minimum gives spontaneous symmetry breaking of the Z2 symmetry and a continuous phase transition. The order parameter is the expectation in a selected ordered state; averaging equally over both states gives zero. A Z2 symmetry does not guarantee a continuous phase transition: a negative quartic coefficient stabilized by a positive sextic coefficient can instead give a first-order phase transition.

Relaxing the Z2 symmetry permits odd terms. A nonzero linear source generally rounds this ordinary continuous phase transition. A cubic term can instead give a first-order phase transition: for $V(\varphi )=r{\varphi }^2/2+w{\varphi }^3/3+u{\varphi }^4/4$, $u>0$ and $w\ne 0$, equal minima occur atThe order parameter jumps from zero to ${\varphi }_{\ast }$. A continuous phase transition without an exact Z2 symmetry is still possible with additional tuning; odd terms do not logically exclude it.

For the multicritical even Landau potential, set $r={\mu }^2=a(T-T_c)$ and assume an integer $n\ge 2$, ${\lambda }_n>0$ and $\gamma >0$. For $n>2$, all lower even interactions must be absent or tuned to zero to obtain these mean-field critical exponents. The stationary equation isIts nonzero solutions are minima because $V^{\prime \prime }({\varphi }_0)=-(2n-2)r>0$. Thus the order-parameter critical exponent isSubstituting into the minimum free energy density givesThe singular heat capacity per unit volume is $c_s=-T{\partial }_T^2{f}_{\min }$. Smooth variation of the other coefficients does not change the leading power. ConsequentlyFor $n=2$, this means a finite heat capacity jump, with ${\alpha }_{\mathrm{MF}}=0$; for $n=3$, the tricritical point has ${\beta }_{\mathrm{MF}}=1/4$ and ${\alpha }_{\mathrm{MF}}=1/2$. The case $n=1$ would contain only a quadratic potential and would not stabilize an ordered phase.

The Gaussian fluctuation correction near a critical point is more singular than the mean-field approximation contribution whenThis is the upper critical dimension of an even scalar interaction. Equivalently, its coupling has engineering dimension $2n-(n-1)d$, positive below $d_c$. Dominant fluctuations signal breakdown of the mean-field approximation; the Gaussian expression is not then a calculation of the exact interacting heat-capacity critical exponent. At $d=d_c$, equality of the powers allows logarithmic corrections.

Take $b>0$ for a stable quartic Landau free energy. The cubic-term removal in a conserved quartic Landau free energy uses $\varphi =\psi -c/(3b)$ and gives, apart from a constant,For a closed binary fluid mixture, the compositional order parameter has fixed integral. Adding $d\int \varphi$ therefore adds the same constant to every allowed state. Equivalently, in the common-tangent construction for phase coexistence, a linear term changes the tangent slope, hence the chemical potential, by $d$, but leaves the coexistence compositions unchanged. This is why linear composition bias leaves coexistence compositions unchanged; it would not mean an unchanged composition at a fixed externally imposed chemical potential.

In the shifted variable, the binodal compositions are ${\psi }_{\pm }=\pm \sqrt{-a^{\prime }/b}$ for $a^{\prime }<0$. They merge atThe continuous phase transition therefore has the same scalar quartic Landau theory as the symmetric binary fluid mixture, with a shifted critical composition and control parameter. In the mean-field approximation, the composition difference vanishes with order-parameter critical exponent $1/2$. This argument presumes the critical composition lies in the physically accessible composition range; conservation affects the dynamics, not this static phase coexistence construction.

The nematic order parameter is a symmetric second-rank tensor and a traceless second-rank tensor describing orientational anisotropy. For molecular unit axes $\mathbf{s}$, $Q_{ij}$ is proportional to $⟨s_i{s}_j-{\delta }_{ij}/3⟩$. It vanishes in an isotropic phase and is unchanged by head-tail reversal $\mathbf{s}\mapsto -\mathbf{s}$, unlike a polar order parameter. For uniaxial nematic order, the nematic director is thus an unoriented axis.

One convention for the Landau-de Gennes free energy through fourth order, respecting rotational symmetry, isFor a traceless second-rank tensor in three dimensions, the Cayley-Hamilton theorem gives $\mathrm{Tr}{Q}^4=(\mathrm{Tr}{Q}^2{)}^2/2$, so there is only one independent quartic rotational invariant of a symmetric traceless tensor. The only possible linear scalar is $\mathrm{Tr}Q=0$; without an external anisotropy no linear term survives.

The cubic rotational invariant of a symmetric traceless tensor distinguishes prolate and oblate forms of uniaxial nematic order. Head-tail reversal leaves $Q$ unchanged and does not impose $Q\mapsto -Q$. Thus a cubic term is allowed in three dimensions and generically produces a first-order phase transition, rather than a symmetry-enforced continuous onset. In two dimensions a symmetric traceless second-rank tensor has eigenvalues $s,-s$, hence $\mathrm{Tr}{Q}^3=0$: the cubic invariant vanishes identically in two dimensions. This is a statement about the Landau free energy; fluctuations in two dimensions require a separate treatment.

Write $m_i={\mu }_i^2$ and $r^2={\varphi }_1^2+{\varphi }_2^2$. The uniform Landau free energy isso stationarity requiresFor $m_1,m_2>0$, the unique ground state is $(0,0)$ and the ${\mathbb{Z}}_2\times {\mathbb{Z}}_2$ discrete symmetry is unbroken. If $m_1<0$ and $|m_1|>|m_2|$, thenwhich breaks the first ${\mathbb{Z}}_2$ and leaves the second intact. This includes the case in which both masses are negative, because $m_1$ is then the more negative one. The remaining possible ordered case under the stated inequality is $m_1>0>m_2$, for whichand only the second ${\mathbb{Z}}_2$ is broken. The Hessian matrix in each ordered state is positive because the uncondensed direction has squared mass $m_k-m_j>0$, where $m_j$ is the condensed, more negative mass.

Near either continuous transition the nonzero order parameter is proportional to $(-m_i{)}^{1/2}$. Hence the mean-field critical exponents are

The lower critical dimension is the dimension at or below which fluctuations destroy the proposed finite-temperature ordered phase. Here the broken symmetry is discrete, so $d_{\mathrm{l}}=1$. In one dimension a domain wall interpolating between the two signs has finite energy, whereas its possible position gives an entropy growing as $\log L$. Domain walls therefore occur with nonzero density at every positive temperature and split the system into domains of finite typical length. Thus there is no finite-temperature ordered phase in one dimension.

Landau theory represents the appropriate thermodynamic potential as an analytic function of a small order parameter, retaining every low-order term allowed by the system's symmetry. At fixed control parameters, the equilibrium phase is the global minimum of the Landau free energy; local minima describe metastable phases. A continuous phase transition occurs when a minimum changes continuously and loses stability, whereas a first-order phase transition occurs when distinct minima exchange global stability.

Forthe stationary points satisfyIf $\epsilon >0$, $\varphi =0$ is the unique minimum. If $\epsilon <0$, $\varphi =0$ is a maximum and the two degenerate minima areThus the reflection symmetry $\varphi \mapsto -\varphi$ is spontaneously broken below $\epsilon =0$, and

The equilibrium magnetization is a global minimum of the Landau free energy. Its candidates are the stationary pointsThus $m=0$, or $x=m^2\ge 0$ is a nonnegative root ofOne retains candidates with nonnegative curvature $f^{\prime \prime }(m)$ and compares their free energies; the candidate with the smallest value is the equilibrium state. Equal global minima describe phase coexistence.

At the tricritical point, $a_4=0$ and the zero-field Landau free energy is $f=a_2{m}^2+a_6{m}^6$. Below $T_c$, minimization givesSince $a_2\sim T-T_c$, the order-parameter critical exponent isAt this minimum, $f_{\mathrm{sing}}=a_2{m}^2+a_6{m}^6$ is proportional to $-|T-T_c{|}^{3/2}$. Comparing this with $f_{\mathrm{sing}}\sim |T-T_c{|}^{2-\alpha }$ gives the heat-capacity critical exponentAfter adding the magnetic contribution $-Bm$, the inverse zero-field magnetic susceptibility is the curvature $f^{\prime \prime }(m)$. Above $T_c$ it is $2a_2$, while below $T_c$ it is $-8a_2$, so $\chi \sim |T-T_c{|}^{-1}$ and the magnetic-susceptibility critical exponent isFinally, exactly at $T_c$ the equation of state is $B=6a_6{m}^5$. Hence $m\sim B^{1/5}$ and the critical-isotherm exponent is

A real symmetric traceless $2$ by $2$ matrix has eigenvalues $\lambda$ and $-\lambda$ and can be writtenfor a unit nematic director $\mathbf{n}\sim -\mathbf{n}$. Since $Q_{ij}{Q}_{ji}=2{\lambda }^2$, the uniform Landau free energy isFor $a<0<b$, its nonzero minima satisfyand henceThe signs $\pm {\lambda }_0$ amount to exchanging the two orthogonal eigenvectors, so the chosen convention takes ${\lambda }_0\ge 0$.

The equilibrium magnetization is a global minimum of the Landau free energy. Its stationary values solve the polynomial equationand a local minimum must satisfyOne compares the value of $f$ at every such local minimum and chooses the smallest. Since $a_6>0$, the polynomial tends to positive infinity as $|m|$ tends to infinity, so a global minimum exists.

Write $t=T-T_c$, take ${\alpha }_2=at$ with $a>0$, and include the magnetic term $-Bm$. At $B=0$, minimizing the Landau free energy gives $m=0$ for $t>0$ andfor $t<0$, so the order-parameter critical exponent is $\beta =1/2$. Substitution gives a singular free-energy density proportional to $-t^2$ below $T_c$, whose second temperature derivative has a finite jump, so the heat-capacity exponent is $\alpha =0$. Above $T_c$, the equation ${\alpha }_{2}m+{\alpha }_4{m}^3=B$ gives the magnetic susceptibility $\chi =(\partial m/\partial B{)}_{B=0}=1/{\alpha }_2\sim t^{-1}$, hence $\gamma =1$. At $t=0$, $B={\alpha }_4{m}^3$, so $m\sim B^{1/3}$ and $\delta =3$.

A system can split into macroscopic regions with distinct local order parameters, densities or compositions. In a short-range system at phase coexistence, regions of two phases with means $M_1,M_2$ and volume fractions $q,1-q$ have spatial mean $M=q{M}_1+(1-q)M_2$. Their interface contribution is subextensive, so their thermodynamic free-energy density is the corresponding convex combination of the phase densities. This can lie below the homogeneous-branch Landau free energy at the same $M$. The equilibrium constrained order-parameter free energy is consequently convexified, with a straight coexistence segment described by the Maxwell construction. A nonconvex local potential remains useful for homogeneous branches, metastability and interfaces, but must not be identified with the full equilibrium constrained density throughout a coexistence interval.

For a real statistical source convention $Z[h]=\int \mathcal{D}\varphi e^{-H_0[\varphi ]+\int h\varphi }$, define $F=-\log Z$ and the displayed Legendre transform. On a differentiable stable branch, $\delta \Gamma /\delta m=h$. In the Landau approximation, the branch expression is ${\Gamma }_{\mathrm{L}}[m]=H_0[m]$. The exact Legendre effective free energy is convex; a bare nonconvex Landau free energy is a local approximation and requires branch or coexistence interpretation.

For the Landau free energy $G(\varphi )={\varphi }^6/6+g{\varphi }^4/4+\epsilon {\varphi }^2/2$, positive $g$ gives a continuous phase transition at $\epsilon =0$. For negative $g$, phase coexistence between the disordered global minimum $\varphi =0$ and the ordered global minima occurs on $\epsilon =3g^2/16$, with ${\varphi }^2=-3g/4$. Indeed, on that locus the polynomial is $G(\varphi )={\varphi }^2({\varphi }^2+3g/4{)}^2/6\ge 0$, so these three zeros are global minima. For $g<0$, the disordered and ordered spinodal points are respectively $\epsilon =0$ and $\epsilon =g^2/4$; equality of stationary free energies determines phase coexistence, while loss of a local minimum determines a spinodal point.