pair correlation functions in nematics: free-energy functional and isotropic-nematic transition

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Pair Correlation Functions in Nematics: Free-Energy Functional and Isotropic-Nematic Transition Pankaj Mishra and Yashwant Singh Department of Physics, Banaras Hindu University, Varanasi-221 005, India (Received 6 March 2006; published 25 October 2006) We develop a free-energy functional for an inhomogeneous system that contains both symmetry conserved and symmetry broken parts of the direct pair correlation function. These correlation functions are found by solving the Ornstein-Zernike equation with the Percus-Yevick closure relation. The method developed here gives the pair correlation functions in the ordered phase with features that agree well with the results found by computer simulations. The theory predicts accurately the isotropic-nematic transition in a system of anisotropic molecules and can be extended to study other ordered phases such as smectics and crystalline solids. DOI: 10.1103/PhysRevLett.97.177801 PACS numbers: 64.70.Md, 05.70.Ce, 64.70.Dv The freezing of a fluid of anisotropic molecules into a nematic phase is a typical example of a first-order phase transition in which the continuous symmetry of the iso- tropic phase is broken [1]. In a nematic phase, molecules are aligned along a particular but arbitrary direction so as to have a long-range order in orientation while the trans- lational degrees of freedom remain disordered as in an isotropic fluid. At the isotropic-nematic transition the iso- tropy of the space is spontaneously broken and, as a con- sequence, correlations in distribution of molecules lose their rotational invariance. By computer simulations of a system of ellipsoids Phuong and Schmid [2] evaluated the effect of breaking of rotational symmetry on pair correla- tion functions (PCFs) and showed that in a nematic phase there are two qualitatively different contributions: one that preserves rotational invariance and the other that breaks it and vanishes in the isotropic phase. The symmetry preserv- ing part of PCFs passes smoothly without any abrupt change through the transition. The correlation functions which describe the distribu- tion of molecules in a classical fluid can be given as the simultaneous solutions of an integral equation, the Ornstein-Zernike (OZ) equation, and a closure relation that relates correlation functions to the pair potential. Well-known closure relations are the Percus-Yevick (PY) relation, the hypernetted-chain (HNC) relation, and the mean spherical approximation (MSA) [3]. This approach has been used quite successfully to describe the structure of isotropic fluids. However, the application of the theory to ordered phases has so far been very limited, though no feature of the theory inherently prevents it from being used to describe structures of the ordered phases. Holovko and Sokolovska [4] have used the MSA and the Lovett equation [5] which relates one-particle density to PCFs to solve analytically the OZ equation for a model of spherical particles with the long-range anisotropic interaction and determined the PCFs in a nematic phase. However, when Phuong and Schmid [2] used the PY and the Lovett equa- tions and solved the OZ equation numerically for a system of soft ellipsoids, nematic phase was not found and for this the PY closure was blamed. Here we adopt a method based on density-functional formalism and show that the PY relation gives nematic phase with PCFs harmonic coeffi- cients that have features similar to those found by simula- tions [2] and by analytical solution [4]. A density-functional theory (DFT) requires an expres- sion of the grand thermodynamic potential of the system in terms of one- and two-particle distribution functions and a relation that relates the one-particle density distribution x to PCFs. Such a relation is found by minimizing the grand thermodynamic potential with respect to x with appropriate constraints [6]. The correlation functions that appear in these equations are of the ordered phase and are functional of x. The free-energy functionals that exist in the literature [7,8] and have been used to study the freezing transitions replace these correlations by that of the iso- tropic fluids [6]. This approximation limits the applicabil- ity of the theory and needs improvement. We first show how the fact that PCFs in the nematic phase have two distinct parts leads us to divide the OZ equation and the closure relation into two sets of equations. The solutions of these equations give both the symmetry conserving and the symmetry breaking parts of PCFs. Using these correlation functions we construct a free- energy functional. This free-energy functional is then used to locate the isotropic-nematic transition in a model system of elongated rigid molecules interacting via the Gay-Berne (GB) pair potential [9]. The GB potential be- tween a pair of molecules (i, j) is written as u ^ r ij ; ^ e i ; ^ e j 4 ^ r ij ; ^ e i ; ^ e j R 12 R 6 , where R r ij ^ r ij ; ^ e i ; ^ e j 0 = 0 and ^ e i is the unit vector specifying the axis of symmetry of the ith molecule. The expressions for the angle dependent range parameter and potential well depth function contain four parameters x 0 , k 0 , , and . These parameters measure the anisotropy in the repul- sive and attractive forces. The parameters 0 and 0 scale PRL 97, 177801 (2006) PHYSICAL REVIEW LETTERS week ending 27 OCTOBER 2006 0031-9007= 06=97(17)=177801(4) 177801-1 © 2006 The American Physical Society

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Page 1: Pair Correlation Functions in Nematics: Free-Energy Functional and Isotropic-Nematic Transition

Pair Correlation Functions in Nematics: Free-Energy Functionaland Isotropic-Nematic Transition

Pankaj Mishra and Yashwant SinghDepartment of Physics, Banaras Hindu University, Varanasi-221 005, India

(Received 6 March 2006; published 25 October 2006)

We develop a free-energy functional for an inhomogeneous system that contains both symmetryconserved and symmetry broken parts of the direct pair correlation function. These correlation functionsare found by solving the Ornstein-Zernike equation with the Percus-Yevick closure relation. The methoddeveloped here gives the pair correlation functions in the ordered phase with features that agree well withthe results found by computer simulations. The theory predicts accurately the isotropic-nematic transitionin a system of anisotropic molecules and can be extended to study other ordered phases such as smecticsand crystalline solids.

DOI: 10.1103/PhysRevLett.97.177801 PACS numbers: 64.70.Md, 05.70.Ce, 64.70.Dv

The freezing of a fluid of anisotropic molecules into anematic phase is a typical example of a first-order phasetransition in which the continuous symmetry of the iso-tropic phase is broken [1]. In a nematic phase, moleculesare aligned along a particular but arbitrary direction so asto have a long-range order in orientation while the trans-lational degrees of freedom remain disordered as in anisotropic fluid. At the isotropic-nematic transition the iso-tropy of the space is spontaneously broken and, as a con-sequence, correlations in distribution of molecules losetheir rotational invariance. By computer simulations of asystem of ellipsoids Phuong and Schmid [2] evaluated theeffect of breaking of rotational symmetry on pair correla-tion functions (PCFs) and showed that in a nematic phasethere are two qualitatively different contributions: one thatpreserves rotational invariance and the other that breaks itand vanishes in the isotropic phase. The symmetry preserv-ing part of PCFs passes smoothly without any abruptchange through the transition.

The correlation functions which describe the distribu-tion of molecules in a classical fluid can be given as thesimultaneous solutions of an integral equation, theOrnstein-Zernike (OZ) equation, and a closure relationthat relates correlation functions to the pair potential.Well-known closure relations are the Percus-Yevick (PY)relation, the hypernetted-chain (HNC) relation, and themean spherical approximation (MSA) [3]. This approachhas been used quite successfully to describe the structure ofisotropic fluids. However, the application of the theory toordered phases has so far been very limited, though nofeature of the theory inherently prevents it from being usedto describe structures of the ordered phases. Holovko andSokolovska [4] have used the MSA and the Lovett equation[5] which relates one-particle density to PCFs to solveanalytically the OZ equation for a model of sphericalparticles with the long-range anisotropic interaction anddetermined the PCFs in a nematic phase. However, whenPhuong and Schmid [2] used the PY and the Lovett equa-

tions and solved the OZ equation numerically for a systemof soft ellipsoids, nematic phase was not found and for thisthe PY closure was blamed. Here we adopt a method basedon density-functional formalism and show that the PYrelation gives nematic phase with PCFs harmonic coeffi-cients that have features similar to those found by simula-tions [2] and by analytical solution [4].

A density-functional theory (DFT) requires an expres-sion of the grand thermodynamic potential of the system interms of one- and two-particle distribution functions and arelation that relates the one-particle density distribution��x� to PCFs. Such a relation is found by minimizing thegrand thermodynamic potential with respect to ��x� withappropriate constraints [6]. The correlation functions thatappear in these equations are of the ordered phase and arefunctional of ��x�. The free-energy functionals that exist inthe literature [7,8] and have been used to study the freezingtransitions replace these correlations by that of the iso-tropic fluids [6]. This approximation limits the applicabil-ity of the theory and needs improvement.

We first show how the fact that PCFs in the nematicphase have two distinct parts leads us to divide the OZequation and the closure relation into two sets of equations.The solutions of these equations give both the symmetryconserving and the symmetry breaking parts of PCFs.Using these correlation functions we construct a free-energy functional. This free-energy functional is thenused to locate the isotropic-nematic transition in a modelsystem of elongated rigid molecules interacting via theGay-Berne (GB) pair potential [9]. The GB potential be-tween a pair of molecules (i, j) is written as u�rij; ei; ej� �

4��rij; ei; ej��R�12 � R�6�, where R � �rij ���rij; ei; ej� � �0�=�0 and ei is the unit vector specifyingthe axis of symmetry of the ith molecule. The expressionsfor the angle dependent range parameter � and potentialwell depth function � contain four parameters x0, k0,�, and�. These parameters measure the anisotropy in the repul-sive and attractive forces. The parameters �0 and �0 scale

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Page 2: Pair Correlation Functions in Nematics: Free-Energy Functional and Isotropic-Nematic Transition

the distance and energy, respectively. The value of x0, k0,�, and � are taken 3.0, 5.0, 2.0, and 1.0, respectively.

The OZ equation which relates the total PCF, h�x1;x2�,with DPCF, c�x1;x2�, in an inhomogeneous system iswritten as [6,10] h�x1;x2� � c�x1;x2� �

Rc�x1;x3� �

��x3�h�x3;x2�dx3, where xi indicates both position riand orientation �i of the ith molecule, dx3 � dr3d�3.The PY relation is expressed as c�x1;x2� � �e�x1;x2� �1��1� h�x1;x2� � c�x1;x2��, where e�x1;x2� �exp���u�x1;x2��. We now write the pair correlationfunctions h and c as a sum of symmetry conserved andsymmetry broken parts, i.e., h � h�0� � h�n� and c �

c�0� � c�n�. This allows us to write the OZ and PYequationsas

h�0��x1;x2� � c�0��x1;x2�

� �0

Zc�0��x1;x3�h�0��x3;x2�dx3 (1)

c�0��x1;x2� � �e�x1;x2� � 1��1� h�0��x1;x2�

� c�0��x1;x2�� (2)

and

h�n��x1;x2� � c�n��x1;x2� �Zc�0��x1;x3��n�x3�h

�0��x3;x2�dx3 �Z��0 � �n�x3���c

�0��x1;x3�h�n��x3;x2�

� c�n��x1;x3�h�0��x3;x2� � c�n��x1;x3�h�n��x3;x2��dx3 (3)

c�n��x1;x2� � �e�x1;x2� � 1��h�n��x1;x2� � c�n��x1;x2��:

(4)

Here ��x3� � ��0 � �n�x3��, where �0 is the bulk numberdensity and �n�x3� � �0�f��3� � 1�. f��� is the singleparticle orientation distribution function normalized tounity.

Equations (1) and (2) give relations that are identicalto the ones used in calculating PCFs in an isotropic

phase. Relations given by (3) and (4) are new and givePCFs arising due to the breaking of symmetry. We chose acoordinate frame where the z axis points in the direction ofdirector n (director frame). All orientation dependent func-tions are expanded in spherical harmonics Ylm��� [2,11].This yields (for uniaxial nematic phase of axially symmet-

ric molecules) f��� �Pl�even�

������������������2l� 1�

pPlYl0���=

�������4�p

and

�r;�1;�2� �X

l1l2lm1m2m

l1l2lm1m2m�r�Yl1m1��1�Yl2m2

��2�Ylm�r�; (5)

where stands for h, c, or e. Pl is the order parameter; itsvalue is zero in the isotropic phase and nonzero in thenematic phase. In a uniaxial symmetric phase of axiallysymmetric molecules, m1 �m2 �m � 0 and l1 � l2 � las well as each l are even. Because h�0�, c�0�, and e preservethe rotational symmetry, for them l1l2lm1m2m�r� � l1l2l�r�Cg�l1l2lm1m2m�, where Cg is the Clebsch-Gordan coefficient.

We solved (1) and (2) for the GB potential using amethod described in [12] and determined the values ofc�0�l1l2lm1m2m

�r� and h�0�l1l2lm1m2m�r� for values of l, li up to

lmax � 8 at reduced temperature T� kBT=�0� � 1:0 andfor densities 0 � �� ��3

0� � 0:36. To solve (3) and (4)we first set up linear equations for h�n�l1l2lm1m2m

�r� and

c�n�l1l2lm1m2m�r�, using the expansions described above. In

these equations h�0�l1l2lm1m2m�r�, c�0�l1l2lm1m2m

�r� and the orderparameters Pl appear. Here we restrict ourselves to onlyone order parameter P2 and solve these equations for 0 �P2 � 0:70 at the interval of �P2 � 0:05 for all densitiesbetween 0 and 0.34 and for l, li up to lmax � 4. The solutionis found using the same iterative method [12] as in the caseof (1) and (2) but with two additional precautions: ascoefficients h�n�l1l2lm1m2m

�r� show oscillations (Fig. 2) whichextend to r� r=�0� � 20 we extended the range of

r�i:e:; rmax � 40� to ensure proper convergence. The otherpoint which needed special care is related to the pro-nounced long-range tail which occurs in coefficientsh�n�l1l2lm1m2m

�r� with m1, m2 � 1 (Fig. 3). For this weadopted a method discussed in [2,13]. This ensured thatthe finite size effect on the tail as well as its effect on otherharmonic coefficients are accounted for accurately.

The reduced free energy A��� of an inhomogeneoussystem is a functional of density ��x� and is written as[6] A��� � Aid��� � Aex���, where Aid��� �

Rdx��x��

�lnf��x��g � 1� is the ideal gas part. The excess partAex��� is related with the DPCF of the system as

�2Aex

���x1����x2�� �c�0��x1;x2;�0� � c

�n��x1;x2; ����:

(6)

Aex��� is found by functional integration of (6). In thisintegration the system is taken from some initial density tothe final density ��x� along a path in the density space; theresult is independent of the path of the integration [14]. Forthe symmetry conserving part c�0� the integration in densityspace is done taking isotropic fluid of density �l (thedensity of coexistence fluid) as reference. This leads to

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Page 3: Pair Correlation Functions in Nematics: Free-Energy Functional and Isotropic-Nematic Transition

A�0�ex ��� � Aex��l� �1

2

�Zdx1

Zdx2���x1����x2��c�x1;x2�; (7)

where �c�x1;x2��2Rd

Rd0c�0�fx1;x2;�l�

0��0��l�g, ���x� � ��x� � �l, Aex��l� is the excess reducedfree energy of the isotropic fluid of density �l and �0 isthe average density of the ordered phase.

In order to integrate over c�n����, we characterize thedensity space by two parameters and which vary from0 to 1. The parameter raises density from 0 to �0 as itvaries from 0 to 1 whereas parameter raises the orderparameter from 0 to P2 as it varies from 0 to 1. Thisintegration gives

A�n�ex ��� � �1

2

Zdx1

Zdx2��x1���x2�~c�x1;x2�; (8)

where

~c�x1;x2� � 4Z 1

0d

Z 1

0d0

Z 1

0d

Z 1

0d0

� c�n��x1;x2; 0�0;0P2�:

Note that while integrating over , P2 is kept fixed andwhile integrating over , �0 is kept fixed. The result doesnot depend on the order of integration. The free-energyfunctional of an ordered phase is the sum of Aid, A�0�ex , andA�n�ex . Note that the RY [7] free-energy functional is the sumof only A0

id and A0ex and contains an additional approxima-

tion in which �c�x1;x2� in (7) is replaced by c�x1;x2;�l�.The grand thermodynamic potential defined as �W �

A� ��Rdx��x�, where � is the chemical potential, is

preferred to locate the transition as it ensures that thepressure and chemical potential of the two phases remainequal at the transition. The transition point is determinedby the condition �W � Wl �W � 0. The order parame-ters are determined from equations found by minimizingthe grand thermodynamic potential with appropriate con-straints [6,13]. The isotropic-nematic transition at T �1:0 with one order parameter is found to take place at�l �� �l�3

0� � 0:3325 with ��� ��o � �l�=�l� �0:0086 and order parameter P2 � 0:40. For the RY free-energy functional the transition takes place at �l � 0:3570with �� � 0:0055 and P2 � 0:439. The symmetry break-ing part of PCFs makes the isotropic phase unstable andinduces the emergence of the ordered phase at lowerdensity.

In Fig. 1 we show some harmonic coefficients of DPCFin the director space for T � 1:0, � � 0:3361, and P2 �0:44. While the coefficients c220 000�r

� and c2201�10�r�

shown in Fig. 1(a) survive both in isotropic and nematicphases, the coefficients c200 000�r� and c002 000�r� shownin 1(b) survive only in the nematic phase and vanish in theisotropic phase. The contribution arising due to symmetrybreaking to coefficients c220 000�r� and c2201�10�r� is

found to be small compared to the symmetry conservingpart. Few selected harmonic coefficients of h are shown inFigs. 2 and 3 in director space. In Fig. 2 we plot theharmonic coefficients h200 000�r

� and h002 000�r� which

survive only in the nematic phase and note the oscillatorybehavior which continues to survive for large values of r.In Fig. 3 we plot coefficient h2201�10�r� which is offundamental importance as it defines nematic elastic con-stants [1] and decays as 1=r at large distance. This long-range tail behavior is attributed to the director transversefluctuations [4] which give rise to orientational wave ex-citations, i.e., the Goldstone modes. This can be seen bytaking the tensor order parameter Q�� �

1N

PNi�1

32 �

�ei�ei� �13����, where �, � � x, y, z, and ei� is the �

component of the molecular axis vector ei of each mole-cule and ��� the Kronecker symbol and calculating (as-suming that the director is along z and the y axis isperpendicular to wave vector q) the correlationhQxz�q�Qxz��q�i. The result involves coefficients

0

10

20

30

c 2000

00(r

* )

0 1 2 3

r*(=r/σ0)

0

50

100

150

c 2201

-10(r

* )

-150

-100

-50

0

c 2200

00(r

* ) cc

(0)

c(n)

0 2 4 6

r*

-10

-5

0

5

c 0020

00(r

* )

(a) (b)

ρ∗=0.3361

T*=1.0

P2=0.44

ρ∗=0.3361T

*=1.0

P2=0.44

FIG. 1. Harmonic coefficients cl1l2lm1m2m�r� in the director

frame. In (a) we show two those coefficients which preservethe rotational invariance while in (b) the coefficients that arisedue to symmetry breaking. In [2] harmonic coefficients arelabeled as cl1m1l2m2lm�r

�.

0 5 10 15 20

r*

-10

-5

0

h 2000

00(r

* )

0 5 10 15 20

r*

0

5

10

15

h 0020

00(r

* )

(a) (b)

ρ∗=0.3361

T*=1.0

P2=0.44

ρ∗=0.3361T

*=1.0

P2=0.44

FIG. 2. Coefficients hl1l2lm1m2m�r� which survive only in thenematic phase.

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Page 4: Pair Correlation Functions in Nematics: Free-Energy Functional and Isotropic-Nematic Transition

h�n�l1l2lm1m2m�q� with jm1j, jm2j � 1. These coefficients

which are the Fourier transform of h�n�l1l2lm1m2m�r� (Fig. 3)

behave as 1=q2 for q! 0. This is the case of the Goldstonemode of zero mass.

When the Ward identity which must be satisfied in thenematic phase is expressed in the functional differentialform it reduces to the Lovett equation [4] and is written as

1 � ��Xl1

Xl0

���������������2l0 � 1p

Pl0

��������������������������������������2l1 � 1��2l0 � 1�

20�

s

� Cg�l1; l0; 2; 0; 0; 0�Cg�l1; l

0; 2; 1; 0; 1�

�Zr2drcl1201�10�r�: (9)

Using the values of c2201�10�r�, c4201�10�r

�, and P2 in thenematic region we find the relation is fully satisfied.

The density-functional approach allows one to includemore order parameters in the theory even though they arenot included in calculating the PCFs. This is done throughthe parametrization of ��x� [6]. When we take two orderparameters P2 and P4 and use the free-energy functionaldeveloped here the transition takes place at T � 1 with�l � 0:317, �� � 0:026, P2 � 0:644, and P4 � 0:332.These values compare well with the simulation values,�l � 0:32, P2 � 0:66, and P4 � 0:29 [15]. This compari-son suggests that the effect of order parameter P4 on PCFsis small.

We now briefly comment on how the theory developedhere can be applied to the ordered phases which need fortheir description n�n � 2� number of order parameters. Insuch a case we can think of a n-dimensional order parame-ter space; a point in this space defines the values of all the n

order parameters. To obtain ~c, the integration in (8) can bedone along a straight line path that connects origin to apoint corresponding to the final values of the n orderparameters. This path is parametrized by a single variable. However, c�n� appearing in (8) has to be written asc�n��x1x2;0�0;0

�����������Pni�1

p�2i �, where �i is the ith order

parameter.In conclusion, we developed a method of solving the OZ

equation with a closure relation to get both the symmetryconserving and symmetry breaking parts of PCFs. Usingthese correlation functions we constructed a free-energyfunctional to study the freezing transition and other prop-erties of an ordered phase. Since the symmetry breakingparts of PCFs have features of the ordered phase includingits geometrical packing, the free-energy functional pro-posed here will allow us to study various phenomena ofthe ordered phases [13].

We thank J. Ram for his help in computation. This workwas supported by a research grant from DST of Govt. ofIndia, New Delhi.

[1] P. G. de Gennes and J. Prost, The Physics of LiquidCrystals (Clarendon, Oxford, 1993).

[2] N. H. Phuong and F. Schmid, J. Chem. Phys. 119, 1214(2003).

[3] C. G. Gray and K. E. Gubbins, Theory of Molecular Fluids(Oxford, New York, 1984).

[4] M. F. Holovko and T. G. Sokolovska, J. Mol. Liq. 82, 161(1999).

[5] R. A. Lovett, C. Y. Mou, and E. P. Buff, J. Chem. Phys. 65,570 (1976); M. S. Wertheim, J. Chem. Phys. 65, 2377(1976).

[6] Y. Singh, Phys. Rep. 207, 351 (1991).[7] T. V. Ramakrishnan and M. Yussouff, Phys. Rev. B 19,

2775 (1979); A. D. J. Haymet and D. Oxtoby, J. Chem.Phys. 74, 2559 (1981).

[8] A. R. Denton and N. W. Ashcroft, Phys. Rev. A 39, 4701(1989); A. Khein and N. W. Ashcroft, Phys. Rev. Lett. 78,3346 (1997).

[9] J. G. Gay and B. J. Berne, J. Chem. Phys. 74, 3316 (1981).[10] H. Workman and M. Fixman, J. Chem. Phys. 58, 5024

(1973); J. M. Caillol and J. J. Weis, J. Chem. Phys. 90,7403 (1989); H. Zhong and R. G. Petschek, Phys. Rev. E51, 2263 (1995).

[11] I. Paci and N. M. Cann, J. Chem. Phys. 119, 2638 (2003);S. H. L. Klapp and G. N. Patey, J. Chem. Phys. 112, 3832(2000); L. Blum and A. J. Torruella, J. Chem. Phys. 56,303 (1972).

[12] P. Mishra, J. Ram, and Y. Singh, J. Phys. Condens. Matter16, 1695 (2004).

[13] P. Mishra and Y. Singh (to be published).[14] W. F. Saam and C. Ebner, Phys. Rev. A 15, 2566 (1977).[15] L. Longa et al., Eur. Phys. J. E 4, 51 (2001).

0 5 10 15

r*

-25

-20

-15

-10

-5

0

h 2201

-10(r

* )hh

(0)

h(n)

0 0.1 0.2 0.3 0.4

1/r*

-6

-4

-2

0

h 2201

-10

ρ∗=0.3361T

*=1.0

P2=0.44

FIG. 3. Harmonic coefficient h2201�10 in the director frame.Details are same as in Fig. 1. Inset shows the plot of h2201�10

harmonics with respect to 1=r; the dotted line shows theextrapolated part.

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