The Symmetry Rules in the Landau-Lifshitz Theory of Second-order Transitions

An Application to Order-disorder Transformations

March 20, 2014

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Introduction

A phase transition is the thermodynamical transformation of a system from one state of matter to another and it can be classied in dierent ways. In 1933 Ehrenfest proposed a classication based on the lowest order of the derivative of the Helmholtz free energy with respect to temperature that has a discontinuity at the transition point.1, 4 In this way, rst-order transitions have a discontinuity in (G/T )TC whereas second-order transitions show a discontinuity in ( 2 G/T 2 )TC . Third-order and higher-order transitions would be dened in a similar fashion. It is now known that this classication oversimplies reality. This is because at the critical point uctuation due to long-range correlations require the use of renormalization theory. This has lead to a modern classication that separates transformations into rst-order and continuous, such as lambda transitions. Nevertheless, Ehrenfests classication and the implicit assumptions of this classical theory remain valid in some cases. In the scope of Ehrenfests classication, Landau developed a phenomenological theory for second-order transitions. Even though its restricted validity at the critical temperature, the symmetry rules derived from the theory are still valid3 and they are in fact a depiction of the more important concept of symmetry breaking (SB). This phenomenon has acquired an enormous signicance in physics, specially in modern theoretical physics. As an example, SB has been used to explain how the electromagnetic and weak forces were the same force at an early stage of the formation of the Universe and how they were separated due to a cooling of the universe that originated a phase transition and a reduction in the symmetry. This symmetry breaking split this force, called electroweak, into the two dierent forces. This is known as the Higgs mechanism.1 In this report a more earthly occurrence of symmetry breaking is going to be studied. The symmetry rules derived from the Landau-Lifshitz (LL) theory that predict whether a secondorder transition is possible or not will be presented briey. In particular, they will be used to analyze order-disorder transformations in solids where its application immediately feels natural and remains valid. In order to do this, the work of Khachturyan found in his book, Theory of Structural Transformations in Solids, as well as the article of De Fontaine, K-Space Symmetry Rules for Order-disorder Reactions, will be summarized focusing on the expansion that these authors made to LL theory. In particular, these authors use the symmetry rule in reciprocal space in order to predict and explain the continuous formation of ordered structures in the context of an implicit mean-eld theory based on the Ising Model. Some other references will be used as well in order to support the theoretical presentation. 1

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Second-order Transitions and Symmetry Breaking

One of Landaus greatest contribution to the theory of phase transformations was to introduce the order parameter dened in such a way that it is identically zero for the high-temperature, high-symmetry phase and non-zero for the low-temperature, broken-symmetry phase. Since this order parameter goes continuously to zero, even if the symmetry changes abruptly, the Helmholtz free energy can be expanded in terms of this parameter keeping only the lowest terms, i.e. fourth-order term. For the transformation to be possible there are several selection rules resulting from a purely group theoretical analysis. The rst one says that the symmetry group of the low-temperature phase, H , has to be a subgroup of G, the symmetry group of the high-temperature phase. In terms of ordered-disorder transformations, H corresponds to the ordered phase and G to the disordered structure. This selection rule is the reason why the low-temperature phase is also called the hidden phase, since its symmetry is already present in the high-temperature phase. Topology can be used to better understand, or to explain in an alternative way, LL theory. The following is from the summary made by Sen. Morse Theory determines the lower bounds for the number and kind of critical points of a real function on a manifold in terms of the Betti numbers. These numbers are topological invariants of the manifold. For example, in the case of a crystal with point group Oh the manifold is a 3-sphere and the Betti numbers are the number of 4D holes, b3 = 1; the number of 3D holes, b2 = 0; the number of 2D holes, b1 = 0; and the number of connected pieces, b0 = 1. The Morse inequalities are n 0 b0 n1 n0 b1 b0 n2 n1 + n0 = b2 b1 + b0 n3 n2 + n1 + n0 = 0 where the last relation is the Euler characteristic, n0 is the number of minima, n1 is the number of saddle points and n2 is the number of maxima. Now, if X0 is a three dimensional vector such that the free energy F (X0 ) has a critical point and n(G) is the order of the group G then there are n(G) critical points with the same characteristics, i.e. minimum, saddle point or maximum. Then, when the symmetry is broken into a group H , the number of dierent n(G) critical points is going to be equal to the integer n . For example, if the symmetry was not (H )
n(G) broken then n = 1 and we have the same critical point that X0 gave us. Thus, the number (H ) of critical points is constrained by group theory. This fact connects the ideas of group theory

(1)

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and topology. To illustrate how this concepts gives us the selection rules for allowed transitions let us have the example of the group Oh and see if a broken symmetry group of order 2 is possible. If this is the case then we have 48 = 24 critical points because 48 is the order of group Oh . We know that 2 a polynomial of order n and m variables has (n 1)m critical points. Landaus Free Energy is order four and we have three dimensions. The number of critical points is 33 +1 = 28 by adding an extra one due to the maximum at innity. From the Morse inequalities we get n0 = 24 and n1 23. From group theory, the values of the ns have to be the orders of the subgroups of Oh : 24, 12, 8, 6, so that n1 = 24 Since the sum of the real critical points n3 + n2 + n1 + n0 28, but n0 = 24 and n1 = 24 and therefore the transition is not allowed.

Static Concentration Waves

The alternative development just presented is equivalent to the traditional Landau and Lifshitz symmetry rules stated explicitly:3 1. The space group of the low-temperature phase must be a subgroup of the high-temperature phase. 2. The vectors that generate the ordered phase must minimize the free energy. 3. It must not be possible to construct a third-order invariant from the vectors that minimize the free energy. It is easier to treat the vectors mentioned in these rules in reciprocal space through the method of concentration waves developed by Khachaturyan.5 This method is a particular application of the general LL symmetry rules to the case of transformations in solid solutions such as orderdisorder transformations and spinodal decomposition. What follows is from (Khachaturyan, 1983). First, we explicitly dene the occupation probability n(r) as the probability of nding a solute atom at the lattice position r. If the disordered phase is the stable phase, then n(r) = c, where c is the atomic fraction of the solute. n(r) can be taken to reciprocal space by expanding it in a Fourier series: n (r) = c + Q (kj ) eikj r (2)
j

where kj are wavevectors, i.e. vectors in reciprocal space, referred in Rule 2. Now, if some kind of order or heterogeneity with respect to the occupation of lattice sites by the solute atom becomes stable the occupation probability is reexpressed as n(r) = c + (r) where (r) 3

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represents the heterogeneous uctuations of the atoms preferring one site over the other. Being the free energy a function of the arrangement of the atoms F (r) it can be expanded in a Taylor series: F = F0 +
r

A(r)(r) +

1 2!

B (r, r )(r)(r ) +
r,r

1 C (r, r , r )(r)(r )(r ) + ... (3) 3! r,r ,r

where A(r), B (r, r ) and C (r, r , r ) are the Taylor coecients. Since all the disordered crystal sites are equivalent and from the denition of the occupation probability the rst-order term vanishes.5 Considering only the second-order term for now and expanding the free energy in a Fourier series we obtain N F = b(k) |Q(k)|2 (4) 2 k For the disordered phase all the amplitudes of the uctuations Q(k) are zero. If all the coefcients b(k) are positive any nonzero Q(k) will result in a positive increase in the free energy. Thus, the disordered state is stable when all b(k) > 0. If at least one b(k0 ) 0 the ordered state becomes stable with the heterogeneity given by k0 . Being b(k0 ) a thermodynamic function it has to obey the two conditions at the critical temperature Tc : b (k0 , T, c, p) = 0 b (k, T, c, p) k =0
k0

(5a) (5b)

The rst condition states the fact that b(k) has to pass through zero at Tc when the ordered phase becomes more stable than the disordered phase. The second condition is necessary in order for the system to be stable with k = k0 as the instability wavevector. It is worth noting that when k0 = 0 we are dealing with a spinodal decomposition otherwise it is an order-disorder transformation. Due to the symmetry of the disordered phase, a wavevectors k0 will have other wavectors k01 , k02 , ..., k0j associated to it that will minimize the function b(k) as well. These wavevectors are actually cristallographically equivalent to k0 and can be obtained by applying the dierent symmetry operations of the space group . The set of all these equivalent vectors is called the star, {k0 }, and we can restrict ourselves to treat them only in the rst Brillouin zone. Including all the therms that were neglected in eq. 4 the Fourier expansion of the free energy
The space group to which the star {k0 } corresponds is that of the reciprocal space of the crystal, e.g. for a direct space space group Fm 3m (fcc) the reciprocal space space group would be Im 3m (bcc).

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can be expressed as F = 1 1 b(k) |Q(k)|2 + C (k0j1 , k0j2 , k0j3 ) Q(k0j1 )Q(k0j2 )Q(k0j3 ) 2 k 3! j1 ,j2 ,j3 1 + D (k0j1 , k0j2 , k0j3 , k0j4 ) Q(k0j1 )Q(k0j2 )Q(k0j3 )Q(k0j4 ) + . . . 4! j1 ,j2 ,j3 ,j4

(6)

Applying a translation equal to a lattice vector T to this expression such that r r + T it becomes: F = 1 2 b(k) |Q(k)|2 +
k

1 C (k0j1 , k0j2 , k0j3 ) Q(k0j1 )Q(k0j2 )Q(k0j3 )e(k0j1 +k0j2 +k0j3 )T 3! j1 ,j2 ,j3

1 + D (k0j1 , k0j2 , k0j3 , k0j4 ) Q(k0j1 )Q(k0j2 )Q(k0j3 )Q(k0j4 )e(k0j1 +k0j2 +k0j3 +k0j4 )T + . . . 4! j1 ,j2 ,j3 ,j4 (7) Comparing equations 6 and 7 and requiring invariance between them due to the translational symmetry we can summarize the following conditions: C (k0j1 , k0j2 , k0j3 ) = D (k0j1 , k0j2 , k0j3 , k0j4 ) =
= = = =

0 if k0j1 + k0j2 + k0j3 = 2 H 0 otherwise 0 if k0j1 + k0j2 + k0j3 + k0j4 = 2 H 0 otherwise

(8a)

(8b)

where H is a fundamental reciprocal lattice such that ei2HT = 1. If we now introduce the order parameter dened by Q (k0j ) = j ,
j

|j |2 = 1

(9)

we can expand the free energy in terms of , F = 2 1 N b(k0 , T, c) 2 + C (T, c) 3 + D(T, c) 4 + . . . 2 3! 4! (10)

As it was already explained, at the critical temperature goes to zero continuously. In order to be at equilibrium the free energy has to have a minimum on at Tc . This can only happen if C (Tc , c) = 0 and D(Tc , c) > 0. Looking at the condition 8a it can be concluded that in order to have a second-order transformation the following should always hold: k0j1 + k0j2 + k0j3 = 2 H (11) 5

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This is the symmetry rule 3 stated in terms of the reciprocal wavectors k0j which makes it easier to use it in practical applications. In fact, the star {k0 } can be obtained by using a diraction technique. This is one of the reasons why the Khachaturyans version of the LL symmetry rules might be seen as an expansion or an improvement to the original Landau and Lifshitz formulation. Determining if a transformation is second-order or not, or if the transformation is even possible based solely on the space symmetry group of the parent and resultant phases becomes very easy. The other important reason is that the method of concentration waves can be adapted very easily to solve the mean-eld model of order-disorder transformations, but this falls out of the scope of this report. Is is important to note two things. The rst one is that the condition of the third-order invariance is one of necessity and not of suciency. The second point is that the expansion of the free energy at the critical point is not mathematically correct; however, the symmetry rules are still valid if we evaluate the free energy just below Tc .3 This formalism can be used to classify the dierent types of transformations. This is done by de Fontaine. He actually goes further and distinguishes the dierent types of reactions according not only to the conditions already stated but to another types of analysis not included in this report by including all the dierent kinds of resultant ordered structures in a Venn diagram (see Fig.1).

Figure 1: Venn diagram for the classication of the dierent ordered structures.3 6

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Conclusions

The purpose of this report was to explore some of the theoretical advances and expansions done to the theory of second-order phase transitions developed by Landau and Lifshitz, particularly the symmetry rules derived from it. It is well known that Landaus expansion of the free energy function in the critical point is not mathematically valid, nevertheless it has also been shown that the symmetry ruless utility holds. They have been used to classify dierent structures resulting from order-disorder reactions by de Fontaine as well as the basis for the method of concentration waves developed by Khachaturyan. This method was presented very briey showing, by doing so, that it can be easier to use in practical situations. The method is based on an expansion of the free energy in terms of the reciprocal wavectors. This means that the observation done in x-ray, neutron or electron diraction can be directly used to predict the order or type of a phase transformation.

Bibliography
[1] Blundell, Stephen, and Katherine M. Blundell. Concepts in Thermal Physics. Oxford: Oxford UP, 2006. Print. [2] Callen, Herbert B., and Herbert B. Callen. Thermodynamics and an Introduction to Thermostatistics. New York: Wiley, 1985. Print. [3] De Fontaine, D. K-Space Symmetry Rules for Order-disorder Reactions. Acta Metallurgica 23.5 (1975): 553-71. Print. [4] Jaeger, Gregg. The Ehrenfest Classication of Phase Transitions: Introduction and Evolution. Archive for History of Exact Sciences 53.1 (1998): 51-81. [5] Khachaturyan, Armen Gurgenovich. Theory of Structural Transformations in Solids. New York: Wiley, 1983. Print. [6] Landau, L. D., E. M. Lifshits, and L. P. Pitaevskii. Statistical Physics. Oxford: Pergamon, 1980. Print. [7] Marder, Michael P. Condensed Matter Physics. New York: John Wiley, 2000. Print. [8] Sen, Siddhartha. Symmetry, Symmetry Breaking and Topology. Symmetry 2.3 (2010): 1401-422. Print.