Z. Phys.

B - Condensed Matter 44, 317-323 (1981) Condensed

Matter
Zeitschrift
fQr Physik B
9 Springer-Verlag 1981

On the Kinetics of the First Order Phase Transitions

Krzysztof Parlil~ski
Institute of Nuclear Physics, Cracow, Poland

Piotr Zielifiski
Institute of Physics, Jagiellonian University, Cracow, Poland

Received March 12, 1981

An attempt is made to analyse the kinetics of the first order structural phase transitions
on the basis of the Landau-Ginzburg equation. Two simple solutions are proposed:
One in the form of one-dimensional solitary wave which can be considered as a planar
interface separating two phases and travelling along direction normal to the interface.
Any direction of propagation is possible. The other solution has a form of a one-
dimensional kink-antikink couple which under supercooling conditions reveals proper-
ties of a critical nucleus. A short discussion of the free energy density form for one- and
multidimensional order parameters, and of the symmetry of the quadratic gradient term
is included.

I. Introduction

The Landau theory of phase transition provides a
basis for deriving several important features of the
structural phase transitions for which the space
groups of the crystalline phases fulfil the group-
subgroup relationship. The theory provides a tool
for selecting the active irreducible representation
which specifies the order parameter and which is
responsible for the change in the crystal's space
group. It also allows the expansion of the free en-
ergy F of the high symmetry phase in terms of the
order parameter. Thus the symmetry criteria con-
tained in the theory indicate whether the phase tran-
sition may be of continuous or discontinuous (first
order) type. In the first case, the minimum of the
free energy expansion corresponding to the low sym-
metry phase emerges continuously from the mini-
mum which describes the stability of the high sym-
metry phase. For the systems which undergoes the
first order phase transition, and in the vicinity of the
coexistence line, the free energy as a function of
order parameter components posesses a few minima
separated by energetic bariers. One of the minima
corresponds to the high symmetry phase and the
others correspond to different domains of the low
symmetry phase.
At the coexistence line all the minima of the free
energy are of the same depth. When the external
conditions are changed the minima which corre-
spond to the metastable phase become higher than
those of the stable phase.
This approach does not take into account the spatial
fluctuations of the order parameter which occur, for
example, at the boundary between the two phases.
To include these fluctuations at least partly, one
usually introduces the free energy density function
(instead of the free energy function) which depends
upon the local value of the order parameter and of
its gradient. In the renormalization group theory
such a form of the free energy density function is a
starting point for any calculations of the critical
behaviour around a continuous phase transition. It
is well-known that at the critical temperature only
the fluctuations of large spatial extend (but relatively
small in amplitudes) become crucial.
In the case of the strongly first-order phase tran-
sitions the instability occurs with respect to a fluc-
tuation that is large in amplitude but rather small in
spatial extend. The transition arises before the in-
stability point is reached. This fluctuation locally
transforms the system from one minimum of the free

0340-224X/81/0044/0317/$01.40
318
energy to another. The consequence is that the sys-
tem becomes separated into two phases with an
interface between them. Under appropriate external
conditions the interface can travel, thus enlarging
the volume of one phase at the expense of the other.
It is tempting to identify the mentioned fluctuation
with the local change of the value of the order
parameter components used in the Landau theory.
The formation of the stable phase from the meta-
stable one is governed by the time-dependent Onsager
equation for the order parameter component r/(r, t)
[i].
8 t/if, t)
- ~ C'(r-r') ~ 8F d3r,
8t
where F ' ( r - r ' ) is a function of kinetic coefficients
associated with dissipative effects during relaxation
and F is the total free energy, so that 8F/6r 1 is the
thermodynamic force that drives the system towards
equilibrium.
Equation (1) can be reduced to either the Landau-
Ginsburg or Cahn equations. In order to do so, one
has to perform the space Fourier transform of (1) and
expand the even function of kinetic coefficients in
terms of k : F ' ( k ) = F ( k = O ) + ~ k 2 + .... Leaving the
constant zeroth term only and returning to the
space variables one gets the Landau-Ginsburg equa-
tion
8r#r, t) 8F
- F - -
at 6 t/(r, t)
which describes the most probable evolution of the
system towards equilibrium [1].
This approximation is valid when the order parame-
ter is a non-conserved quantity like the amplitude of
normal phonon or deformation modes in structural
phase transitions. If, however, the components of the
order parameter are conserved quantities, i.e., if
~/(r, t) d3r =const,
the zeroth term F ( k = 0 ) vanishes and (i) is reduced
to the Cahn equation
8o(r, t) [72 (~F
- 7 - -
at 6 r/(r, t)"
This equation describes, for example, the kinetics of
the order-disorder phase transition, specified by an
active irreducible representation of a concentration
field of atoms of a given kind.
The understanding of the thermodynamic of inter-
phases between two phases and the mechanism of
the first order phase transitions has recently been
improved in the work of Metiu, Kitahara, Ross [1].
K. Parlihski and P. Zielifiski: First Order Phase Transitions
The main effort has been directed towards a deri-
vation of the Landau-Ginsburg equation that de-
scribes the kinetics of some phase transitions. On
the basis of this equation Sai-Kit Chan [2] was able
to derive an approximate steady-state solution of the
spherical interface which may propagate with a
shape-preserving profile.
In this paper two analytical solutions of the Landau-
Ginsburg equation for a one-dimensional system are
presented, one in the form of a simple kink and
second in the form of kink-antikink couple. It is
shown that the shapes and velocities of the kinks
depends on the level of supercooling. The kink-anti-
(1) kink solution reveals properties of a one-dimen-
sional critical nucleus. In that case at very small
separation of two kinks the couple evidently ceases
to be the solution of the Landau-Ginzburg equation.
In structural phase transitions in real crystals the
above mentioned kinks can be treated as a planar
interfaces and then their parameters will depend
upon the orientation of the interface with respect to
the lattice.
II. Landau Expansion
First, let us consider a crystal having a structural
phase transition. Then the free energy density expan-
sion can be written in the form
(2) F = F 0 + ~ [~p(t/(r, t))+f(t/(r, t))] d3r, (5)
where
cP(t/)=89 +~ln+2 bt/"+2 + 2 n ~ cr/2"+2 (61
f (t/)= 89, ~.=1d~j . (7)
The polynomials (6) are associated with the homo-
geneous situation. The gradient term (7) describes
(3)
any inhomogeneity in the system. The phase tran-
sition driven by a one-dimensional active represen-
tation is described by the free energy (6) with n = 2 .
It is of the first order, provided b < 0 and c >0. For
some cases, the free energy expansion of the multi-
(4) component order parameter for a desired group-
subgroup relation can also be written in an abbre-
viated form (6) with n = 1 or n = 2. To arrive at form
(6) one has to introduce the effective order parame-
ter that is a linear combination of all components of
the order parameter with the constant coefficients
which ensure the reduction of the symmetry of high
symmetry phase to a desired low symmetry phase.
Such approach concerns the cases when the effective
order parameter is allowed to vary in the space of
K. Parlifiski and P. Zieliflski: First Order Phase Transitions
the order parameter along a watershed straight line.
The line joins the two minima of the free energy
which correspond to the two phases under consid-
eration. For example, the phase transition from the
point group 432 to the point group 422 driven by
the two-dimensional irreducible representation E at
k = 0 is represented by the free energy (6) with n = 1.
The path joining the two minima of F is a straight
line along the first component of the order parame-
ter, with the second component always remaining
zero [3].
The homogeneous part of the free energy (6) pos-
seses several extrema in the t/o positions to be
found from
(a+b~; +c;l~") rlo =0.
The solutions
~/o= 0,
1 [_b+]/b2_4ac],
~; =Uc-c
correspond to the high symmetry, (9) and low sym-
metry, (10), phases, respectively, provided b < 0 . We
accept the usual assumption of a soft mode concept,
i.e., we assume that the coefficient a(T)=cffT-T~)
depends linearly on temperature. The T~ is the in-
stability temperature of the high symmetry phase (~o
=0). Hence, a(Tc)=O. The coexistence temperature
To is reached when the values of the homogeneous
free energy (6) for high and low symmetry phases
become equal. Then
(n+2)2ac=(n+l)b 2 at TO.
The instability temperature T c of the low symmetry
phase 070 4=0) is define by the condition
b2
a(TC)=~cc at Tq
For the displacive phase transitions for which the
components of the order parameter can be identified
with the normal modes of the phonons, the coef-
ficient a=a(kc)=co2(kc) describes the square of the
phonon mode of the soft branch and can be mea-
sured by inelastic scattering methods. In the com-
bined type of phase transitions when the order pa-
rameter consists of modes other than phonons, for
example of the occupation modes of equivalent
orientations of molecular group or concentration
modes, the coefficient a=a(k~) still represents a gen-
eralized soft mode, although its value cannot be
measured directly.
The coefficients dgj in the gradient term (7) are not
always independent. To see that, let us consider a
319
non-degenerate generalized soft mode of the one-
component order parameter, which occurs at the
critical wave vector k C. The generalized soft mode
a(k) as a function of the wave vector k is invariant
with respect to the symmetry elements of a crystal-
lographic point group Pk~ appropriate to a given
critical wave vector k c. In the vicinity of ke, the
single mode a(k) has a symmetry Pko- Expanding it
around k c one finds
3
a(k)=a(k~)+ ~ d~j(k~)(k-k~)i(k-k~)j (13)
i,j_l
where a=a(kc) and dzj=dzj(ke) and where the linear
term disappears, provided the Lifshitz invariant van-
(8) ishes by symmetry. The ( k - k c ) is described by the
vector representation of the point group Pko" There-
fore, the matric (di) should have a symmetry of the
(9) symmetrized tensor of second rank [V 2] [4J. Hence,
in a conventional crystallographic coordinate system
(10) the matrix (di) has the following form: in cubic
point groups Pko it is diagonal with dll=dzz=d33;
in trigonal, hexagonal and tetragonal point groups
Pko it is diagonal, with dll =d22 ; in orthorombic P~
the d~j is diagonal with different elements; in mono-
clinic and triclinic Pk~ the matrix can be transformed
into a diagonal form by a rotation depending on the
value of parameters, but not on symmetry. In a
particular case, of displacive phase transitions the
matrix (dz) describes the curvature of the square of
the soft phonon mode in the vicinity of k c.
The matrix (dg) accounts for the interracial free en-
ergy of the crystal. Once brought into a diagonal
(11) form, the elements are necessarily positive, otherwise
a one-phase state would never be stable.
III. One Kink Solution
(12)
To study the solutions of the Landau-Ginsburg
equation let us first rotate the Cartesian coordinate
system (XlXzX3) into a new rectangular coordinate
system (X 1XzX3) where X t = ~ elix i. The gradient
i
term (7) in the new coordinate system can be written
as
(14)
t, ,, \C~Xm!
where
u~m = F. e. e.,j d~j. (15)
ij
Using the free energy density (5-7) and the transfor-
mation (15) one can write down the Landau-Ginz-
320 K. Parlifiski and P. Zieliflski: First Order Phase Transitions

burg equation (2) for non-conserved order parame- , i i , ,

ter rl(X 1 X 2 X 3 , t) in an explicit form: -]42

1 ~/~ 02 9,8
FOt ~Dz" ~+arl+brl"+~+Crl2"+~=O" (16)
~., axt a x ~ o~
The general solution of this nonlinear partial differ- o
ential equation is a serious problem. However, a
particular solution can be found under the assump- - o,4

tion that the order parameter is a function of one

space variable only: -qO
1,4 ~cr;
~/(X~ X 2 Xa, t) = r/(X,, t). (17) -12
l,2
Such solution may correspond to a planar infinite
7,Oi
interface with its normal that is directed along X,. i
qe
The direction X 1 is not restricted by any condition
and therefore is quite arbitrary. With the simplifi- J2o(rJ ],2
cation (17), the (16) describes a one-dimensional i
I,o
problem and becomes I q~
J
2
t &/ 0 t/ ,+1 1 i I I I 1 i 1

_F_ _c~t
_ D Ox T + a tl + b tl "4-C~ 2n+ =0, (18)
Fig. l. The amplitude of the order parameter tlo, the reciprocal
width ~ and the velocity v of one-kink solution as a function of
where r/=~/(X, t); D=Dal and the index 1 at X 1 has temperature for the free energy with n=2, b=-4a(To)/rl2(To); c
been supressed. One of the solutions of (18) has a
= 3a(To)/q~(To), D=4a(To)/(3c~2(To)) and F = 3 ~ v(Tc)/]/a(To)D,
form of a kink where a(To), tlo(To), 62(To) are defined at the coexistence tempera-
ture To, and v(T~) is a velocity at the instability temperature of
1
~(X, t)=~o{1 + e x p [ c s ( X - v t - X o ) ] } 7 (19) the high symmetry phase Tc

which one can check by a direct insertion into (18).

As a result, one finds
(23). On one its side the phase is characterized by
g2 [-D C52 VCS] DC52 vcs] the order parameter rlo=0 of the high symmetry
t n~ @ + g [ n @ phase and on the other by t/o:#0 of the low sym-
metry phase. The numerator of the expression (23) is
, -~- cr/o2,,
=a(1 +g)2 +b(1 +g) r/o (20)
equivalent to the relation (11) fulfilled at the coexis-
where tence line. At that temperature TO the velocity of the
kink vanishes and its width is given by
g = exp [C5(X - v t - X0) ].
n2a
By equating to zero the coefficients standing by the C52(T~ = D (24)
same power of g the following expressions can be
derived: The sign of v defines the direction in which one
a + brl~o+ Crl2o"=O, (21) phase grows at the expense of the other.
The temperature dependence of the velocity v, the
C52_ n2(a+brl~~ n2 ctlZ" (22)
reciprocal width C5 and the order parameter tl0 for
(n+l)D (n+l)O'
the model n = 2 are illustrated in Fig. 1. The position
nV [(n + 2) a + b q~] of the kink is, of course, arbitrary and X o is not
v= (23) specified by (18).
(n+1)c5
The free energy of a crystal formed from two phases
The first one, (21), is identical to (8) and describes being not at equilibrium and separated by a planar
the non-zero value of the order parameter at the interface can be found through the integration of the
minimum free energy density which corresponds to free energy density (5-7) over the volume of the
the low symmetry phase. crystal together with the kink solution (19). Hence,
The solution (19) has a shape of a kink of the width the excess of the free energy over the high symmetry
l/c5 (22). The kink moves with a constant velocity v, phase for an area S of the interface is
K. Parliflski and P, Zieliflski: First Order Phase Transitions
1 (~2 __
e(t)-eos (x~ +~t) ~o(,~o)-?q,(,1o)
. ('~)/"
lp=l P+~2 [2D ~ _ F (n2 + ]6n
~ 2+4~]J (25)
provided X~ >>vt.
The first term denotes the excess of a bulk free
energy of the low symmetry phase and X t there
denotes the linear size of this region. At non-equilib-
rium situation the term changes in time enlarging or
reducing the volume of the low symmetry phase.
The second term gives a correction to the bulk free
energy comming from the interface. The last term is
due to the surface energy incorporated in the in-
terface. At equilibrium the free energy is no longer a
function of time, and using (24) we have
f - F o r/o2 ,SD n
S -2(n+2)-2(n+2) r/2 a ~ ' (26)
Hence, the preferable orientation of the interface is
where the coefficient D at the gradient term (14) is
the smallest. Generally speaking any direction of
propagation is possible.
IV. K i n k - A n t i k i n k Solution
Up to now we have considered the simplest solution
of the Landau-Ginzburg equation (18) in the form of
a moving kink, Now, we shall look for a solution in
the form of a kink and antikink couple
1 62
t/(r, t)=r/o {1 +exp[--5(X--XA(t))]}-;
1
9 {1 + exp [ 5 ( X - XB(t))]} ,. (27)
For any time XA(t ) <XB(t ). Inserting this expression
into the Landau-Ginzburg equation (18) and pro-
ceeding in a way similar to the one that led us to
the one kink solution, we end up with the equation
resembling (20). In the process of calculating one
notices that the product e x p [ - ~ ( X - X A(t))]
x exp[d(x-r~(t))] is a function of the difference
(XB(t)--XA(t)) only. Therefore the quantity
h(~) = exp [ - 6 (XB(t) -- X A(t))] (28)
can be treated as a known parameter at a desired
time t. Equating to zero the coefficients standing by
the same powers of the exponents, one finds the
following values for the parameters of the kink-
antikink solution
a+btl~(l+h) ~+ct/2"(1-h) 2 ----~- I ) A q, (29)
nF
321
l~2 Clzl2n
(n + 1) D(1 - h)2' (30)
nF[(n + 2) a + brf~(1 +h) -1]
vA= - % - ~[(n+l)+q] (31)
2h
where q = ~ and vA=2,,(t), VB=XB(t) are the ve-
locities of the antikink and kink, respectively, equal
in their absolute values. Equations (29-31) from a
self-consistent system. On solving it one finds the
amplitude of the order parameter t/o, the width of
the kinks 1/~ and their velocities vA= - % .
At any temperature below the coexistence tempera-
ture TO one steady critical kink-antikink couple can
be found. Its existence is defined by VA=--%=0.
This solution occurs for certain critical distance of
the kinks AX~(T)=(X,-XA) ~ characteristic for each
temperature (T< To). When the distance between the
kinks is larger than d X~(T), the low symmetry phase
grows at the expense of the high symmetry phase.
For distances shorter than A Xc(T ) the low sym-
metry phase enclosed between the two kinks is eaten
up by the high symmetry phase. From vA=0 and
(28) and (31) the critical distance is
1 (n + 2) a + b,~;]
A X c ( T ) = - ~ In [ (~7~+2~ ] (32)
and from (29), (30) and from the condition bt/~(1
+h)-l=-(n+2)a the widths of the kinks at
AXc(T ) can be obtained as equal to
1~2 a
- (33)
D
Starting from (29) the critical distance can be calcu-
lated explicity
nV a ( (l~l)ba_(n+2~J" (34)
The critical distance plays a role of a one-dimen-
sional critical nucleus and depends upon the super-
cooling temperature through a=c~(T-T~). Owing to
the relation (11) the AXc(T ) becomes infinite at the
coexistence temperature To . At the absolute insta-
bility temperature of the high symmetry phase where
a(Tc) = 0 the critical distance remains formally finite
n+2 1~
~X~(T~): n n ~ Ibl (35)
but the width of the kinks 1/cS (33) tends to infinity.
Fig. 2 shows the critical distance as a function of
temperature for the model n = 2 and brl~(Ar
322 K. Parlifiski and P. Zielifiski: First Order Phase Transitions

' ' ' , , , i

2.5 ~xd(H 1,6

z~Xc ( Tc)
7,2

0,8 Tc§
20 rc, qao(rc - rc)

~I Tc. O,,75(TC- rc)=~

rc~O,54(rC_rc)
1.5
-0,~ rc,O,34(rc- rc)
rc. ol~(rc-rd
-1,2
I 1
-16
I I I i I I I I I I I
l 2 3 4 5 6 7 8 9 lO II
05 ,~Xd~ ( To)

! I I I I I
Fig. 4. The velocity of the kinks for the kink-antikink solution as
rc ~o a function of separation between the kinks A X = ( X B - - X A ) for
Fig. 2. Temperature dependence of the critical distance A X~ = (X B several temperatures. The cS~(To) denotes the reciprocal width at
- X A ) ~ (34) and of the reciprocal width ~r (33). The AX~(T~) the coexistence temperature and at infinite separation of the
(35) denotes the critical distance at T~ and 6~(T0) is defined at the kinks, and is given by (24). The model parameters are the same
coexistence temperature as in Fig. 1

12
g,~x,rL_;
dMro) < / ] Finding from (36) the t/o for a given h, the value of
and the size of the kink-antikink couple AX=(X~
-XA) can be calculated from (30) and (28), respec-
tively. Solutions for ~ (30) and vA (31) attained in
this way, are presented in Figs. 3 and 4. For dis-
o,95(r - rc ) tances
o.s ~ " rc~Sa(rC-rc)
\ rc§ 0,75(r c- re):r~
04 ~ Tc.O,,54(rC-Fc) AX>>]/~+ llD (37)
02 rc+O'34(rC-rc)
rc. q74{TC-rc) where t/~ is calculated with the help of (10), the
00 ] 2
I
3
I
4 5
I I
6
I
7 8
I i
9
i
70 /7 movement of the kinks is almost independent. For
shorter distances the width of the kink's couple be-
Fig. 3. The reciprocal width 6 ( A X , T) of the kink-antikink comes wider whereas its amplitude r/o becomes smal-
solution as a function of separation between the kinks A X = ( X B ler.
- X a ) , for several temperatures. The 6~(To) denotes the reciprocal
The value of h along all the curves in Figs. 3 and 4
width at the coexistence temperature TO and at infinite separation
of the kinks, and is given by (24). The T~ and T ~ are the in- increases monotonically up to the points where the
stability temperatures of the high and low symmetry phases, re- curves are truncated. These points correspond to the
spectively. The dotted line shows the reciprocal width 6~ (33) of a maximal value of the parameter h above which the
critical nucleus as a function of critical distances A X~. The model quadratic equation (36) looses two real and distinct
parameters are the same as in Fig. 1
solutions. The existence of the truncation point
shows that the solution in the form of the kink-anti-
=or, To)=4.0. a(To) and crl~(AX= oo, To) kink couple is unable to describe small fluctuations
=l.0.a(To) and D62(AX=oV, To)=l.33 a(To). To around one minimum (~/o=0) of the free energy. We
solve the self-consistent system of Eqs. (29-31), let have in mind the fluctuations which are too small to
us insert the velocity vA (3l) into (29). After some everjump the energetic barrier.
simple manipulations one arrives at the quadratic Moreover, all curves of ~ and t/o as functions of AX,
equation for the order parameter amplitude r/o as a (Fig. 3), vary rapidly in the region of A X = ( 3 - 6 )
function of h 6~ol(T0) for all temperatures of interest. In this re-
gion, then, the mentioned quantities depend on time
a{ l +4h+h2 2h[4n+ 5+(5+n)h+(n+
3)h+n+ l through the A X dependence. This observation con-
tradicts the former assumption in (27) that the 5 and
2h(2n + 3+_h) "~ r/o are time independent. Therefore, one should con-
+b l + h (n+3)h+n+lj~l"o+Ctl2"=O. (36)
clude that in the region of small separation of the
K. Parlifiski and P. Zielifiski: First Order Phase Transitions
kink-antikink couple (27) one would expect an
analytical solution of another form.
Figure 3 also shows the critical reciprocal width 6c
(33) of the kink at critical distances (dotted curve)
attributed to a given temperature. One notices that
the nucleus can be satisfactorily described by the
kink-antikink couple only for small supercoolings.
Above, we have considered the nucleus of the low
symmetry phase surrounded by the high symmetry
phase. The opposite case i.e. the nucleus of the high
symmetry phase surrounded by the low symmetry
region can be treated in analogous way for the
model n = 1. Then the solution of the Landau-Gins-
burg equation (18) is
r/(X, t)=r/o-t/o{1 +expE-6'(X-XA(t))]} 1
- { 1 + exp [ a ' ( X - X;(t))]}- '
where t/0 indicates the minimum corresponding to
the low symmetry phase and is given by (21) and t/o,
vA are described by (29), (30) and (31) respectively,
with the additional condition that a, b, and c are
replaced by
a'=a + 2brlo + 3Crl~,
b'= - b - 3 c r l o ,
C'zC.
323
This low symmetry nucleus has generally the same
properties as the previous one, so under overheating
conditions it either increases or decreases depending
on that whether its size is larger or smaller than the
corresponding critical distances. The model n = 2 can
not be considered in the above mentioned way.
It is worth to mention that the Landau-Ginsburg
equation (16) can produce also solutions in the form
of three-dimensional critical nucleus. This work is
under processing ~5].
References
1. Metiu, H., Kitahara, K., Ross, J.: J. Chem. Phys. 64, 292 (1976)
2. Sai-Kit Chan: J. Chem. Phys. 67, 5755 (1977)
3. Parlifiski, K., Sikora, R.: (to be published)
4. Sirotin, Yu., Shaskolskaya, M.P.: Osnovy Kristallofiziki, Table
(38) D.4, Izd. Nauka, Moscow 1975
5. Parliflski, K., Wasiutyfiski, T. : (to be published)
Krzysztof Parliflski
Instytut Fizyki Jadrowej
uI. Radzikowskiego 152
PL-31-342 Krakdw
Poland
Piotr Zielifiski
Instytut Fizyki Uniwersytetu Jagiello/~skiego
ul. Reymonta 4
PL-30-059 Krakdw
(39) Poland