Past exam of the mathematics course of the University of Cambridge / 2018 / iii / Paper 344 / 3

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.

For the stated uniaxial nematic order normalization, the nematic director is an eigenvector of $Q$ with eigenvalue $\lambda$, and the two perpendicular eigenvalues are $-\lambda /2$. ThereforeUsing precisely the Landau-de Gennes free energy convention in the preceding solution givesIf the quartic invariant were instead normalized as $b\mathrm{Tr}{Q}^4/4$, its coefficient would be $\bar{b}=9b/32$; the physical predictions are unchanged after redefining $b$.

For a nonzero global minimizer of the free energy, compare opposite values of the scalar nematic order parameter:The lower one has $\bar{c}\lambda <0$, soThe claim concerns the stable ordered phase, not every metastable stationary point. For $\bar{c}=0$ the two signs are degenerate. For $\bar{c}\ne 0$, equality of the ordered and isotropic free energies, together with stationarity, gives ${\lambda }_t=-\bar{c}/(2\bar{b})$ and ${\bar{a}}_t={\bar{c}}^2/(4\bar{b})>0$. The finite jump ${\lambda }_t$ exhibits the first-order phase transition driven by the cubic invariant.

A scalar coupling linear in the nematic order parameter requires a second-rank anisotropy. A single electric field supplies no such tensor, while $E_i{E}_j$ does. Its isotropic part gives $E^2\mathrm{Tr}Q=0$. Hence the lowest joint order in $E$ and $Q$ of the electric-field coupling to nematic order isTerms depending only on $E$ do not affect minimization over $Q$. With $\vartheta$ the angle between the nematic director and the electric field,For $\chi \lambda >0$, the lowest free energy occurs at ${\cos }^2\vartheta =1$, so the nematic director aligns along either $+\mathbf{E}$ or $-\mathbf{E}$. Then $E_i{Q}_{ij}{E}_j=\lambda E^2$, givingUnlike the linear composition term in a conserved binary fluid mixture, this term changes the equilibrium nematic order parameter: its spatial integral is not fixed.

Within this analytic quartic Landau theory, equilibrium of a nonconserved scalar order parameter requires $f^{\prime }=0$. At a continuous phase transition, its restoring curvature vanishes, so $f^{\prime \prime }=0$. A nonzero $f^{\prime \prime \prime }$ would leave a cubic leading term in the Taylor expansion about that state and prevent it from being a local minimum. Thus a stable critical endpoint of a quartic Landau free energy requires all three derivatives to vanish, with $f^{\prime \prime \prime \prime }>0$. The condition $f^{\prime \prime }=0$ alone can instead identify a spinodal point.

For $f=\bar{b}{\lambda }^4+\bar{c}{\lambda }^3+\bar{a}{\lambda }^2+\bar{d}\lambda$, $\bar{b}>0$, the successive equations areThey giveAt these values, the free energy is exactly $f({\lambda }_c)+\bar{b}(\lambda -{\lambda }_c{)}^4$, proving stability. With no electric field, $\bar{d}=0$, so necessarily $\bar{c}=0$, followed by ${\lambda }_c={\bar{a}}_c=0$.

For $\bar{c}<0$ and $\chi >0$, the electric-field coupling to nematic order supplies the required negative ${\bar{d}}_c$ atTuning the quadratic coefficient to ${\bar{a}}_c$ simultaneously reaches the field-induced critical endpoint of the isotropic-nematic transition. The PDF's $\tilde{c}$ in the last clause is undefined; it is interpreted here as the previously defined $\bar{c}$. The endpoint is a prediction of the stable quartic, small-field mean-field approximation; higher-order terms or a field beyond the expansion's validity can shift it.