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# Smectic ordering in liquid crystal - aerosil dispersions II. Scaling analysis

## I Introduction

The study of the effect of quenched random disorder ($`QRD`$) on phase transitional behavior remains an attractive area of research due to the broad implications outside the laboratory. The underlying physics has applications ranging from unique assemblies of complex fluids to doped semiconductors. Many systems have been the focus of both theoretical and experimental studies. The experimental efforts have concentrated on idealized model systems in the hopes of isolating the essential features of quenched random disorder. They include the still enigmatic superfluid transition of 4He in aerogels and porous glasses, the superfluid transition and phase separation of 4He-3He mixtures in silica aerogels Chan et al. (1996) and doped magnet systems Harris et al. (1997). Relatively recent efforts with liquid crystal (LC) - silica composites Zhou et al. (1997); Iannacchione et al. (1998); Bellini et al. (1998); Jin and Finotello (2001); Marinelli et al. (2001); Park et al. (2002); Bellini et al. (2001) have demonstrated that these are especially interesting model systems. They are of particular importance as a way to access ”soft” (elastically weak) phases of continuous symmetry, which are directly coupled to surfaces and external fields.

The general consensus is that the physics of $`QRD`$ in liquid crystals is essentially contained by a Random-Field approach Pelissetto and Vicari (2000). Recent theoretical efforts predict that an Ising system with quenched random fields will move towards a new Random-Field Ising ($`RFI`$) fixed point with increasing disorder. However, a Random-Field $`XY`$ ($`RFXY`$) system has no new fixed point that is stable. Here, with increasing strength of the disordering random field, an $`RFXY`$ system still has flows toward the $`XY`$ fixed point until long-range order is destroyed Pelissetto and Vicari (2000). Thus one expects, in general, that a $`3D`$-$`XY`$ system subject to random-field perturbations has no true long-range order (LRO). A detailed theoretical study of $`QRD`$ effects on smectic ordering in liquid crystals Radzihivsky and Toner (1999) concludes that arbitrarily small amounts of $`QRD`$ destroy even quasi-LRO and hence, no true smectic phase exists since the smectic correlation length remains finite for all strengths of disorder and all temperatures. This theoretical conclusion is in agreement with a recent x-ray study of octylcyanobiphenyl (8CB)+aerosil dispersions Park et al. (2002), the detailed results of which are presented in the companion paper to this work, denoted hereafter as paper I Leheny et al. (2002). This x-ray study reveals a finite, though large, smectic correlation length for all temperatures and densities of silica. However, smectic thermal fluctuations still exist above a pseudo nematic to smectic transition at T (close to but below T$`{}_{}{}^{o}{}_{NA}{}^{}`$ for pure 8CB). These smectic fluctuations are expected to remain in the $`XY`$ universality class but also show crossover behavior from Gaussian tricritical ($`TC`$) to $`3D`$-$`XY`$ with increasing strength of disorder Leheny et al. (2002).

In all fluid systems studied to date as models of such $`QRD`$ effects, including the liquid crystal system mentioned above, the random perturbations are introduced via the embedding of a random (gel-like) solid structure into the phase ordering material. An open question remains as to the connection between the concentration of such solid inclusions and the strength of the random disordering field. Also, the identification of $`QRD`$ is complicated by finite-size effects which could, in principle, play a dominant role in such systems. In simple finite-size scaling ($`FSS`$), where the confining surfaces play no interactive role, the $`\mathrm{𝑏𝑢𝑙𝑘}`$ critical correlation fluctuations are cut-off at a length dictated by the distance between surfaces, which corresponds to a minimum reduced temperature where the transition is ”truncated”. However, when the surfaces are arranged in a random manner with high void connectivity in order to introduce $`QRD`$, the distance between surfaces no longer acts as an upper length scale in the system, and changes in the transition’s critical behavior may also occur. Given the absence of LRO in such perturbed systems, the required characterization of the critical behavior may not be possible. In spite of this, if a critical power-law analysis of the transition heat capacity data is available, then, through two-scale universality, the critical behavior of the correlation length for T $`>`$ T may be estimated and compared with direct measurements. Finally, if the introduced random surfaces have in addition the freedom of an elastic response, then coupling between the gel and host elasticities can occur. This latter effect has only begun to be explored theoretically Olmsted and Terentjev (1996); Meeker et al. (2000); not (a).

The particular system that is the focus of this paper is a silica colloidal gel of aerosil particles dispersed in a liquid crystal denoted as LC+aerosil. The analysis will also be applied to another, earlier, system of an aerogel (fused silica gel) structure embedded within a liquid crystal denoted as LC+aerogel. The two are nearly identical in every respect $``$ fractal-like nature of the gel structure, surface chemistry, and density $``$ save for their relative elasticity. Additionally, the ease at achieving nearly arbitrary silica densities for the aerosil system allows for greater control of the disorder. For the 8CB+aerosil system, thermal evidence for two regimes of behavior has been found Iannacchione et al. (1998): low-density gels where pseudo-critical behavior is closely related to that for the pure LC and higher density gels where all transition features appear to be smeared. More rigid aerogels in LC+aerogel systems are crudely like the LC+aerosil gels in the high density regime but differ in some important ways since the elastic strain imposed by the random anchoring surfaces of aerogels is fully quenched. It appears that the disorder introduced by an aerogel is so great that all ”transition” features are dramatically smeared and the physics of such systems may be more closely related to static random-elastic strain disorder.

In spite of the loss of smectic LRO, Paper I Leheny et al. (2002) and an earlier calorimetric study of 8CB+aerosils Iannacchione et al. (1998) show that smectic thermal fluctuations still play an important role in LC+aerosil systems. Many concepts from pure materials such as finite-size scaling, two-scale universality, and tricritical-to-$`XY`$ crossover due to variable de Gennes coupling need to be considered in addition to intrinsic new quenched random effects that dominate at temperatures below an effective transition temperature. The present paper is organized as follows. The relevant characteristics of an aerosil gel are described in Section II. Section III reviews the essential features of LC+aerosil behavior near the N-SmA transition. The application of scaling analysis to calorimetric and x-ray results on the 8CB+aerosil system is presented in Section IV with comparisons made to the 8CB+aerogel system. Section V summarizes the conclusions that can be drawn from such scaling analysis and discusses the issue of the relationship between the $`RF`$ strength and the aerosil density. Appendix A reviews the relevant N-SmA critical behavior in pure liquid crystals, and Appendix B presents the necessary background for two-scale universality and finite-size scaling.

## II General description of aerosil gels

For liquid crystal systems, the introduction of quenched random disorder typically requires the inclusion of random solid surfaces. This can be accomplished by the percolation of a low-volume-fraction gel structure randomly arranged throughout the LC host. Such gels can be physically realized by a diffusion-limited-aggregation process which forms fractal-like structures having a wide distribution of void length scales. In practical terms, the fractal-like character is limited to length scales much larger than the size of the basic unit and smaller than some macroscopic size limiting the gel, i.e., the sample size.

Because of the hydroxyl groups on the surface of the $`70`$ Å diameter hydrophilic aerosil (SiO2) spheres used in this work, hydrogen-bonding is possible between aerosil particles Deg . When dispersed in an organic liquid medium, aerosil particles comprising $`3`$ to $`4`$ lightly fused spheres and having a mean radius of gyration of $`240`$ Å Iannacchione et al. (1998) will attach to each other and form a gel by a diffusion-limited aggregation process. This gel can be thought of as a randomly crossing ”pearl necklace” of silica and a cartoon depiction is given in Fig. 1. The hydrogen-bonded nature of the silica ”links” is relatively weak and gives these gels the ability to break easily and reform on moderate time scales (such gels are termed thixotropic). In addition, because of the diffusion-limited aggregation process by which gelation occurs, the structure of the final gel may become anisotropic if the gelation occurs in an anisotropic fluid, i.e., gelation in a well aligned nematic or smectic liquid crystal. This gives such colloidal gels very attractive uses in future research as a route to studying anisotropic random disorder not (b).

These aerosil gels are very similar in structure to the well-known and previously studied aerogels, which are another type of fractal silica gel. Aerogels are formed by a reaction-limited aggregation process and form a gel nearly identical to that of aerosils except that the basic silica units in aerogels are chemically fused together. Thus, aerogels have a large shear modulus (they break before yielding) while in contrast aerosil gels have a quite small, density-dependent, shear modulus Sonntag and Strenge (1987). Thus, aerosil gels can respond elastically to strains, which may turn out to be a crucial difference as will be discussed later. For the present work, the thixotropic character ensures that the silica strands mainly dictate, at low silica concentrations, the local nematic director without imposing high-energy elastic strains over the material throughout the void. As the silica density increases, the aerosil gel eventually becomes stiff enough to elastically strain the host fluid.

For any random gel structure, a mean distance between solid (gel) surfaces or a mean void size, $`l_o`$, can be uniquely defined despite the wide distribution of void sizes. The definition of $`l_o`$ in terms of macroscopic, and experimentally accessible, quantities begins by imagining a ”straw” of uniform cross-section $`A`$ sent through the gel; see Fig. 1. The places where the gel randomly intersects the ”straw” defines a solid length while the distance between intersections defines a void length. The relevant macroscopic quantities are the specific surface area $`a`$ in total surface area per mass (given as $`300`$ m2 g-1 Deg  for the type R300 aerosil used in the 8CB+aerosil samples) and the reduced density, $`\rho _S=`$ mass of solid per open volume or in our case grams of silica per cm3 of LC. Since the cross-section of this imaginary straw is uniform, the proper summing of the total void and solid volumes of the straw depends only on the void and solid lengths respectively, noting that each void must be bounded by two walls. The sum of the total solid length and the total void length is simply the length of the straw which spans the sample.

The two requirements for volume and length defined above allow the definition of the average void length as

$$l_o=2/a\rho _S.$$
(1)
See Ref. Iannacchione et al. (1998) and Porod (1982) for a more detailed derivation. Strictly speaking, this definition of $`l_o`$ is valid only in the dilute regime where the addition of more solid does not significantly change the specific surface area. However, as the concentration of solid increases, more surface area is lost due to multiple connections (”clumping” of basic units); thus the specific surface area should be a decreasing function of the solid volume fraction $`\mathrm{\Phi }`$. A limiting case of interest is when completely enclosed pores occur. Here, the open volume is now bounded on all sides and a re-derivation of the mean void (now pore) size along the lines described above yields $`l_o=6/a\rho _S`$. This can be recast into the form given in Eq. (1) if $`a_{pore}a_{void}/3`$. Thus, Eq. (1) is quite general for a random gel structure if the variation of $`a`$ with $`\rho _S`$ is known. The exact variation of $`a`$ with solid concentration depends on the specific process of densification of the gel. Since the gel structures for both aerosil gels and aerogels are nearly identical, results for void sizes determined from small-angle x-ray scattering (SAXS) of various density aerogels Wu et al. (1995) can be used to estimate the variation of $`a(\rho _S)`$, in m2 per gram, as $`a=300103.8\rho _S`$, where $`\rho _S`$ has the units grams of SiO2 per cm3 of LC. The condition for closed pores is crudely predicted to occur at $`\rho _S1.97`$ g cm-3 (assuming a continuous process of diffusion-limited aggregation). For all LC+aerosil and LC+aerogel samples studied to date, the density of silica employed has been well below that limit and the use of this estimate of $`a(\rho _S)`$ in Eq. (1) reproduces quite closely the SAXS measured void sizes of aerogels. This provides some confidence that a useful representation of a characteristic length scale $`l_o`$ for fractal-like gels is available.

From the above discussion, the reduced density $`\rho _S`$ is an attractive quantity to describe the gel and its disordering character not (c). Note that the volume fraction of LC in a silica boundary layer of thickness $`l_b`$ is given by $`\mathrm{p}=l_ba\rho _S`$ Iannacchione et al. (1998). This quantity $`\mathrm{p}`$ is the fraction of LC filling the voids that is in direct contact with the solid surfaces and thus considered strongly ”pinned”. Since $`\mathrm{p}`$ is a natural measure of the ”disordering strength” of the gel, $`\rho _S`$ is expected to be linearly related to this $`QRD`$ strength for low to moderate $`\rho _S`$ values not (d).

## III Nematic - smectic-A behavior for liquid crystal - silica dispersions

The essential feature of importance here is the observation that low silica density LC+aerosil samples exhibit pseudo-critical behavior that is parallel to the critical behavior exhibited by pure LCs in spite of the absence of smectic long range order in LC+aerosils. In Paper I, the usual scaling concepts are shown to hold for the relationship between the normalized thermal fluctuation amplitude $`\sigma _1^N`$ and the parallel correlation length $`\xi _{}`$ for T $`>`$ T, where T is an effective N-SmA transition temperature. These concepts also hold for the temperature dependence of the normalized integrated area of the static ($`QRD`$) fluctuation term in the x-ray structure factor for T $`<`$ T, where this area is proportional to $`a_2^N`$, and we drop hereafter the superscript $`N`$ denoting normalization. In the latter case, it is shown in Paper I that $`a_2(`$T$`{}_{}{}^{}`$T$`)^x`$, where the ”critical” exponent $`x`$ is essentially the same as $`2\beta `$ for the smectic order parameter squared in pure liquid crystals. Calorimetric data for 8CB+aerosils Iannacchione et al. (1998) support this view that effective critical behavior occurs for low silica density LC+aerosil samples.

The background given in App. A for trends in N-SmA critical behavior for pure liquid crystals as a function of the McMillan ration $`R_M=`$T$`{}_{NA}{}^{}/`$TNI is pertinent to LC+aerosil systems. It appears that increasing the density $`\rho _S`$ of the thixotropic gel of aerosils decreases the smectic-nematic coupling described in App. A. Indeed, there is a simple empirical connection between the variable $`R_M`$ for pure LCs and the variable $`\rho _S`$ for LC+aerosils. As described in Section IV of Paper I, an effective McMillan ratio $`R_M^{eff}`$(sil) for LC+aerosil systems can be defined as

$$R_M^{eff}(\mathrm{sil})=0.9770.47\rho _\mathrm{S}.$$
(2)
Figure 11 in Paper I demonstrates this equivalence of $`R_M`$ and $`\rho _S`$ as measures of changes in the smectic-nematic coupling in pure LCs and LC+aerosils. This connection will be discussed further in Sec. IVB.

The full power-law form in terms of the reduced temperature $`t=`$T$``$T$`{}_{}{}^{}/`$ T used to analyze experimental specific heat data associated with the N-SmA phase transition is Garland and Nounesis (1994)

$`\mathrm{\Delta }C_p(NA)=C_p(\mathrm{observed})\mathrm{C}_\mathrm{p}(\mathrm{background})`$
$`=A^\pm t^\alpha (1+D^\pm t^{\mathrm{\Delta }_1})+B_c,`$ (3)
where the critical behavior as a function of reduced temperature $`t`$ is characterized by an exponent $`\alpha `$, an amplitude $`A^\pm `$ above and below the transition, a critical background term $`B_c`$, and corrections-to-scaling terms characterized by the coefficients $`D^\pm `$ and exponent $`\mathrm{\Delta }_10.5`$. The excess N-SmA specific heat (heat capacity per gram of LC) data for 8CB+aerosil samples Iannacchione et al. (1998) is reproduced in Fig. 2 in log-log form in order to illustrate the quantities described above. Figure 2 highlights the quality of the fits to the standard power-law form for 8CB+aerosil samples with low $`\rho _S`$. Note the importance of the inclusion of the corrections-to-scaling term, seen as curvature at high $`t`$. In fact the quality of the fit for the lowest density 8CB+aerosil sample rivals that observed for most pure LCs. In addition, the changing shape of the N-SmA heat capacity peak with $`\rho _S`$ is clearly evident. As discussed in Ref. Iannacchione et al. (1998), it is clear from Fig. 2 that a fit to the data with Eq. (III) can include only data for $`t>t_m^\pm `$ since the $`\mathrm{\Delta }C_p`$ peak is truncated at a finite maximum value $`h_M\mathrm{\Delta }C_p^{max}(NA)`$.

The role of pseudo-critical behavior for the 8CB+aerosil system is fully described in Paper I and Ref. Iannacchione et al. (1998). In the present paper, the applicability of two-scale universality and finite-size scaling in describing the pseudo-critical behavior in LC+aerosils is investigated. Essential scaling background material is introduced in App. B, and these concepts are implemented in Sec. IV for the analysis of the N-SmA ”transition region” for 8CB+aerosils.

## IV Analysis of the nematic - smectic-A transition in the 8CB+sil system

### IV.1 Specific heat behavior

In order to utilize the scaling analysis described in App. B, the maximum length scale $`\xi _M`$ and the appropriate critical fluctuation parameters must be substituted into Eqs. (13) and (14), which are repeated here for convenience

$$\delta T^{}/T^{}2t_m^+=2(\xi _M/\xi _o)^{1/\nu _{}}$$
(4)
$$h_M=A^\pm (\xi _M/\xi _o)^{\alpha /\nu _{}}(1+D^\pm (\xi _M/\xi _o)^{\mathrm{\Delta }_1/\nu _{}})+B_c,$$
(5)
to describe the fractional temperature rounding of the transition and the specific heat maximum, respectively. In this paper, two approximations will be explored. In the first case, we use the mean void size as the cutoff length scale $`\xi _M=l_o`$ and the $`\mathrm{𝑏𝑢𝑙𝑘}`$ critical parameters are used. This approach represents conventional finite-size scaling, denoted as $`FSS`$, where the cut-off length scale is set by a natural length of the ”confinement”. In the second case, we use the calorimetrically determined 8CB+aerosil critical parameters and two-scale predictions for the bare correlation length and exponent and set the cutoff length scale to the saturated parallel smectic correlation length found by the x-ray analysis in Paper I, i.e., $`\xi _M=\xi _{}^{LT}`$. This analysis recognizes that the random-field effects truncate the growth of order and tests whether two-scale universality is obeyed on approaching this truncation. We label this approach random-field scaling, or $`RFS`$ for short.

The specific heat maximum $`h_M\mathrm{\Delta }C_p^{max}(NA)`$ is plotted versus $`\rho _S`$ in Fig. 3 for 8CB+aerosil and 8CB+aerogel samples. Given as a dashed line on this log-log plot is the simple scaling prediction using only the leading singularity of the pure 8CB heat capacity and the mean-void size as the truncation length. This ignores the critical background and corrections-to-scaling terms in Eq. (5) and yields a straight line having a slope of $`\alpha /\nu _{}=0.45`$. This is the usual theoretical $`FSS`$ prediction for $`h_M`$, and its failure highlights the importance of using the full expression given by Eq. (5). Surprisingly, the full analysis denoted as $`FSS`$, which uses the pure 8CB critical parameters and $`\xi _M=l_o`$ from Eq. (1), appears to work very well over the entire range of $`\rho _S`$. This is surprising since the critical behavior of the 8CB+aerosil samples is changing with $`\rho _S`$ as seen in Fig. 2 and the saturated parallel smectic correlation length $`\xi _{}^{LT}`$ is much larger than $`l_o`$ for all $`\rho _S`$ Leheny et al. (2002). Thus, we are suspicious that this agreement may be accidental.

The analysis denoted as $`RFS`$ uses the evolving specific heat critical behavior and two-scale universality predictions (see App. B) for the equivalent correlation length critical behavior at each $`\rho _S`$. The low-temperature experimentally measured saturated parallel correlation length $`\xi _{}^{LT}`$ is used as the truncation length $`\xi _M`$. This analysis reproduces very closely the observed heat capacity maximum and is completely consistent with both the effective critical behavior and the maximum smectic correlation length. Unfortunately, this analysis is only applicable up to $`\rho _S0.1`$ since a critical analysis of $`\mathrm{\Delta }C_p(NA)`$ is not possible for larger $`\rho _S`$ Iannacchione et al. (1998). Note that $`h_M`$ for 8CB+aerogel samples can not be described by either scaling methods. For either scaling approximation to reproduce the aerogel results, a far smaller $`\xi _M`$ is required, which indicates that the aerogel has a much stronger disordering influence than the aerosil at any given $`\rho _S`$ value.

The fractional rounding of the transition $`\delta `$T$`{}_{}{}^{}/`$T for 8CB+aerosil and 8CB+aerogel samples is given versus $`\rho _S`$ in Fig. 4. For samples where critical specific heat fits were not possible, i.e., 8CB+aerosil for $`\rho _S>0.1`$ and all 8CB+aerogel samples, the fractional rounding is estimated ad hoc as $`10\%`$ larger than the width between inflection points in $`\mathrm{\Delta }C_p`$. As was seen in Fig. 3, the $`FSS`$ analysis works well for $`\mathrm{𝑎𝑙𝑙}`$ densities of 8CB+aerosil samples. As before, this is surprising given the known changes in critical behavior and the fact that $`\xi _{}^{LT}>l_o`$. The $`RFS`$ analysis predicts a somewhat sharper transition than is observed. The observed rounding is not likely influenced by the amplitude of temperature oscillations employed by the ac-calorimetric technique in Refs. Iannacchione et al. (1998) and Wu et al. (1995), which is on the order of $`5`$ mK and would account for a fractional rounding of only $`10^5`$. The estimation $`t_m^{}=t_m^+`$ explicit in Eq. (4) may be in question as it assumes that the unknown critical behavior of the correlation length below T is the same as that above T. A consequence of these arguments is that the agreement of $`FSS`$ is likely accidental although intriguing. Again, the 8CB+aerogel fractional rounding is much larger than that for the 8CB+aerosil samples, which is an indication that a smaller $`\xi _M`$ is required and supports the view of a stronger disordering influence for the aerogel than the aerosil.

Figure 5 presents the N-SmA transition enthalpy $`\delta H_{NA}`$ versus $`\rho _S`$ for 8CB+aerosil and 8CB+aerogel samples. Unlike $`h_M`$ and $`\delta `$T$`{}_{}{}^{}/`$T which are measures of truncation effects on $`\mathrm{\Delta }C_p`$ very close to the peak at T, $`\delta H_{NA}=\mathrm{\Delta }C_p(NA)𝑑T`$ is sensitive to both truncation and changes in the shape of $`\mathrm{\Delta }C_p`$ over its entire temperature range. This is clearly seen in Fig. 2 and is discussed in detail in Ref. Iannacchione et al. (1998). A finite-size scaling analysis for $`\delta H_{NA}`$ proceeds by integrating the available $`\mathrm{\Delta }C_p`$ critical form approximately $`\pm 3`$ K about T ($`|t|10^2`$) to the point corresponding to $`t_m^\pm `$. As an approximation, a linear evolution of $`\mathrm{\Delta }C_p`$ between $`t_m^+`$ and $`t_m^{}`$ is assumed. The $`FSS`$ analysis, given by the solid line in Fig. 5, does not agree well with the data for either system. The failure of this model is not surprising since it ignores any changes in the $`\mathrm{\Delta }C_p`$ critical parameters such as $`A^\pm `$ and $`\alpha `$ with $`\rho _S`$. A $`RFS`$ analysis would not be very meaningful for $`\delta H_{NA}`$ since for $`\rho _S<0.1`$, the input parameters for this model automatically insure perfect agreement. Also, the necessary input critical parameters cannot be obtained for 8CB+aerosil samples with $`\rho _S>0.1`$ or for any of the 8CB+aerogel samples.

### IV.2 Smectic-A x-ray scattering for T $`>`$ T\*

Two-scale universality is reviewed in App. B, where it is assumed that the $`3D`$-$`XY`$ result

$$\alpha A^+(\xi _o\xi _o^2)0.647$$
(6)
should hold for 8CB+aerosil samples. To proceed further, two additional assumptions are adopted that are inherent in the x-ray analysis presented in Paper I: $`(\nu _{}\nu _{})`$ and $`(\xi _o/\xi _o)`$ for 8CB+sil samples have the pure 8CB values of $`0.16`$ and $`2.22`$ respectively for all $`\rho _S`$. For those 8CB+aerosil samples where critical $`\mathrm{\Delta }C_p(NA)`$ fits are available, the three above assumptions allow the prediction of $`\xi _o`$, $`\xi _o`$, $`\nu _{}`$, and $`\nu _{}`$. These parameters will vary somewhat with $`\rho _S`$ since the $`\alpha `$ and A+ values from the critical heat capacity fit vary with $`\rho _S`$. The resulting $`\xi _{}`$($`\rho _S`$, T) ”critical” behavior for T $`>`$ T permits the $`RFS`$ calculations of $`h_M`$ and $`\delta `$T$`{}_{}{}^{}/`$T presented Sec. IVA.

Given two-scale universality and the assumptions outlined above, both the bare smectic correlation length and the effective critical exponent may be estimated from the critical analysis of the heat capacity data. Thus, the self-consistent critical behavior predicted here can be directly compared to those measured in Paper I.

Presented in Fig. 6 are the experimentally measured $`\xi _{}`$ values as a function of reduced temperature for the 8CB+aerosil data taken from Paper I Leheny et al. (2002). The two lines given in Fig. 6 show the observed critical behavior in pure 8CB Ocko et al. (1986), where Tc is used for T\*, and the two-scale prediction for $`\xi _{}`$ for the 8CB+aerosil sample where the predicted correlation lengths differ most from those of 8CB ($`\rho _S=0.092`$). Note that although $`\nu _{}`$ and $`\xi _o`$ both vary with $`\rho _S`$, the predicted overall trends of $`\xi _{}(t)=\xi _ot^\nu _{}`$ values differ only slightly from pure 8CB. The experimental $`\xi _{}(t)`$ data for various $`\rho _S`$ agree well with each other within the scatter but all 8CB+aerosil values are consistently $`\mathrm{𝑙𝑎𝑟𝑔𝑒𝑟}`$ than scaling prediction. The significance of this observation is not known.

As an analog to Figure 11 of Paper I, the experimentally measured heat capacity exponents $`\alpha `$ for the N-SmA transition in pure LCs and the effective exponents $`\alpha _{eff}`$ for the N-SmA pseudo-transition for 8CB+aerosil samples can be plotted versus $`R_M`$ and $`\rho _S`$ respectively, and this is shown in Fig. 7. In addition, the variation of the mean correlation length exponent $`\overline{\nu }(\nu _{}+2\nu _{})/3`$ for pure LCs (versus $`R_M`$) and those predicted by our two-scale analysis (versus $`\rho _S`$) are also plotted. Going from left to right in Fig. 7 corresponds to $`\mathrm{𝑑𝑒𝑐𝑟𝑒𝑎𝑠𝑖𝑛𝑔}`$ nematic-smectic coupling along the lines given in Ref. Garland and Nounesis (1994) for pure LCs. The two-scale predicted critical evolution of the average correlation length exponent with respect to $`\rho _S`$ is in good agreement with the corresponding evolution in pure LCs with respect to $`R_M`$. This match is completely consistent with the correlation between $`\rho _S`$ and $`R_M`$ seen from the experimentally measured exponents $`\alpha `$ and $`x2\beta `$ in Paper I and given previously in Eq. (2). Fig. 7 demonstrates that the two-scale predicted behavior given in this analysis for the correlation lengths is consistent with other observed trends in the evolution of pseudo-critical behavior with $`\rho _S`$.

## V Discussion and conclusions

Despite the loss of long-range smectic order, quasi-critical thermal fluctuations remain important at high temperatures for low silica density 8CB+aerosil samples. In addition, two-scale universality analysis provides a link between the SmA quasi-critical behavior of the heat capacity and the correlation lengths. The smectic fluctuations are modified from the pure 8CB behavior due to the effects of quenched-random-disorder. A collection of effective critical exponents for the 8CB+aerosil system and selected pure LCs as a function of $`\rho _S`$ and $`R_M`$, respectively, is presented in Table 1. As shown in Paper I and here, the density $`\rho _S`$ of an aerosil gel is directly correlated to the McMillan ratio $`R_M`$ of pure LCs, both of which are indicators of the strength of smectic-nematic coupling. The flow of the effective critical behavior for the N-SmA transition shown in Table 1 and Fig. 7 (see also Fig. 11 of Paper I) as a function of this $`QRD`$ induced decoupling is consistent with theoretical predictions that no new fixed point is present for the $`RFXY`$ model Pelissetto and Vicari (2000). For the liquid crystal - silica dispersion system studied here, the flow is from near a Gaussian tricritical point toward the $`3D`$-$`XY`$ fixed point.

This crossover behavior is explained for pure LCs by a decrease in nematic – smectic coupling as $`R_M`$ decreases. For 8CB+aerosils, an increase in $`\rho _S`$ appears to have the same effect. Recent work has found that aerosil gels exhibit dynamics which can couple to a host liquid crystal Retsch et al. (2002) presumably through direct coupling to director fluctuations. Also, recent deuterium NMR studies of 8CB+aerosils Jin and Finotello (2001) found no appreciable change in the magnitude of orientational order above T for $`\rho _S<0.1`$. The reason appears to be that the aerosil particles form a hydrogen-bonded thixotropic $`3D`$ gel network that provides (a) random anchoring surfaces for 8CB molecules and (b) because of the flexible/fragile nature of the silica gel, random elastic dampening of elastic (director) fluctuations in the liquid crystal. Both effects will reduce the nematic orientational susceptibility by suppressing $`\mathrm{𝑑𝑖𝑟𝑒𝑐𝑡𝑜𝑟}`$ fluctuations. Thus, increasing $`\rho _S`$ in LC+aerosil samples is equivalent to decreasing $`R_M`$ in a pure liquid crystal, which in the case of 8CB drives its critical behavior towards $`XY`$. This may have important consequences for the $`\mathrm{𝑏𝑢𝑙𝑘}`$ N-SmA behavior as theoretical efforts have mostly concentrated on the de Gennes type of smectic coupling to the magnitude of nematic order parameter, and it appears that the coupling to director fluctuations may play an important role in the crossover behavior.

Because the random disorder is introduced by the inclusion of network gel structures within the liquid crystal, finite-size effects can exist and may play a role in truncating thermally driven fluctuations. Such effects would explain the increasing suppression of the heat capacity peak with increasing $`\rho _S`$, which corresponds to decreasing the mean distance between solid surfaces. Scaling analysis provides a good description of the maximum heat capacity and the fractional rounding (or truncation) of the transition for all 8CB+aerosil samples. However, $`FSS`$ analysis does not provide a good prediction of the trend with $`\rho _S`$ for the transition enthalpy $`\delta H_{NA}=\mathrm{\Delta }C_p(NA)𝑑T`$. The reason for this is the fact that the trend in $`\delta H_{NA}`$ is dominated not by the truncation of the $`\mathrm{\Delta }C_p(NA)`$ peak but by the changes in shape and size of $`\mathrm{\Delta }C_p(NA)`$ over its entire range, and the latter effect is due to crossover rather than finite-size.

Below the pseudo-transition temperature T, the correlation lengths and the amplitudes of the thermal term in the smectic structure factor for 8CB+aerosils saturate and are approximately temperature independent Leheny et al. (2002). Quenched random disorder imposed by the aerosil gel network dominates the smectic fluctuations below the pseudo-transition. Plotted in Fig. 8 are the low-temperature parallel correlation lengths $`\xi _{}^{LT}`$ taken from Paper I plus the corresponding perpendicular $`\xi _{}^{LT}`$ values and the mean correlation lengths $`\overline{\xi }=(\xi _{}\xi _{}^2)^{1/3}`$. Also plotted are the ”isotropic” smectic correlation lengths reported at low temperature for 8CB+aerogel samples Bellini et al. (2001), the mean-void size $`l_o`$ based on Eq. (1), and an estimate of the saturated $`\mathrm{𝑛𝑒𝑚𝑎𝑡𝑖𝑐}`$ $`\mathrm{𝑑𝑖𝑟𝑒𝑐𝑡𝑜𝑟}`$ correlation length $`\xi _N`$ measured in 6CB+aerosil samples Bellini et al. (1998). As discussed in Paper I, the parallel correlation length is much larger than $`l_o`$ but smaller than $`\xi _N`$ for all 8CB+aerosil samples studied. The first fact indicates than the smectic domains span many ”voids” and it is thus reasonable to expect that their influence is of a random-field type, while the latter fact is physically reasonable since the observed smectic domains cannot be larger than the size of a nematic domain. However, 6CB does not exhibit a smectic phase, so it remains unknown how the director correlation length would change, if at all, due to the onset of smectic order. Interestingly, the low-temperature 8CB+aerogel correlation lengths appear to agree fairly well with $`l_o`$, while the aerogel $`\mathrm{\Delta }C_p(NA)`$ peak is severely rounded, indicating that 8CB is very strongly perturbed by the rigid fused silica gel.

In spite of the applicability of the pseudo-critical scaling ideas discussed here and in Paper I, quenched random disorder plays a dominate role in the behavior of 8CB+aerosils for temperatures below T. In particular, consider the x-ray structure factor below T, which is dominated by the ”Lorentzian-squared” type term expected for random-field disordered systems Leheny et al. (2002). Random-field theories postulate a random-field at each $`i^{\mathrm{th}}`$ ”spin” site of strength $`\stackrel{}{h}_i`$ whose average is $`\stackrel{}{h}_i=0`$ but whose square defines the variance of the disorder $`\mathrm{\Delta }\stackrel{}{h}_i\stackrel{}{h}_i=|h^2|`$ Aharony and Pytte (1983). The x-ray analysis presented in Paper I uses a structure factor analogous to that used for the analysis of random-field magnets given in Ref. Aharony and Pytte (1983); see Eq. (1) in Paper I, Thus, the saturated (low-temperature, denoted by the superscript $`LT`$) values of the mean smectic correlation length $`\overline{\xi }^{LT}=(\xi _{}\xi _{}^2)^{1/3}`$, and the amplitude of the thermal contribution $`\sigma _1^{LT}`$, as well as the amplitude of the $`QRD`$ contribution $`a_2`$ to the structure factor can be compared to the predicted scaling for random-field disorder. Note that $`a_2`$ is temperature dependent over the entire temperature range, thus we use a value for $`a_2(\mathrm{\Delta }T)`$ at $`\mathrm{\Delta }T=TT^{}=6`$ K in what follows. The relevant scaling relations predicted for random-field systems at low temperatures are

$`\overline{\xi }\mathrm{\Delta }^{\nu _\mathrm{\Delta }}`$
$`\sigma _1\overline{\xi }^3`$ (7)
$`a_2\overline{\xi }^0=constant`$
$`a_2/\sigma _1\overline{\xi }^3`$
where $`\nu _\mathrm{\Delta }=1/(d_cd)`$, $`d_c`$ is the lower critical dimension, and $`d=3`$ is the physical dimension of the random-field system Aharony and Pytte (1983). We have dropped the superscript $`LT`$ for convenience here and in the rest of this discussion. For a pure, continuous symmetry, $`XY`$ system that exhibit true long-range order $`d_c(XY)=2`$, which shifts upward for a random-field $`XY`$ system to $`d_c(RFXY)=4`$ Aharony et al. (1976). Although the N-SmA phase transition is not a simple member of the $`3D`$-$`XY`$ universality class, Eqs.(V) are expected to be reasonably applicable for smectics. Thus $`\nu _\mathrm{\Delta }=1`$ for the divergence of the smectic correlation length with the strength of the random-field. Substituting this value of $`\nu _\mathrm{\Delta }`$ and eliminating $`\overline{\xi }`$ from the expressions for the scattering amplitudes in Eqs. (V), we find the predicted scaling relations solely in terms of the random-field variance for an $`RFXY`$ system as

$`\overline{\xi }\mathrm{\Delta }^1|h|^2`$
$`\sigma _1\mathrm{\Delta }^3|h|^6`$ (8)
$`a_2\mathrm{\Delta }^0=constant`$
$`a_2/\sigma _1\mathrm{\Delta }^3|h|^6`$
The scaling of these quantities with respect to $`\rho _S`$ can be compared to the predicted scaling behavior with respect to $`\mathrm{\Delta }`$ in order to make a connection between $`\mathrm{\Delta }`$ and ultimately $`|h|`$ with $`\rho _S`$. In Paper I the simple assumption that $`\mathrm{\Delta }\rho _S`$ is made, while the assumption $`\rho _S|h|\mathrm{\Delta }^{1/2}`$ has been made elsewhere Bellini et al. (2001).

As discussed in Paper I in terms of $`\xi _{}`$, a one-regime $`\rho _S`$ analysis (a single trend over the entire range of $`\rho _S`$ values studied) yields for the 8CB+aerosil system $`\overline{\xi }\rho _S^{1.0\pm 0.2}`$. Similarly, the scattering amplitude ratio as a function of $`\overline{\xi }`$ yields $`a_2/\sigma _1\overline{\xi }^{2.68\pm 0.26}`$ at $`\mathrm{\Delta }T=6`$ K. The scatter in the experimental values of $`a_2(\mathrm{\Delta }T)`$ as a function of $`\rho _S`$ only allows a very rough estimate of its scaling, but it appears to be very weakly dependent on either correlation length or silica density. Unfortunately, the uncertainties in $`\sigma _1^{LT}`$ values arising from fitting the x-rays profiles at low temperatures (where the quenched random term greatly overshadows the thermal fluctuation term) and the added uncertainties from normalization make it unsuitable for testing as a function of $`\rho _S`$. However, the ratio $`a_2(\mathrm{\Delta }T)/\sigma _1^{LT}`$ is better characterized since it is independent of the normalization procedure.

One possible explanation for the observed systematic deviations from the simple power-law forms given above is that there is a finite maximum aerosil density above which no smectic correlations can exist. This maximum $`\rho _S`$ corresponds to a minimum mean void size, $`l_c`$, below which the liquid crystal has insufficient space to form smectic layers. Since at low densities the void size $`l_o`$ is inversely related to $`\rho _S`$ as shown in Sec. II, we propose an empirical relationship

$$\overline{\xi }=A(l_ol_c)$$
(9)
for a linear scaling of the mean correlation length with the corrected void size $`l_ol_c`$. The variation of both $`\overline{\xi }`$ and $`a_2(`$T$`{}_{}{}^{}6`$ K$`)/\sigma _1`$ with $`(l_ol_c)`$ is given in Fig. 9, where $`A0.93`$ and $`l_c80`$ Å were found by a best linear fit of $`\overline{\xi }`$ with Eq. (9) not (e). The solid line in the top panel shows the result of this fit. In addition, the solid line in the lower panel of Fig. 9 shows the expected behavior of $`a_2(\mathrm{\Delta }T)/\sigma _1^{LT}`$ given the empirical relationship of Eq. 9 with $`l_c=80`$ Å and the random-field scaling predicted in Eq. (V). A fit with $`a_2(\mathrm{\Delta }T)/\sigma _1^{LT}(l_ol_c)^y`$, allowing $`y`$ to be a free parameter and fixing $`l_c=80`$ Å, yielded the dashed line in the lower panel and the exponent value $`y=2.6`$. Since this small $`l_c`$ value is approximately twice the smectic partial bilayer thickness in 8CB, it is reasonable that no smectic ordering can occur when $`l_ol_c`$. The overall behavior shown in Fig. 9 as compared to the random-field scalings for an $`XY`$ system suggests that the random-field strength $`\mathrm{\Delta }=|h|^2\rho _S`$, at least for small $`\rho _S`$ (and thus large $`l_o`$). This use of the empirical relationship in Eq. (9) allows us to bring the observed results into better agreement with predictions for scaling in random-field systems.

There is a second possible explanation for the clear deviations from a simple power-law dependence on $`\rho _S`$ shown in Paper I and here in Fig. 8. This second possibility is the existence of a more complex relationship between $`\mathrm{\Delta }`$ and $`\rho _S`$. The correlation lengths appear to have a weaker $`\rho _S`$ dependence than the mean void size below $`\rho _S=0.1`$, while above this density the opposite occurs not (f). In addition, the value of the ratio $`a_2(\mathrm{\Delta }T=6`$ K$`)/\sigma _1^{LT}`$ exhibits distinctly different power-law dependencies on $`\rho _S`$ above and below this silica density; see Fig. 10 and also Fig. 12 in Paper I for further details. Using separate power-law characterizations for low density ($`\rho _S0.1`$) and high density ($`\rho _S0.1`$), we find

$`\overline{\xi }\rho _S^{0.5\pm 0.1}(low\rho _S),\rho _S^{1.4\pm 0.1}(high\rho _S)`$ (10)
$`a_2/\sigma _1\rho _S^{1.2\pm 0.1}(low\rho _S),\rho _S^{3.7\pm 0.3}(high\rho _S)`$
These two-regime fits are shown for $`\overline{\xi }`$ and $`a_2/\sigma _1`$ in Fig. 10. Recall that the concept of a low density regime ($`\rho _S<0.1`$) and a high density regime ($`\rho _S>0.1`$), shown in Eq. (10), is supported by the specific heat data Iannacchione et al. (1998), where power-law fits were possible when $`\rho _S<0.1`$ but not when $`\rho _S>0.1`$.

In order to establish a connection between the disorder variance $`\mathrm{\Delta }`$ (a measure of the overall disordering strength of the individual random fields $`h_i`$, $`\mathrm{\Delta }=|h|^2`$) and the silica density $`\rho _S`$ for low and high $`\rho _S`$ regimes, we compare Eqs. (V) and (10) for $`\overline{\xi }`$ and the ratio $`a_2(\mathrm{\Delta }T)/\sigma _1^{LT}`$, which are the two best characterized quantities. For $`\rho _S0.1`$ the result is $`\mathrm{\Delta }\rho _S^{0.5}`$. In contrast, for $`\rho _S>0.1`$ the result is $`\mathrm{\Delta }\rho _S^{1.3}`$. This idea of two regimes may be consistent with the picture of the aerosil gel described earlier where, in addition to the random silica strands (”pearl-necklace” of aerosil beads) providing the random-field dictating the local orientation of the nematic director, there perhaps exists an elastic coupling of these tenuous strands to the nematic director. This coupling would dampen the size of director fluctuations analogous to the effect of a wider nematic temperature range, and this gives a physical interpretation to the critical flow with random-field strength towards the underlying $`XY`$ fixed point. The apparent increase in the relative effect of the elastic coupling seen by the stronger scaling of the quenched random disorder strength with silica density may be an indication that the aerosil gel has become significantly stiffer when $`\rho _S>0.1`$ suggesting the possibility that a rigidity transition has occurred in the gel.

In conclusion, a combination of finite-size effects and two-scale universality concepts has yielded a successful connection between 8CB+aerosil thermal behavior and x-ray correlation length behavior. The truncation of $`\mathrm{\Delta }C_p(NA)`$ peaks, measured by $`h_M`$ and $`\delta `$T$`{}_{}{}^{}/`$T, and the observation of high-temperature 8CB+aerosil correlation lengths that are close to those for pure 8CB are both well explained. The observed dependence of the integrated area $`\delta H_{NA}`$ on $`\rho _S`$ is not properly described by finite-size scaling, and the reason for this failure is clear. Trends in $`\delta H_{NA}`$($`\rho _S`$) reflect the changing shape of $`\mathrm{\Delta }C_p`$ peaks over a wide temperature range as $`\rho _S`$ varies. As described in Paper I Leheny et al. (2002) and in Sec. IV of the present paper, quenched random disorder plays a dominant role in changing the effective pseudo-critical exponents that describe the smectic behavior in 8CB+aerosils. The density $`\rho _S`$ for 8CB+aerosil samples can be equated to the McMillan ratio $`R_M`$ for pure LCs; see Eq. (2). Since in pure LCs a larger McMillan ratio implies a larger nematic susceptibility, increasing $`R_M`$ corresponds to increasing the smectic-nematic coupling. Increasing $`\rho _S`$ for LC+aerosils has the opposite effect, as expected. The linearity of the relationship between $`\rho _S`$ and $`R_M`$ provides support for the view that the aerosil gel is involved in decoupling the nematic and smectic order parameters. It seems possible that the elasticity of the aerosil gel plays an important part in the theory of gels as a random perturbation acting on the N-SmA transition in liquid crystals. Theory incorporating such elastic aspects is in progress not (a). Finally, reasonable scaling was observed of the smectic correlation length and scattering amplitudes with respect to the silica density or mean void size, which were roughly consistent with predictions for random-field type disorder. However, the theoretical predictions for random-field systems were for uncorrelated random fields, while the disorder due to the aerosil gel are correlated, over some small length scale, due to their fractal structure not (g). The effect of algebraic correlations in the disorder on the random-field scaling predictions would be an attractive avenue for theoretical investigation.

###### Acknowledgements.

We thank P. Clegg, T. Bellini, L. Radzihovsky, N. A. Clark, and A. Aharony for helpful discussions. This work was supported by the NSF under the NSF-CAREER award DMR-0092786 (WPI), the NSF-CAREER award DMR-0134377 (JHU), and Contract No. DMR-0071256 (MIT) and by the Natural Science and Engineering Research Council of Canada (Toronto).

## Appendix A Relevant nematic - smectic-A behavior in pure liquid crystals

### A.1 General Description of the N-SmA phase transition

Although there is still some theoretical debate, the best experimental evidence to date points to $`3D`$-$`XY`$ as the underlying critical behavior for the N-SmA transition over experimentally accessible ranges of reduced temperature $`t`$ Garland et al. (1993). For pure liquid crystals, smectic ordering is strongly influenced by two types of coupling to nematic order: coupling to the magnitude of nematic order ($`S`$) and to the nematic director fluctuations ($`\delta \widehat{n}`$).

### A.2 Smectic coupling to the nematic order parameter

The first type of nematic - smectic coupling is the so-called de Gennes coupling of the form $`\psi ^2S`$. Such a term affects the coefficient $`b`$ of the quartic term $`b\psi ^4`$ in the mean-field Landau expansion of the smectic free-energy in terms of the complex smectic order-parameter $`\psi `$ de Gennes and Prost (1993). Since the nematic elastic constants are proportional to the square of $`S`$, this coupling reflects the effect of the ”softness” of the nematic order prior to the onset of smectic order. The strength of this coupling depends on the magnitude of the nematic susceptibility, $`\chi _N`$, and such a coupling can drive the N-SmA transition from $`XY`$-like ($`b0`$) to $`TC`$ ($`b=0`$) to weakly first-order ($`b<0`$) with increasing $`\chi _N`$. This is clearly seen as a trend with the width of the nematic temperature range, or the McMillan ratio $`R_M=`$ TNA/TNI, which directly influences $`\chi _N`$ Garland and Nounesis (1994). As an example, the heat capacity critical exponent varies from $`\alpha =0.50`$ to $`0.10`$ as this ratio varies from $`R_M=0.994`$ for a $`2`$-K wide nematic range to $`0.954`$ for a $`15`$-K wide nematic range. For LC samples with large nematic ranges, $`R_M0.898`$ ($`45`$-K wide) to $`R_M0.660`$ ($`189`$-K wide), the experimental exponent is $`\alpha \alpha _{XY}=0.013`$ Lipa et al. (1996); Campostrini et al. (2000).

### A.3 Smectic coupling to director fluctuations

Smectic order coupling to the director fluctuations has the form $`\psi ^2\delta \widehat{n}`$. Thus, in addition to the ”softness” of the nematic, fluctuations in the director orientation compete with the establishment of smectic order by exciting anisotropic elastic deformations in the smectic. The theory for such coupling is not yet complete nor are all the implications of this effect understood, but a self-consistent one-loop model has been put forward Andereck and Patton (1994). This type of coupling leads to anisotropy in the correlation lengths parallel and perpendicular to the nematic director (a feature not present in a normal $`3D`$-$`XY`$ system) and a very gradual crossover from a broad weakly-anisotropic critical correlation regime $`\nu _{||}\nu _{}`$ (weak coupling limit) toward a strongly-anisotropic $`\nu _{||}=2\nu _{}`$ regime (strong coupling limit). The strength of this coupling depends on the magnitude of the splay elastic constant K11, which should vary as K$`{}_{11}{}^{}S^2`$. Note that the $`XY`$ model has no such splay component. Thus, a liquid crystal with a small nematic range will have a small K11 at TNA and should lie deep in the anisotropic crossover regime. Liquid crystals with a large nematic range will have a relatively large K11 at their TNA and should straddle isotropic and weak-anisotropic regimes. The latter is observed experimentally, but strong anisotropy, $`\nu _{||}=2\nu _{}`$, is not seen for any smectic since the narrow nematic range condition also induces the de Gennes coupling and thus crossover to tricritical and even first-order behavior Garland and Nounesis (1994).

## Appendix B Scaling background

### B.1 Finite-size scaling

The concept of finite-size effects is a straightforward and basic idea in the modern theory of phase transitions Barber (1983); Binder (1992). Ignoring specific surface interactions, finite-size effects stem from the saturation upon cooling of the growing correlation length in a disordered phase to a finite length scale. In traditional finite-size scaling ($`FSS`$), the maximum length is dictated by the ”container” size. This effect truncates the transition prematurely and leads to three observable effects on the calorimetric data: a suppressed heat capacity maximum, a rounding of the transition in temperature, and a suppression of the transition enthalpy. In addition, for a transition that breaks a continuous symmetry, random-fields lead to a saturation in the growth of order. The hypothesis dictating our approach is that the same analysis can be applied in the case of either type of truncation, provided changes in the critical behavior due to the disorder are accounted. In the case of random-fields, we call this analysis random-field scaling ($`RFS`$).

In order to proceed, the power-law behavior of the smectic correlation length in the nematic phase needs to be considered. It is common practice to ignore corrections-to-scaling terms and use simple pure power laws although this is inconsistent with theory as discussed in Ref. Garland et al. (1993). The correlation lengths of pure LCs are anisotropic with respect to the smectic layer normal (i.e., the nematic director for smectic-A phases) and are represented by effective critical exponents that are free parameters Garland et al. (1993); Ocko et al. (1986)

$$\xi _{}=\xi _ot^\nu _{}$$
(11)
$$\xi _{}=\xi _ot^\nu _{}$$
(12)
where $`\xi _o`$ and $`\xi _o`$ are the bare correlation lengths and $`\nu _{}`$ and $`\nu _{}`$ are the exponents parallel and perpendicular to the layer normal, respectively.

For smectic liquid crystals, the parallel correlation length is always larger than the perpendicular, and so our analysis uses this length scale for the definition of the minimum reduce temperature. Defining the maximum possible correlation length as $`\xi _M`$, one solves Eq. (11) for the $`\mathrm{𝑚𝑖𝑛𝑖𝑚𝑢𝑚}`$ reduced temperature above T as $`t_m^+=(\xi _M/\xi _o)^{1/\nu _{}}`$. It is not possible to define a similar minimum reduced temperature below the transition since the critical correlation length behavior below T is not known. Thus, the equation for the fractional rounding (truncation) of the transition due to finite length effects is estimated to be

$$\delta T^{}/T^{}=(|t_m^+|+|t_m^{}|)2t_m^+=2(\xi _M/\xi _o)^{1/\nu _{}}.$$
(13)
Substituting $`t_m^+`$ into Eq. (III) gives the relationship for the heat capacity maximum $`h_M`$ at the N-SmA transition as

$$h_M=A^\pm (\xi _M/\xi _o)^{\alpha /\nu _{}}(1+D^\pm (\xi _M/\xi _o)^{\mathrm{\Delta }_1/\nu _{}})+B_c.$$
(14)
Because of the importance of corrections-to-scaling for the analysis of $`\mathrm{\Delta }C_p(NA)`$, a log-log plot of $`h_MB_c`$ versus $`\xi _M`$ would not yield a straight line of slope $`\alpha /\nu _{}`$. The $`FSS`$ effect on the N-SmA transition enthalpy is obvious since it involves replacing the singular $`\mathrm{\Delta }C_p(NA)`$ peak between $`t_m^+`$ and $`t_m^{}`$ by $`h_M`$ and thus decreasing the integral of $`\mathrm{\Delta }C_p(NA)`$ over T.

### B.2 Two-scale universality for T $`>`$ T\*

Two-scale theory of critical phenomena relates the non-universal coefficient of the heat capacity’s leading singularity to the non-universal bare correlation volume Bagnuls and Berviller (1985); Campostrini et al. (2000), and it also yields the hyperscaling relation between the critical exponents $`\alpha `$ and $`\nu `$. For liquid crystals, there is an anisotropic version of hyperscaling Lubensky (1983)

$$2\alpha =\nu _{}+2\nu _{},$$
(15)
which is empirically supported by the somewhat scattered available data on pure LCs like 8CB Garland and Nounesis (1994). If such hyperscaling holds, then a two-scale relation can be written as

$$\alpha A^+(\xi _o\xi _o^2)=k_B(R_\xi ^+)^3=13.8(R_\xi ^+)^3,$$
(16)
where $`k_B`$ is the Boltzman constant and the value $`13.8`$ pertains when the correlation lengths are in units of Å and A+ is in units of J K-1 g-1. The quantity $`R_\xi ^+`$ has a different universal value for each universality class. For the $`3D`$-$`XY`$ model, the value of $`13.8(R_\xi ^+)^3`$ is 0.647 Campostrini et al. (2000) and several pure LCs have been shown to have $`\alpha A^+(\xi _o\xi _o^2)`$ values close to this Garland et al. (1993); the value for 8CB is $`0.651`$ Iannacchione et al. (1998); Ocko et al. (1986). Assuming that hyperscaling and $`XY`$-like pure LC values of $`R_\xi ^+`$ hold for 8CB+sil samples independent of $`\rho _S`$, then

$$\alpha A^+(\xi _o\xi _o^2)0.647.$$
(17)
Thus, heat capacity critical behavior ($`\alpha `$ and A+ values) for LC+aerosils will allow the determination of $`\nu _{}+2\nu _{}`$ and $`(\xi _o\xi _o^2)`$.


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# Concurrence as a Relative Entropy with Hilbert-Schmidt Distance in Bell Decomposable States

## 1 Introduction

Perhaps, quantum entanglement is the most non classical features of quantum mechanics  which has recently been attracted much attention. It plays a central role in quantum information theory . Entanglement is usually arise from quantum correlations between separated subsystems which can not be created by local actions on each subsystem. By definition, a mixed state $`\rho `$ of a bipartite system is said to be separable (non entangled) if it can be written as a convex combination of pure product states

$$\rho =\underset{i}{}p_i|\varphi _i^A\varphi _i^A||\psi _i^B\psi _i^B|,$$
(1-1)
where $`|\varphi _i^A`$ and $`|\psi _i^B`$ are pure states of subsystems $`A`$ and $`B`$, respectively. Although, in a pure state of bipartite systems it is easy to check whether a given state is, or is not entangled, the question is yet an open problem in the case of mixed states.

There is also an increasing attention in quantifying entanglement, particularly for mixed states of a bipartite system, and a number of measures have been proposed . Among them the entanglement of formation has more importance, since it intends to quantify the resources needed to create a given entangled state. Vedral et al. in  introduced a class of distance measures suitable for entanglement measures. They also showed that the quantum relative entropy and the Bures metric satisfy three conditions that a good measure of entanglement must satisfy and can therefore be used as generators of measures of entanglement.

Hilbert-Schmidt distance have been used as a measure of distance in . They obtained the entanglement of Bell decomposable states and part of pure states for $`22`$ systems according to H-S distances.

In this paper we show that H-S distance reduces to Euclidean distance for special kind of $`22`$ states, called Bell decomposable states. Based on this, we can rather easily calculate entanglement measure associated with H-S distance of these states. We also show that thus obtained quantity is equal to the concurrence and thus can be used to generate entanglement of formation.

Finally, we present a new measure of distance in operators space and show that the corresponding entanglement measure reduces to concurrence. Starting from BD sates, we perform quantum operations and classical communications (LQCC)  and as consequence one obtains new entangled mixed density matrices with entanglement measure with a functionality analogous to the concurrence.

The paper is organized as follows. In section 2 we review BD states and present a perspective of their geometry. In section 3 we show that H-S distance of these states reduces to Euclidean distance. In section 4 we give a brief review of Wootters’ concurrence, then we evaluate entanglement measure associated with H-S distance and show that it is equal to the concurrence. In section 5 we introduce a new measure of distance and show that its corresponding entanglement measure is also equal to the concurrence for BD states. We perform LQCC action on these states and show that under LQCC, the corresponding entanglement measure transforms in the same way as the concurrence transforms. The paper is ended with a brief conclusion.

## 2 Bell Decomposable States

In this section we briefly review Bell decomposable (BD) states and some of their properties. A BD state is defined by

$$\rho =\underset{i=1}{\overset{4}{}}p_i|\psi _i\psi _i|,0p_i1,\underset{i=1}{\overset{4}{}}p_i=1,$$
(2-2)
where $`|\psi _i`$ is Bell state given by

$`|\psi _1=|\varphi ^+={\displaystyle \frac{1}{\sqrt{2}}}(|+|),`$ (2-3)
$`|\psi _2=|\varphi ^{}={\displaystyle \frac{1}{\sqrt{2}}}(||),`$ (2-4)
$`|\psi _3=|\psi ^+={\displaystyle \frac{1}{\sqrt{2}}}(|+|),`$ (2-5)
$`|\psi _4=|\psi ^{}={\displaystyle \frac{1}{\sqrt{2}}}(||).`$ (2-6)
In terms of Pauli’s matrices, $`\rho `$ can be written as

$$\rho =\frac{1}{4}(II+\underset{i=1}{\overset{3}{}}t_i\sigma _i\sigma _i),$$
(2-7)
where

$$\begin{array}{cc}\hfill t_1=& p_1p_2+p_3p_4,\hfill \\ \hfill t_2=& p_1+p_2+p_3p_4,\hfill \\ \hfill t_3=& p_1+p_2p_3p_4.\hfill \end{array}$$
(2-8)
From positivity of $`\rho `$ we get

$$\begin{array}{cc}\hfill 1+t_1t_2+t_3& 0,\hfill \\ \hfill 1t_1+t_2+t_3& 0,\hfill \\ \hfill 1+t_1+t_2t_3& 0,\hfill \\ \hfill 1t_1t_2t_3& 0.\hfill \end{array}$$
(2-9)
These equations form a tetrahedral with its vertices located at $`(1,1,1)`$, $`(1,1,1)`$, $`(1,1,1)`$, $`(1,1,1)`$ . In fact these vertices are Bell states given in Eqs. (2-3) to (2-6), respectively.

According to the Peres and Horodecki’s condition for separability , a 2-qubit state is separable if and only if its partial transpose is positive. This implies that $`\rho `$ given in Eq. (2-7) is separable if and only if $`t_i`$ satisfy Eqs. (2-9) and

$$\begin{array}{cc}\hfill 1+t_1+t_2+t_3& 0,\hfill \\ \hfill 1t_1t_2+t_3& 0,\hfill \\ \hfill 1+t_1t_2t_3& 0,\hfill \\ \hfill 1t_1+t_2t_3& 0.\hfill \end{array}$$
(2-10)
Inequalities (2-9) and (2-10) form an octahedral with its vertices located at $`O_1^\pm =(\pm 1,0,0)`$, $`O_2^\pm =(0,\pm 1,0)`$ and $`O_3^\pm =(0,0,\pm 1)`$. Hence, tetrahedral of Eqs. (2-9) is divided into five regions. Central regions, defined by octahedral, are separable states. There are also four smaller equivalent tetrahedral corresponding to entangled states. Each tetrahedral takes one Bell state as one of its vertices. Three other vertices of each tetrahedral form a triangle which is its common face with the octahedral (See Fig. 1).

## 3 Hilbert-Schmidt distance for BD states

In the Hilbert-Schmidt (H-S) space density matrices are regarded as vectors rather than operators in the conventional quantum mechanics. The inner product between two operators $`A`$ and $`B`$ in H-S space is defined as

$$A,B=tr(A^{}B),$$
(3-11)
where $`A`$ and $`B`$ are $`4\times 4`$ matrices.

Using definition of inner product, we can define the norm of a given vector $`A`$ in H-S space as

$$A=\sqrt{A,A}=\sqrt{tr(A^{}A)},$$
(3-12)
which is called trace norm. Hence it is natural to obtain the distance between two vectors $`A`$ and $`B`$ in H-S space as

$$d=AB.$$
(3-13)
Now, we show that for BD states H-S distance is equivalent to Euclidean distance. Let us consider two density matrix $`\rho `$ and $`\rho ^{}`$. Using Eq. (2-7) we can expand them in terms of Pauli’s matrices

$`\rho ={\displaystyle \frac{1}{4}}(II+{\displaystyle \underset{i=1}{\overset{3}{}}}t_i\sigma _i\sigma _i),`$ (3-14)
$`\rho ^{}={\displaystyle \frac{1}{4}}(II+{\displaystyle \underset{i=1}{\overset{3}{}}}t_i^{}\sigma _i\sigma _i).`$ (3-15)
Using the above equations one can straightforwardly evaluate their H-S distance, where we have

$$\rho \rho ^{}=\sqrt{tr(\rho \rho )^2}=\frac{1}{2}\sqrt{\underset{i=1}{\overset{3}{}}(t_it_i^{})^2}.$$
(3-16)
Now we can to use the above results to obtain concurrence in the next section.

## 4 Concurrence as relative entropy with H-S distance

From the various measures proposed to quantify entanglement, the entanglement of formation has a special position which in fact intends to quantify the resources needed to create a given entangled state . Wootters in  has shown that for a 2-qubit system entanglement of formation of a mixed state $`\rho `$ can be defined as

$$E(\rho )=H(\frac{1}{2}+\frac{1}{2}\sqrt{1C^2}),$$
(4-17)
where $`H(x)=x\mathrm{ln}x(1x)\mathrm{ln}(1x)`$ is binary entropy and $`C(\rho )`$, called concurrence, is defined by

$$C(\rho )=\mathrm{max}\{0,\lambda _1\lambda _2\lambda _3\lambda _4\},$$
(4-18)
where the $`\lambda _i`$ are the non-negative eigenvalues, in decreasing order, of the Hermitian matrix $`R\sqrt{\sqrt{\rho }\stackrel{~}{\rho }\sqrt{\rho }}`$ and

$$\stackrel{~}{\rho }=(\sigma _y\sigma _y)\rho ^{}(\sigma _y\sigma _y),$$
(4-19)
where $`\rho ^{}`$ is the complex conjugate of $`\rho `$ when it is expressed in a fixed basis such as $`\{|,|\}`$, and $`\sigma _y`$ is $`\left(\begin{array}{cc}0& i\\ i& 0\end{array}\right)`$ on the same basis.

Now, let us consider a Bell decomposable state given by (2-7). One can show that for these states $`\stackrel{~}{\rho }=\rho `$ and thus $`R=\sqrt{\sqrt{\rho }\stackrel{~}{\rho }\sqrt{\rho }}=\rho `$. Calculating the eigenvalues of $`R`$ we get

$$C=\mathrm{max}\{0,\frac{1}{2}(1+t_1+t_2+t_3)\}=\mathrm{max}\{0,2p_41\}.$$
(4-20)
In the sequel we obtain concurrence given in Eq. (4-20) from an entirely different approach. Vedral et al. in  introduced a class of distance measures suitable for entanglement measures. According to their methods, entanglement measure for a given state $`\rho `$ is defined as

$$E(\rho )=\underset{\sigma 𝒟}{\mathrm{min}}D(\rho \sigma ),$$
(4-21)
where $`D`$ is any measure of distance (not necessarily a metric) between two density matrix $`\rho `$ and $`\sigma `$ and $`𝒟`$ is the set of all separable states. They have also shown that quantum entropy and Bures metric satisfy three conditions that a good measure of entanglement must satisfy and can therefore be used as generators of measures of entanglement.

Witte et al. used H-S distance as a candidate for Eq. (4-21). They obtained entanglement of the BD states based on H-S distance from a rigorous method.

Now entanglement of BD states can be easily evaluated by using Eq. (3-16), where H-S distance is equal to Euclidean distance.

Let us consider state $`\rho `$ in the entangled tetrahedral corresponding to singlet state ($`p_4\frac{1}{2}`$). It can be easily seen that the nearest separable surface to this state is $`x_1+x_2+x_3+1`$ which is its common face with octahedral (See Fig. 2). If $`\rho _s`$ denotes nearest separable density matrix to $`\rho `$, then it must lie on this separable surface. This means that $`p_4^{}=\frac{1}{2}`$. Minimizing the Euclidean distance between $`\rho `$ and $`\rho _s`$ with the constraints $`p_4^{}=\frac{1}{2}`$ and $`_{i=1}^4p_i^{}=1`$, we get

$`p_i^{}=p_i+{\displaystyle \frac{1}{3}}\left(p_4{\displaystyle \frac{1}{2}}\right)\text{f}ori=1,2,3\text{and}p_4^{}={\displaystyle \frac{1}{2}}.`$ (4-22)
In terms of parameters $`t_i`$, Eq. (4-22) takes the following form

$$t_i^{}=t_i\frac{1+t_1+t_2+t_3}{3}.$$
(4-23)
Using the above result and Eq. (3-16) we obtain

$$D(\rho \sigma )=\frac{1+t_1+t_2+t_3}{2\sqrt{3}}=\frac{C}{\sqrt{3}},$$
(4-24)
Now we can define entanglement of $`\rho `$ as

$$E(\rho )=\sqrt{3}D(\rho \sigma )=C$$
(4-25)
Right hand side of Eq. (4-25) is the concurrence given in Eq. (4-20).

## 5 Tilde norm

Here in this section, we introduce a new norm defined as

$$\stackrel{~}{A}:=\sqrt{tr(A\stackrel{~}{A})},$$
(5-26)
where $`\stackrel{~}{A}`$ is defined according to Eq. (4-19). With respect to this norm the distance between two density matrices $`\rho _1`$ and $`\rho _2`$ is defined by

$$d=\stackrel{~}{\rho _1\rho _2}=\sqrt{tr((\rho _1\rho _2)(\stackrel{~}{\rho }_1\stackrel{~}{\rho }_2))}.$$
(5-27)
In the sequel we use Eq. (5-27) as a measure of distance. We define entanglement of a state $`\rho `$ by

$$E(\rho ):=\underset{\sigma 𝒟}{\mathrm{min}}\stackrel{~}{\rho \sigma }.$$
(5-28)
It is straightforward to see that for BD states the above distance reduces to H-S distance. Hence the separable state $`\sigma `$ which minimize expression (5-28) is the same as $`\rho _s`$ given in Eq. (4-23).

In the sequel we perform local quantum operations and classical communications (LQCC) on BD states to study the change of entanglement.

A general LQCC transformation is defined by

$$\rho ^{}=\frac{(AB)\rho (AB)^{}}{tr((AB)\rho (AB)^{})},$$
(5-29)
where operators $`A`$ and $`B`$ can be written as

$$AB=U_Af^{\mu ,a,𝐦}U_Bf^{\nu ,b,𝐧},$$
(5-30)
where $`U_A`$ and $`U_B`$ are unitary operators acting on subsystems $`A`$ and $`B`$, respectively and the filters $`f^{\mu ,a,𝐦}`$ and $`f^{\nu ,b,𝐧}`$ are defined by

$$\begin{array}{cc}\hfill f^{\mu ,a,𝐦}=& \mu (I_2+a𝐦.\sigma ),\hfill \\ \hfill f^{\nu ,b,𝐧}=& \nu (I_2+b𝐧.\sigma ).\hfill \end{array}$$
(5-31)
As it is shown in Refs. , the concurrence of the state $`\rho `$ transforms under LQCC of the form given in Eq. (5-29) as

$$C(\rho ^{})=\frac{\mu ^2\nu ^2(1a^2)(1b^2)}{t(\rho ;\mu ,a,𝐦,\nu ,b,𝐧)}C(\rho ),$$
(5-32)
where $`t(\rho ;\mu ,a,𝐦,\nu ,b,𝐦)=tr((AB)\rho (AB)^{})`$.

Now we perform LQCC transformation on states $`\rho `$ and $`\rho _s`$

$`\rho ^{}={\displaystyle \frac{U_Af^{\mu ,a,𝐦}U_Bf^{\nu ,b,𝐧}\rho f^{\mu ,a,𝐦}U_A^{}f^{\nu ,b,𝐧}U_B^{}}{t(\rho ;\mu ,a,𝐦,\nu ,b,𝐧)}},`$ (5-33)
$`\rho _s^{}={\displaystyle \frac{U_Af^{\mu ,a,𝐦}U_Bf^{\nu ,b,𝐧}\rho _sf^{\mu ,a,𝐦}U_A^{}f^{\nu ,b,𝐧}U_B^{}}{t(\rho _s;\mu ,a,𝐦,\nu ,b,𝐧)}}.`$ (5-34)
Under LQCC transformation $`\stackrel{~}{\rho }`$ and $`\stackrel{~}{\rho }_s`$ change as

$`\stackrel{~}{\rho }^{}={\displaystyle \frac{U_Af^{\mu ,a,𝐦}U_Bf^{\nu ,b,𝐧}\stackrel{~}{\rho }f^{\mu ,a,𝐦}U_A^{}f^{\nu ,b,𝐧}U_B^{}}{t(\rho ;\mu ,a,𝐦,\nu ,b,𝐧)}},`$ (5-35)
$`\stackrel{~}{\rho }_s^{}={\displaystyle \frac{U_Af^{\mu ,a,𝐦}U_Bf^{\nu ,b,𝐧}\stackrel{~}{\rho }_sf^{\mu ,a,𝐦}U_A^{}f^{\nu ,b,𝐧}U_B^{}}{t(\rho _s;\mu ,a,𝐦,\nu ,b,𝐧)}}.`$ (5-36)
Now, taking into account that $`f^{\mu ,a,𝐦}f^{\mu ,a,𝐦}=\mu ^2(1a^2)I_2`$ and $`f^{\nu ,b,𝐧}f^{\nu ,b,𝐧}=\nu ^2(1b^2)I_2`$, and using Eq. (5-27) we can evaluate the distance between two states $`\rho ^{}`$ and $`\rho _s^{}`$, where we have

$$\rho ^{}\rho _s^{}=\mu ^4\nu ^4(1a^2)^2(1b^2)^2tr\left(\left(\frac{\rho }{t(\rho )}\frac{\rho _s}{t(\rho _s}\right)\left(\frac{\stackrel{~}{\rho }}{t(\rho )}\frac{\stackrel{~}{\rho }_s}{t(\rho _s)}\right)\right)$$
(5-37)
where $`t(\rho )`$ and $`t(\rho _s)`$ are defined according to Eqs. (2-7)and (4-23) as

$$\begin{array}{cc}\hfill t(\rho )=t(\rho ;\mu ,a,𝐦,\nu ,b,𝐧)=& \mu ^2\nu ^2\left((1+a^2)(1+b^2)+4ab_{i=1}^3m_it_in_i\right)\hfill \\ \hfill t(\rho _s)=t(\rho _s;\mu ,a,𝐦,\nu ,b,𝐧)=& \mu ^2\nu ^2\left((1+a^2)(1+b^2)+4ab_{i=1}^3m_it_i^{}n_i\right)\hfill \\ \hfill =& t(\rho )\frac{4}{3}\mu ^2\nu ^2ab𝐦.𝐧(1+t_1+t_2+t_3)\hfill \\ \hfill =& t(\rho )\frac{2}{3}\mu ^2\nu ^2ab𝐦.𝐧C,\hfill \end{array}$$
(5-38)
where in the last line we used concurrence $`C`$ given in (4-20). In the sequel we make special choices for LQCC transformations. Let us consider cases that either $`𝐦.𝐧=0`$ or $`ab=0`$, that is, $`t(\rho )=t(\rho _s)`$. In this cases we get

$$E(\rho ^{})=\frac{\mu ^2\nu ^2(1a^2)(1b^2)}{t(\rho ;\mu ,a,𝐦,\nu ,b,𝐦)}E(\rho ).$$
(5-39)
Comparison of the above result with Eq. (5-32) shows that under the action of LQCC, the newly defined measure of entanglement changes in the same way as the concurrence changes, therefore it is the same as the concurrence.

Conclusion
We have shown that H-S distance is equivalent to Euclidean distance for BD sates. Based on this, H-S entanglement measure of these states are easily obtained and it has been shown that, H-S entanglement measure is equal to the concurrence. Based on spin flipping transformation of density matrices, we have introduced a new measure of distance, and we have shown that its corresponding measure of entanglement is equal to the concurrence for BD states. Starting from BD states together by performing restricted LQCC action, we have shown that the transformed entanglement measure is equal to the concurrence.

Figure Captions

Figure 1: All BD states correspond to the interior points of tetrahedral. Vertices $`P_1`$, $`P_2`$, $`P_3`$ and $`P_4`$ denote projectors corresponding to Bell states defined by Eqs. (2-3) to (2-6), respectively. The interior points of octahedral correspond to separable states.

Figure 2: Entangled tetrahedral corresponding to singlet state. The points of line $`P_4C`$ correspond to entangled Werner states. Points $`t`$ and $`t^{}`$ correspond to a generic BD state $`\rho `$ and associated nearest separable state $`\rho _s`$, respectively.