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# Time-resolved impulse response of the magnetoplasmon resonance in a two-dimensional electron gas

## I INTRODUCTION

The far infrared properties of two-dimensional electron gas (2DEG) systems have been studied extensively. Common examples are observations of cyclotron resonanceT.A.Kennedy et al. (1975); Seidenbusch et al. (1987), magnetoplasmon resonanceTheiss et al. (1977); Theiss (1977), and edge magnetoplasmonsAshoori et al. (1992). Here we address a new approach to these measurements and demonstrate the time resolved detection of the magnetoplasmon resonance. Normally, it is necessary to fabricate a grating on the top of the sample in order to allow coupling of far infrared radiation to the plasmon component of a magnetoplasmon modeAshoori et al. (1992). One then excites with continuous wave radiation and looks at a particular optical property, such as transmission, which averages the time dependent behavior of the carriers. With our technique, the grating restriction is removed and we are able to directly time resolve the effect of the applied field on the resonance.

The magnetoplasmon resonance is formed by the coupling of the two-dimensional plasmon and the cyclotron motion of carriers. The cyclotron resonance frequency is given byKittel (1996) $`\omega _c=eB/m^{}`$ , where $`e`$ is the electron charge, $`B`$ is the perpendicular component of the magnetic field, and $`m^{}=.067m_e`$ is the effective mass of an electron in GaAs. The dispersion relation for 2D plasmons is given approximately byDavies (1998) $`\omega _p^2`$=$`e^2n_{2D}q/(2\epsilon _0\epsilon _bm^{})`$ where $`n_{2D}`$ is the two dimensional density of electrons, q is the 2D plasmon wave vector, and $`\epsilon _b`$ is the dielectric constant of GaAs. When a magnetic field is applied to a 2DEG, the cyclotron and plasmon couple yielding a magnetoplasmon mode with a resonant frequencyAshoori et al. (1992) $`\omega ^2=\omega _p^2+\omega _c^2`$.

A novel method for measuring conductivity resonances in 2DEG systems is to incorporate the 2DEG as part of a three conductor coplanar waveguide (CPW)Engel et al. (1993). The fringing fields from the conductors capacitively couple to the 2DEG allowing it to affect waveguide losses and dispersion. Typically, to perform measurements at frequencies up to 30GHz, one feeds microwaves to the CPW through a coaxial cable, and then either measures transmitted power with a detector near the sampleEngel et al. (1993), or couples the microwaves back out of the system for analysis of amplitude and phase shiftYe et al. (2002). The guiding of microwaves in and out of cryogenic systems, as well as impedance matching to the CPW on the sample in order to eliminate back reflections, can be an arduous task. With this approach, one is also limited to frequencies that can be generated through microwave electronics. In order to circumvent these difficulties we used a similar waveguide, two-conductor coplanar strip transmission line (CPS), excited optoelectronically through illumination of Auston switchesAuston (1983). In this work, Auston switches are formed by patterning conductors on low temperature grown GaAs (LT GaAs). This material has recombination time of approximately one picosecondZandmer et al. (1999) and allows for the generation and detection of electrical pulses on that timescale. In contrast to other experiments which utilized optoelectronic excitationErnst et al. (1996), we also implement optoelectronic sampling of the waveguide signal using a second Auston switch integrated on the waveguide.

## II EXPERIMENT

The CPS consisted of two 6$`\mu m`$ wide, 50$`\AA `$/2000$`\AA `$ thick Ti/Au strips separated by 10$`\mu m`$. These strips were patterned on a multilayer substrate consisting of a 2$`\mu m`$ LT GaAs epilayer, grown by molecular beam epitaxy (MBE), which has been transferred onto a 50$`\mu m`$ thick polyimide sheet using the epoxy bond and stop etch processWeckwerth et al. (1996). The entire structure is then mounted on a silicon substrate which serves as structural support and also allows for the attachment of optical fibers. An MBE grown AlGaAs/GaAs 2DEG with mobility at 4K of $`610^5cm^2V^1s^1`$ and density $`n_{2D}=2.810^{11}cm^2`$ was employed as a superstrate. Figure 1 shows the resulting waveguide and sample structure. The electric field mode for this type of guide is a dipole patternGrischkowski et al. (1987). The fringing fields of this dipole allow for capacitive coupling to the 2DEG. Single mode optical fibers are used to carry 780nm wavelength pump and probe pulses of 3ps duration generated by a Ti:Sapphire laser to the CPS. To launch a pulse, a bias is placed across the CPS conductors, as shown in Fig. 1c. When the pump pulse strikes the area between the CPS conductors, charge displacement and collection, driven by the the DC bias, efficiently excites the CPS modeGrischkowski et al. (1987). Due to the short carrier lifetime of the LT GaAs, this produces an electrical signal with approximately the shape of the optical pulse envelopeAuston (1983). The voltage on the CPS is sampled in time through a similar process by striking the sampling gap, shown in Fig. 1c, with a probe pulse. By delaying the probe pulse with respect to the pump, and monitoring the sampling line signal, we time resolve pulse propagationKetchen et al. (1986). This gives us a measurement of the impulse response of the entire waveguiding structure.

Due to dispersion in the optical fiber, the pulses are broadened by roughly 1ps. Measurements shown in Fig. 2 were taken with approximately 300$`\mu W`$ total laser power in a pumped $`{}_{}{}^{3}He`$ system at T=0.5K. The CPS was biased at 5V giving reasonable signal-to-noise ratio. The pump beam was modulated at 1KHz to allow for lockin detection of the sampling line signal. As shown, the data can be broken up into three regions. The section labeled initial pulse is the first pass of the pulse launched by the pump beam after it has traveled 1mm from the pump gap to the sampling gap. Trailing the initial pulse is a distinctive ringing due to the magnetoplasmon resonanceHasnain et al. (1990). Since our transmission lines did not have an impedance matched termination, there is a large reflection when the pulse reaches the end of the CPS. The location of this reflection is indicated in the data, although most of it has been truncated since it does not contain easily interpreted information. This reflection limits the time window in which we can observe the system response to 30ps in the present structures.

## III ANALYSIS

To gain an approximate understanding of how pulses should propagate with the 2DEG applied as a superstrate, we modeled our system with a dielectric constant of a medium containing Lorentz oscillators. For simplicity, we neglected modal dispersion and used a quasi-TEM approximationHasnain et al. (1990). A short simulated pulse propagated in this manner is shown in Fig. 3 along with data taken at B=0.3T. The frequency of the modeled oscillator was chosen to be 154GHz to match the oscillations of the data in the response region. From the calculations, the first peak we see after the initial pulse should appear at approximately 1.5 periods of the resonant frequency. This is important information since our pulses are broad enough to hide the first ring of the resonance. With this knowledge, peaks found in the the time domain data are converted into resonant frequencies. The data shown in Fig. 2 at zero magnetic field shows that we are exciting a 2D plasmon of approximately 80GHz. A simple estimate using $`q=2\pi /\lambda `$ and taking $`\lambda =20\mu m`$ (corresponding to a half wavelength of the plasmon being the 10$`\mu m`$ line spacing) gives 200GHz. An exact agreement is not expected as the CPS conductors and DC bias likely modify the 2D plasmon dispersionDavies (1998).

Frequencies obtained from the time domain data of Fig. 2, along with other scans not shown, are plotted against perpendicular magnetic field in Fig. 4. The resulting dispersion shows that our measurements follow the expected magnetoplasmon curve. This verifies that our technique can provide information about dipolar resonances without the need of contacting the sample. Although the resonant frequency is readily attained from our data, accurately quantifying the damping of the resonance would require a longer time window.

In the data taken at B=0.38T, it is possible to resolve the decay of the resonance and determine a relaxation time. In the time domain, we fit an exponential decay to the rings, and in the frequency domain, we fit a lorentian lineshape to the power spectrum. Both methods produced a relaxation time of approximately 5ps which is signifcantly lower than the 22ps scattering time obtained from the sample mobility. This result is expected since the cyclotron mobility at low fields is more sensitive to small angle scattering than is the transport mobilitySarma and Stern (1985).

## IV CONCLUSION

With our time-resolved measurement system, we were able to characterize 2DEG resonances as a function of magnetic field. Resonant frequencies obtained from the time domain data presented here match the expected magnetoplasmon dispersion curve well. As discussed, these measurements were taken with 300$`\mu W`$ total laser power resulting in a minimum measurement temperature of T=0.5K in our system. Measurements have been taken with as little as 70$`\mu W`$ total laser power yielding lower temperatures. In the present experiment, temperature was not critical and higher power gave better signal-to-noise. Although the data shown was taken at magnetic fields below 1T, we note that the probe itself had no problems operating at fields up to 8.5T, which was limited only by the magnet in our system. Future design improvements will provide a larger time window in which more precise characterization of the resonance ring-down will be possible.

###### Acknowledgements.

We would like to thank Mike Valenti of Princeton University for assistance in preparation of silicon substrates used in these experiments. E.A. Shaner was supported by a National Defense Science and Engineering graduate fellowship. This work was supported in part by the U.S. Army Research Office under grant $`\mathrm{\#}`$DAAG55-98-1-0270.


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# Separating Thickness from Geometric Thickness

## 1. Introduction and Main Result

The graph-theoretic property of thickness and its variants formalize the concept of layered graph drawing, in which a graph must be drawn in multiple layers (or with multiple colors) so that each edge belongs to a single layer and no two edges in the same layer cross. The vertices of the graph should be represented as points and should exist in the same positions in each layer. There are three important variants of thickness:

1. The thickness of a graph $`G`$, denoted $`\theta (G)`$, is the minimum number of layers for which a drawing of $`G`$ exists, without restriction on the number of bends per edge .
2. The geometric thickness of a graph $`G`$, denoted $`\overline{\theta }(G)`$, also known as real linear thickness or rectilinear thickness, is the minimum number of layers for which a drawing exists without any bends in the edges: each edge must be represented as a straight line segment .
3. The book thickness of a graph $`G`$, denoted $`\mathrm{bt}(G)`$, is the minimum number of layers for which a drawing exists without any bends in the edges and with all vertices placed in convex position .

Since each variant imposes additional constraints on the previous one, these parameters are always ordered: $`\theta (G)\overline{\theta }(G)\mathrm{bt}(G)`$, and it is of interest to determine how tight these inequalities are. Due to Fáry’s theorem , the graphs with thickness one and geometric thickness one coincide (both are just the planar graphs), and are a strict superset of the graphs with book thickness one (the outerplanar graphs). Thickness and geometric thickness were known to differ for infinitely many graphs: in particular, complete graphs on $`n`$ vertices have thickness $`n/6+O(1)`$  but have geometric thickness at least $`n/5.646`$ .

In previous work  we showed that book thickness can not be bounded by any function of the geometric thickness: for any $`t`$ there exists a graph with geometric thickness two and book thickness at least $`t`$. The proof idea is to consider the graphs $`G_2(n)`$ with geometric thickness two, having as vertices the singleton and doubleton subsets of an $`n`$-element set, with an edge between two subsets when one is contained in the other. Ramsey’s theorem shows that, if these graphs are partitioned into $`k`$ layers, for $`k`$ fixed and $`n`$ large, then some two layers include a $`G_2(5)`$. But $`G_2(5)`$ is nonplanar and therefore has book thickness greater than two, so these two layers cannot be part of a book layout. The same bound on the book thickness of $`G_2(n)`$, with the same proof, was independently discovered by Blankenship and Oporowski .

In this paper, we prove a similar separation between thickness and geometric thickness: for any $`t`$ there exists a graph with thickness three and geometric thickness at least $`t`$. This implies that known strategies for approximating thickness (layered drawing with bends) will not lead to good approximation algorithms for layered drawing without bends.

The overall outline of our proof is very similar to the previous separation of geometric thickness from book thickness: we use subset inclusions to define a family of graphs with thickness three, show that some graph in the family does not have geometric thickness three, and use Ramsey’s theorem to conclude that the geometric thickness of the family is unbounded. The difficult part of the proof is to show that some graph in the family does not have geometric thickness three, for which we use an intricate case analysis that also applies Ramsey theory multiple times in order to restrict the argument to drawings of certain uniform types. Our main result is the following theorem.

###### Theorem 1.1.

For every $`t`$, a graph exists with thickness three and geometric thickness at least $`t`$.

###### Proof.

For any $`n>0`$, define a graph $`G_3(n)`$ having as its $`n+\left(\genfrac{}{}{0pt}{}{n}{3}\right)`$ vertices the singleton and tripleton subsets of an $`n`$-element set, with an edge between two subsets when one is contained in the other. $`G_3(4)`$ forms the vertices and edges of a cube; $`G_3(5)`$ is depicted in Figure 1. If we assign the edges of $`G_3(n)`$ to three layers, in such a way that the three edges incident to each tripleton are assigned to different layers, then each layer will form a forest of stars, which is a planar graph, so $`G_3(n)`$ has thickness at most three. We show that there exists an $`n_1`$ such that $`G_3(n_1)`$ has geometric thickness more than three (Lemma 5.1).

By Ramsey’s theorem, there exists an $`n_2`$ such that, if the edges of $`G_2(n_2)`$ are given $`t1`$ colors, one can find a three-colored $`G_3(n_1)`$ subgraph. If the $`(t1)`$-coloring is determined by a geometric embedding with $`t1`$ layers, the subgraph would have a three-layer geometric embedding. Since no such three-layer embedding exists, $`G_3(n_2)`$ does not have a $`(t1)`$-layer geometric embedding. ∎

In the rest of this paper we fill in the details of the proof outline above.

## 2. Restrictions to Coherent Drawings

We use the following classical results of Ramsey theory .

###### Lemma 2.1 (Ramsey’s theorem).

For every three positive integers $`c`$, $`e`$, and $`\mathrm{}`$ there is an integer $`R_e(\mathrm{};c)`$ with the following property: if $`|S|R_e(\mathrm{};c)`$ and the $`e`$-element subsets of $`S`$ are partitioned into $`c`$ classes, then there exists a set $`TS`$ with $`|T|\mathrm{}`$ so that all $`e`$-element subsets of $`T`$ belong to the same class.

For instance, in the proof of Theorem 1.1 we choose $`c=\left(\genfrac{}{}{0pt}{}{t1}{3}\right)+\left(\genfrac{}{}{0pt}{}{t1}{2}\right)+t1`$, $`e=3`$, and $`\mathrm{}=n_1`$. The set $`S`$ is the set of singletons in $`G_3(n_2)`$, and the tripletons in $`G_3(n_2)`$ are partitioned into $`c`$ classes by the colors of their three incident edges. Ramsey’s theorem tells us that we can find a set $`T`$, $`|T|=n_1`$, so that the subgraph $`G_3(n_1)`$ formed by the singleton and tripleton subsets of $`T`$ uses the same three colors for each tripleton; that is, we can find a three-colored $`G_3(n_1)`$ subgraph of $`G_3(n_2)`$.

###### Lemma 2.2 (the Erdős-Szekeres theorem).

For every integer $`k`$ there is an integer $`N(k)`$ with the following property: if $`N(k)`$ points are placed in the plane with no three points collinear, then some subset of $`k`$ points forms the set of vertices of a convex polygon.

Define a convex drawing of $`G_3(n)`$ to be a drawing with geometric thickness three in which all singletons are in convex position. We do not restrict the positions of the tripletons.

###### Lemma 2.3.

If every graph $`G_3(n)`$ has geometric thickness three, then every $`G_3(n)`$ has a convex drawing.

###### Proof.

Sufficiently small perturbations of the vertex locations in a layered drawing will not create or remove crossings, so we can assume no three vertices are collinear. To form a convex drawing of $`G_3(n)`$, apply the Erdős-Szekeres theorem to the singletons of $`G_3(N(n))`$, and form a $`G_3(n)`$ subgraph from the resulting convex set of $`n`$ singletons and their adjacent tripletons. ∎

We number the singleton vertices of a convex drawing in clockwise order from $`0`$ to $`n1`$, starting from an arbitrarily chosen vertex. Using this numbering, we can partition the edges of $`G_3(n)`$ into three classes: a low edge connects a tripleton to the adjacent singleton with the smallest number, a high edge connects a tripleton to the adjacent singleton with the largest number, and a middle edge connects a tripleton to the remaining adjacent singleton. Define a coherent drawing of $`G_3(n)`$ to be a convex drawing in which these three classes form the three layers of the drawing.

###### Lemma 2.4.

If every graph $`G_3(n)`$ has geometric thickness three, then every $`G_3(n)`$ has a coherent drawing.

###### Proof.

By Lemma 2.3 we can assume $`G_3(n)`$ has a convex drawing. Partition the tripletons of such a drawing into 27 classes according to the layers to which the incident low, middle, and high edges belong. By Lemma 2.1 with $`c=27`$ and $`e=3`$, we can find a drawing in which each of the three sets of edges belongs to a single layer. If this results in more than one set belonging to the same layer, we can move sets to distinct layers without introducing any crossings. ∎

In a coherent drawing, we will denote tripletons by triples of symbols $`abc`$, where each letter denotes the position of an adjacent singleton in the clockwise ordering of the drawing, and $`a<b<c`$ according to the clockwise ordering.

## 3. Restriction to Outer Drawings

Define an inner drawing of $`G_3(n)`$ to be a coherent drawing such that there exists a strictly convex curve $`C`$ on which all singletons lie, with all tripletons interior to $`C`$. Similarly, define an outer drawing to be a coherent drawing such that there exists a strictly convex curve $`C`$ on which all singletons lie, with all tripletons exterior to $`C`$. A drawing can be both inner and outer, for instance if all singletons and tripletons are in convex position. Note that, in an inner drawing, all edges are strictly interior to $`C`$; however an edge in an outer drawing may have portions inside $`C`$ and portions outside $`C`$.

###### Lemma 3.1.

Suppose two tripletons $`abc`$ and $`def`$ are part of an inner drawing, with $`a<d<c<f`$. Then either the low edge of $`abc`$ crosses the high edge of $`def`$, or the high edge of $`abc`$ crosses the low edge of $`def`$. However, both types of crossing can not occur simultaneously.

###### Proof.

Consider the two paths formed by the low and high edges of each tripleton. These paths cross $`C`$ and each path separates the endpoints of the other path; therefore the paths must cross an odd number of times. However, each pair of edges can cross only once, and the only types of crossing permitted are those described in the lemma. Therefore exactly one of these crossings occurs. ∎

We say that the two tripletons cross convexly if the low edge of $`abc`$ crosses the high edge of $`def`$, and that they cross concavely in the other case of Lemma 3.1.

###### Lemma 3.2.

There exists an $`n_3`$ such that $`G_3(n_3)`$ does not have an inner drawing.

###### Proof.

Let $`n`$ be sufficiently large, and assume for convenience that $`n=2`$ (mod $`4`$). Consider the sequence of tripletons $`2i,n/2,n/2+2i+2`$ for $`0i<n/22`$; each pair of tripletons meets the conditions of Lemma 3.1. By applying Lemma 2.1 with $`c=2`$, $`e=2`$, and $`\mathrm{}=5`$, for sufficiently large $`n`$, we can obtain a set of five such triples that all cross convexly or all cross concavely. As Figure 2 shows, in either case, the low and high edges of these crossing triples form a grid graph, containing a complete $`2\times 2`$ subgrid. (The quadrilaterals of this grid need not always be convex, but this does not affect our argument.)

Because we chose tripletons using only every other singleton from the ordering, it is now possible to find singletons $`a`$ and $`b`$ that lie between the three low edges forming the $`2\times 2`$ subgrid, and $`e`$ and $`f`$ that lie between the three high edges forming the subgrid (Figure 3). Therefore, any tripleton with a low edge to $`a`$ or $`b`$ and a high edge to $`e`$ or $`f`$ must be forced to lie within a particular square of the subgrid.

Extend the two middle line segments of the subgrid into lines across curve $`C`$ (the thin dotted lines of the figure), partitioning $`C`$ into three curves: the curve clockwise of both extended lines, the curve counterclockwise of the extended lines, and the curve between the two lines. The four points $`n/22`$, $`n/21`$, $`n/2`$, $`n/2+1`$ lie between $`b`$ and $`e`$, and by the pigeonhole principle we can find two of these points $`c<d`$ that are both within the same one of these three curves.

If $`c`$ and $`d`$ are both in the center curve of the three curves (shown in the left side of the figure) then tripletons $`ace`$ and $`bdf`$ must have crossing middle edges. If $`c`$ and $`d`$ are both in the counterclockwise curve (shown on the right side of the figure), then tripletons $`adf`$ and $`bce`$ must have crossing middle edges; the case in which $`c`$ and $`d`$ belong to the clockwise curve is symmetric. Thus, in all cases two tripletons have crossing middle edges, contradicting the assumption that we have a three-layer drawing with no crossings. ∎

###### Lemma 3.3.

If every graph $`G_3(n)`$ has geometric thickness three, then every $`G_3(n)`$ has an outer drawing.

###### Proof.

Assume without loss of generality that $`n`$ is sufficiently large that, by Lemma 3.2, no inner drawing of $`G_3(n)`$ exists. Let $`r=R_3(n;2)`$, as shown to exist in Lemma 2.1. By Lemma 2.4, we can assume $`G_3(r)`$ has a coherent drawing. Let $`C`$ be the convex hull of the singletons of this drawing, and perturb $`C`$ if necessary so that it remains convex and does not pass through any tripletons. Partition the tripletons of the drawing into two classes according to whether they are inside or outside $`C`$, and apply Lemma 2.1 with $`c=2`$ and $`e=3`$ to find a drawing of $`G_3(n)`$ in which all triples are inside $`C`$ or all triples are outside $`C`$. Since no inner drawing exists, all triples are outside $`C`$, and we have an outer drawing of $`G_3(n)`$. ∎

## 4. Classification of Outer Drawings

In an outer drawing, the three angles formed by the three edges incident to a tripleton must include an angle greater than 180, and we can order the three edges clockwise starting at this large angle. Define the type of a tripleton to be a symbol $`xyz`$, where $`x`$, $`y`$, and $`z`$ form a permutation of $`0`$, $`1`$, and $`2`$, and where the positions of the low, middle, and high number in the symbol are the same as the positions of the low, middle, and high edge in the clockwise ordering at the tripleton. There are six possible types: $`012`$, $`021`$, $`102`$, $`120`$, $`201`$, and $`210`$. If all tripletons in a drawing have the same type $`xyz`$, we say that the drawing is of type $`xyz`$.

###### Lemma 4.1.

If every graph $`G_3(n)`$ has geometric thickness three, then every $`G_3(n)`$ has an outer drawing in which all tripletons have the same type.

###### Proof.

By the previous lemma, we can assume that we have an outer drawing with sufficiently many vertices, to which we can apply Lemma 2.1 with $`c=6`$ and $`e=3`$. ∎

We now successively analyze each type of outer drawing and show that, for sufficiently large $`n`$, each type must lead to a crossing.

###### Lemma 4.2.

For $`n4`$, $`G_3(n)`$ has no outer drawing of type $`201`$ or $`120`$.

###### Proof.

In a drawing of type $`201`$, each low edge of a tripleton must cross the convex curve $`C`$ between the middle and high sigletons adjacent to the tripleton. Therefore, in a drawing of $`G_3(4)`$, the low edge from tripleton $`012`$ would cross the low edge from tripleton $`123`$, as shown in Figure 4. Type $`120`$ is equivalent to type $`201`$ under mirror reversal of the drawing and reversal of the clockwise ordering of the singletons. ∎

###### Lemma 4.3.

In any outer drawing of $`G_3(4)`$ of type $`021`$, let $`\theta _i`$ denote the angle at singleton $`i`$ on the convex hull of the singletons. Then $`\theta _1+\theta _2<180^{}`$.

###### Proof.

In order to be of type $`021`$, tripleton $`012`$ must lie in a wedge outside $`C`$ bounded by lines $`02`$ and $`12`$ (the shaded area on the upper right of Figure 5). The low edge $`e_0`$ from $`0`$ to $`012`$ crosses line $`12`$ on the boundary of this wedge. Similarly, the low edge $`e_1`$ from $`1`$ to tripleton $`123`$ crosses line $`23`$. In order for $`e_1`$ to reach this line without crossing $`e_0`$, tripleton $`123`$ must be clockwise from singleton $`0`$ as viewed from singleton $`1`$, so angle $`123`$-$`1`$-$`2`$ must be greater than $`\theta _1`$. But in order for the crossing of $`e_1`$ with line $`23`$ to be on the boundary of the wedge containing $`123`$ (shown as the lower shaded area in the figure), angle $`123`$-$`1`$-$`2`$ must be less than $`180^{}\theta _2`$. Combining these two inequalities gives the result. ∎

###### Lemma 4.4.

For $`n6`$, $`G_3(n)`$ has no outer drawing of type $`021`$ or $`102`$.

###### Proof.

By applying Lemma 4.3 twice, $`\theta _1+\theta _2+\theta _3+\theta _4<360^{}`$, but this is not possible in a convex polygon. Type $`102`$ is equivalent to type $`021`$ under mirror reversal. ∎

###### Lemma 4.5.

In an outer drawing of $`G_3(n)`$ of type $`012`$, the middle edges adjacent to singletons $`2`$, $`3`$, $`\mathrm{}`$, $`n3`$ all pass across line segment $`0`$-$`(n1)`$.

###### Proof.

By the assumption that the drawing is of type $`012`$, the middle edges of the tripletons $`0i(n1)`$ all pass across this segment (Figure 6, left). In any other singleton $`abc`$, the middle edge must pass from $`b`$ across line segment $`ac`$ within the convex curve $`C`$. Unless $`b=1`$ or $`b=n2`$, this crossing with $`ac`$ must occur within a strip bounded by two of the middle edges of tripletons $`0i(n1)`$, and the only way for the middle edge from $`b`$ to exit $`C`$ is at the end of this strip, where it meets segment $`0`$-$`(n1)`$. ∎

###### Lemma 4.6.

Suppose we have an outer drawing of $`G_3(n)`$ of type $`012`$, in which all middle edges cross segment $`0`$-$`(n1)`$. Draw a tangent line to convex curve $`C`$ parallel to line $`0`$-$`(n1)`$, on the opposite side of $`C`$ from that line, and let $`h`$ be a point where the tangent line touches $`C`$. Then, for every tripleton $`ijk`$ where $`i`$ is clockwise from $`h`$, the low edge from $`i`$ to $`ijk`$ crosses $`C`$ either at a point counterclockwise from $`h`$ or between singletons $`0`$ and $`n1`$.

###### Proof.

By the assumption of the drawing type, all low edges must cross line $`0`$-$`n1`$ to the left of the crossing point of the middle edge, which is between points $`0`$ and $`n1`$. If the low edge’s crossing is not also between points $`0`$ and $`n1`$, it must be to the left of point $`0`$. But, within the strip between line $`0`$-$`(n1)`$ and the parallel tangent line, the portion of $`C`$ between $`0`$ and $`h`$ separates the rest of $`C`$ (containing $`i`$) from the points left of point $`0`$ (as shown in Figure 6, right), so the low edge most cross $`C`$ before it reaches its crossing with line $`0`$-$`(n1)`$. ∎

Symmetrically, the high edges from counterclockwise of $`h`$ must cross $`C`$ clockwise of $`h`$.

###### Lemma 4.7.

For sufficiently large $`n`$, $`G_3(n)`$ has no outer drawing of type $`012`$.

###### Proof.

Start with an outer drawing of type $`012`$, and remove singletons $`1`$ and $`n2`$ if necessary so that (by Lemma 4.5) all middle edges cross segment $`0`$-$`(n1)`$. Form the tangent point $`h`$ described in Lemma 4.6, and assume without loss of generality that at least half of the remaining singletons lie clockwise of $`h`$ on convex curve $`C`$. (The case that at least half the singletons lie counterclockwise of $`h`$ is symmetric.) Remove from the drawing all points counterclockwise of $`h`$. The result is an outer drawing of type $`012`$ of a graph $`G_3(m)`$, with at least $`m(n2)/2`$ singletons, in which all low and middle edges cross segment $`0`$-$`(m1)`$. We can now apply the same reasoning as in Lemma 3.2: by choosing an appropriate set of tripletons, we can find a set of low and middle edges forming a grid that contains a complete $`2\times 2`$ subgrid, and use the subgrid to constrain the locations of two more tripletons, forcing two high edges to cross. ∎

###### Lemma 4.8.

In an outer drawing of $`G_3(n)`$ of type $`210`$, each middle edge is completely exterior to convex curve $`C`$.

###### Proof.

Suppose to the contrary that a middle edge for tripleton $`ijk`$ crosses $`C`$ at point $`x`$. If $`x`$ is clockwise of $`j`$, an edge from $`ijk`$ to $`C`$ clockwise of the middle edge can only reach singletons in the range from $`j`$ to $`x`$, contradicting the requirement (from the assumption of the drawing type) that the low edge $`i`$-$`ijk`$ must be clockwise of the middle edge. Symmetrically, if $`x`$ is counterclockwise of $`j`$, an edge counterclockwise of the middle edge can only reach singletons in the range from $`x`$ to $`j`$, contradicting the requirement that the high edge must be clockwise of the middle edge. ∎

The same reasoning as above also proves the following lemma:

###### Lemma 4.9.

In an outer drawing of $`G_3(n)`$ of type $`210`$, suppose that the low edge of tripleton $`ijk`$ crosses the convex curve $`C`$. Then the crossing point is clockwise of singleton $`i`$.

###### Lemma 4.10.

Suppose that $`G_3(n)`$ has a convex drawing of type $`210`$, and let $`n=2^k2`$ Then we can select a subset $`S`$ of the singletons, with $`|S|=k`$, such that no member of $`S`$ is incident to a low edge that crosses the convex hull of $`S`$.

###### Proof.

We use induction on $`k`$. As a base case, for $`k=n=2`$, $`G_3(2)`$ has no edges. Otherwise, consider the sets of low edges incident to singletons $`0`$ and $`1`$ that cross convex curve $`C`$. Since these two sets of low edges do not cross each other (Figure 7), we can partition the portion of $`C`$ clockwise of $`1`$ into two parts, where the clockwise part of $`C`$ is crossed only by low edges from $`0`$ and the counterclockwise part of $`C`$ is crossed only by low edges from $`1`$. One of these two parts contains at least $`(n2)/2`$ singletons. If the clockwise part contains many singletons, we apply the induction hypothesis to these singletons, and form $`S`$ by adding singleton $`1`$ to the resulting set. On the other hand, if the counterclockwise part contains many singletons, we add singleton $`0`$ to the set formed by applying the induction hypothesis to the singletons in this part.

In either case, we get a set $`S`$ of $`(k1)+1=k`$ singletons. The low edges from $`0`$ or $`1`$ (whichever was included in the set) can not cross the hull, because of how we chose which part of $`C`$ to apply the induction hypothesis to. The low edges from the remaining members of $`S`$ can not cross the hull between $`0`$ or $`1`$ and the rest of $`S`$, by Lemma 4.9, and they can not cross the hull elsewhere by induction. Therefore $`S`$ fulfills the conditions of the lemma. ∎

###### Lemma 4.11.

Not every graph $`G_3(n)`$ has an outer drawing of type $`210`$.

###### Proof.

By Lemma 4.10, if $`G_3(n)`$ has such a drawing, then we can find a set of $`k`$ singletons, and a convex curve $`C`$ (the hull of this set), forming an outer drawing of $`G_3(k)`$ in which all low and middle edges avoid the interior of convex curve $`C`$; here $`k=\mathrm{log}_2(n+2)`$. We can now apply the same reasoning as in Lemmas 3.2 and 4.7: by choosing an appropriate set of tripletons, we can find a set of low and middle edges forming a grid that contains a complete $`2\times 2`$ subgrid, and use the subgrid to constrain the locations of two more tripletons, forcing two high edges to cross. ∎

## 5. Completion of the Proof

###### Lemma 5.1.

Not every graph $`G_3(n)`$ has geometric thickness at most three.

###### Proof.

This follows from Lemma 4.1 (showing that we can restrict our attention to outer drawings of fixed type) and Lemmas 4.2, 4.4, 4.7, and 4.11 (showing that each fixed type leads to a forced crossing). ∎

The largest $`n`$ for which $`G_3(n)`$ has no thickness-three drawing must be at least nine, as $`G_3(8)`$ has geometric thickness at most three: draw four singleton subsets in a large square, with the remaining four singletons and all tripletons clustered near the center of the square. The edges incident to the inner four singletons form a planar graph, consisting of a cube $`G_3(4)`$, 24 two-edge paths across the faces of the cube, and 24 tripletons with only a single edge to one of the inner singletons. By choosing an appropriate Fáry embedding of this planar graph, we can draw it in a single layer, and use an additional layer for the edges incident to each pair of opposite outer singletons. Figure 8 shows this drawing in a schematic view, with the outer four vertices and inner cube visible but omitting the remaining tripletons.

## 6. Conclusions

We have shown that thickness and geometric thickness are not asymptotically equivalent. Some interesting open questions remain:

1. How does $`\overline{\theta }(G_3(n))`$ grow as a function of $`n`$? The best upper bound we have been able to obtain is that $`\overline{\theta }(G_3(n))(n2)/2`$, by generalizing the three-layer drawing of $`G_3(8)`$ outlined in the previous section, but this is far from the lower bound given by Theorem 1.1.
2. What can be said about two-layer drawings? It is known that there exist graphs, for instance $`K_{6,8}`$, for which $`\theta (G)=2`$ and $`\overline{\theta }(G)>2`$ . Can $`\overline{\theta }(G)`$ be unbounded when $`\theta (G)=2`$?
3. Four-regular graphs have thickness at most two. Do random four-regular graphs have bounded expected geometric thickness? More generally, do bounded degree graphs have bounded geometric thickness?
4. The two-layer drawing technique for $`G_2(n)`$ generalizes to many other $`2`$-inductive graphs: that is, graphs that can be reduced to the empty graph by repeatedly removing vertices with degree at most two. Is there a $`2`$-inductive graph with geometric thickness greater than two? Can the geometric thickness of such graphs be unbounded?
5. Due to our use of Ramsey theory, our lower bounds on geometric thickness grow only very slowly as a function of the number of vertices. Can we find good upper bounds for geometric thickness as a combination of the graph-theoretic thickness and a slowly growing function of the graph size?
6. What is the complexity of computing $`\overline{\theta }(G)`$ for a given graph $`G`$ ?
7. Thickness is NP-hard  but not difficult to approximate to within a constant factor; e.g., it is within a factor of three of the graph’s arboricity. Our new results imply that these approximations do not directly extend to geometric thickness. Is there an efficient algorithm for layered drawing of graphs without bends, using a number of layers within a constant factor of optimal?


text:
# On (2+1)Dimensional Topologically Massive Non-linear Electrodynamics

## 1 The Pagels–Tomboulis model

Among many gauge theories the Pagels–Tomboulis model

$$L=\frac{1}{4}\left(\frac{F_{\mu \nu }^aF^{a\mu \nu }}{\mathrm{\Lambda }^4}\right)^{\delta 1}F_{\mu \nu }^aF^{a\mu \nu }$$
(1)
has a special place. Here

$$F_{\mu \nu }^a=_\mu A_\nu ^a_\nu A_\mu ^aϵ^{abc}A_\mu ^bA_\nu ^c$$

is the standard field tensor, $`\delta `$ is a dimensionless parameter and $`\mathrm{\Lambda }`$ is a dimensional constant. The gauge field is $`SU(2)`$ type i.e. $`a=1,2,3`$. One can check that this Lagrangian has positively defined energy for $`\delta \frac{1}{2}`$.

The Pagels–Tomboulis theory was originally proposed as an effective model for the low energy (3+1) QCD . In fact, it was shown that in the frame of this model electrical sources are confined for $`\delta \frac{3}{2}`$. Energy of the electric field generated by the external charge is infinite due to the divergence at large distance. Moreover, the dipole-like external source gives a finite energy field configuration. The energy $``$ behaves like

$$=c_0|q|^{\frac{2\delta }{2\delta 1}}\mathrm{\Lambda }^{\frac{4\delta 4}{2\delta 1}}R^{\frac{2\delta 3}{2\delta 1}},$$
(2)
where $`c_0`$ is a numerical constant, $`q`$ is an external charge and $`R`$ is the distance between charges . Interestingly enough for $`\delta =\frac{5}{2}`$ we obtained the $`\sqrt{R}`$ behaviour of the energy, which is in agreement with a phenomenological potential found in fits to spectra of heavy quarkonia . The standard linear potential appears in the limit $`\delta \mathrm{}`$. Highly non-linear gauge models appear in studying of the (2+1) QCD as well. Corresponding confining force has been recently obtained in .

The Pagels-Tomboulis model has been also considered as an example of a field theory with the vanishing trace of the energy-momentum tensor. In case of any $`(n+1)`$-dimensional gauge theory defined by a Lagrangian

$$L=L(F),$$

where $`F=F_{\mu \nu }^aF^{a\mu \nu }`$, the trace $`T=T_\mu ^\mu `$ has the following form

$$T=4\frac{dL}{dF}F(n+1)L.$$
(3)
One can easily find that for any $`(n+1)`$-dimensional space–time there exists the unique Lagrangian (up to a multiplicative constant) , which gives the vanishing trace of the energy–momentum tensor

$$L=\frac{1}{4}(F_{\mu \nu }^aF^{a\mu \nu })^{\frac{n+1}{4}}.$$
(4)
Only in $`(3+1)`$-dimensional space–time such a Lagrangian is a linear function of $`F`$. For instance, in $`(2+1)`$ dimension the pertinent model takes the form

$$L_{2+1}=\frac{1}{4}(F_{\mu \nu }^aF^{a\mu \nu })^{\frac{3}{4}}.$$
(5)
Such particular Lagrangian, in its Abelian version, have been recently used as a source in the Einstein equations. Many static spherically symmetric solutions have been obtained .

This short and incomplete list of applications of the Pagels–Tomboulis model in various areas of theoretical physics shows that the model is very interesting and has rich mathematical structure. Unfortunately, in contradistinction to other non-linear gauge theories (for example the Born–Infeld theory ) it has not been considered in the systematic way.
In the present paper we focus on the (2+1) Abelian Pagels–Tomboulis model with the additional topological term - the Chern–Simons term

$$L=\frac{1}{4}(F_{\mu \nu }F^{\mu \nu })^\delta +\frac{m}{4}ϵ^{\mu \nu \rho }A_\mu F_{\nu \rho }.$$
(6)
Here, for simplicity, the dimensional constant $`\mathrm{\Lambda }`$ has been neglected. This model is the natural generalization of the non–linear electrodynamics (5) considered in . It is well known that the Chern–Simons part of the Lagrangian (6) does not enter explicitly to the expression for the energy. It is due to the fact that this term is metric independent. Thus the energy–momentum tensor remains unchanged in comparison with the pure non-linear electrodynamics case. It has been shown using the field equations that in the Maxwell limit i.e. for $`\delta =1`$ the gauge field from (6) is proportional to the dual strength tensor ,

$$A_\mu =\frac{1}{2m}ϵ_{\mu \nu \rho }F^{\nu \rho }.$$
(7)
Of course, using the $`U(1)`$ gauge transformation $`A_\mu A_\mu +_\mu \psi `$ one can generate the whole family gauge equivalent solutions. The solution (7) corresponds to the Lorentz gauge. This self–dual equation can be derived also from the massive Chern–Simons Lagrangian

$$L_{mass}=\frac{1}{m^2}A_\mu A^\mu \frac{m}{4}ϵ^{\mu \nu \rho }A_\mu F_{\nu \rho }.$$
(8)
In fact, it was shown that these Lagrangians are equivalent.

Let us now generalize these results for all $`\delta >\frac{1}{2}`$. The pertinent equations of motion read

$$_\nu \left[(F_{\sigma \rho }F^{\sigma \rho })^{\delta 1}F^{\nu \mu }\right]+\frac{m}{2\delta }ϵ^{\mu \nu \rho }F_{\nu \rho }=0.$$
(9)
The solution of the second order equations (9) has the generalized form of the self-dual equation (7)

$$A_\mu =\frac{\delta }{2m}(F_{\sigma \lambda }F^{\sigma \lambda })^{\delta 1}ϵ^{\mu \nu \rho }F_{\nu \rho }.$$
(10)
It is immediately seen that after differentiation of both side of generalized self–dual equation and multiplication by $`ϵ^{\alpha \beta \gamma }`$ we obtain (9). As in the Maxwell case, the generalized self–dual equation emerges as a field equation from generalized massive Chern–Simons Lagrangian

$$L_{mass}=\frac{1}{4}(f_\mu f^\mu )^{\frac{\delta }{2\delta 1}}\frac{D\delta }{2\delta 1}ϵ^{\mu \nu \rho }f_\mu _\nu f_\rho ,$$
(11)
where the $`U(1)`$ gauge field in the generalized generalized massive Chern–Simons is denoted by $`f_\mu `$ to distinguish it from the corresponding field in the original Pagels–Tomboulis Lagrangian. The field equations for (11) have the following form

$$ϵ^{\mu \nu \rho }_\nu f_\rho \frac{1}{4D}(f_\nu f^\nu )^{\frac{1\delta }{2\delta 1}}f^\mu =0.$$
(12)
In order to establish the generalized self–dual equation for the new gauge field $`f_\mu `$ one has to rewrite (12) as

$$f_{\mu \nu }f^{\mu \nu }=\frac{1}{8D^2}(f_\nu f^\nu )^{\frac{1}{2\delta 1}}.$$
(13)
Here $`f_{\mu \nu }=_\mu f_\nu _\nu f_\mu `$. Then we express $`f_\mu f^\mu `$ in terms of the corresponding field strength tensor and substitute this into the field equation (12). One eventually gets

$$f_\mu =28^{\delta 1}D^{2\delta 1}\left(f_{\nu \rho }f^{\nu \rho }\right)^{\delta 1}ϵ^{\mu \lambda \sigma }f_{\lambda \sigma }.$$
(14)
This generalized self-dual equation becomes identical to (10) if the constant $`D`$ reads

$$D=\left(\frac{2\delta }{m8^\delta }\right)^{\frac{1}{2\delta 1}}.$$
(15)
One can see that equations (11) and (14) are in agreement with the results presented in , where the case of $`\delta =\frac{p}{q}`$, $`p,qZ`$ was considered. The relation between the topological massive Pagels–Tomboulis model and the generalized massive Chern–Simons model (11) becomes clearly visible when we observe that they have the common origin, that is they follow from a single Lagrangian

$$L_M=\frac{\alpha }{4}(f_\mu f^\mu )^{\frac{\delta }{2\delta 1}}\beta ϵ^{\mu \nu \rho }f_\mu _\nu A_\rho +\frac{m}{2}ϵ^{\mu \nu \rho }A_\mu _\nu A_\rho $$
(16)
where the constants are

$$\frac{\alpha }{\delta }\left(\frac{2\beta ^2}{\alpha ^2}\right)^\delta =1,\frac{\beta ^2}{\alpha }=2m\left(\frac{2\delta }{m8^\delta }\right)^{\frac{1}{2\delta 1}},$$
(17)
and the fields $`A_\mu `$ and $`f_\mu `$ are treated independently. Indeed, after variation of (16) with respect to $`f_\mu `$ one can use the resulting equation to eliminate this field from the Lagrangian and get (6). In the same way the gauge field $`A_\mu `$ can be expressed in terms of $`f_\mu `$. As a result we get the generalized massive Chern–Simons model. The Lagrangian (16) gives in the limit $`\delta =1`$ the so called master Lagrangian .

## 2 The dilaton model

Let us now find the analogous dual structure for the dilaton-like Lagrangian (it is possible to add a potential term for the scalar field but it does not change the result obtained below)

$$L=\frac{\sigma (\varphi )}{4}F_{\mu \nu }F^{\mu \nu }+\frac{m}{4}ϵ^{\mu \nu \rho }A_\mu F_{\nu \rho }+\frac{1}{2}(_\mu \varphi )^2$$
(18)
In fact, as it was shown in  the models (6) and (18) share many features (especially in the context of the low energy QCD where the topological term is omitted). It emerges from the fact that they can be understood as the usual electrodynamics in rather an unusual medium. In the other words both models have the form $`L=ϵF_{\mu \nu }F^{\mu \nu }+\mathrm{}`$ where the dielectric function $`ϵ`$ is a function of $`F_{\mu \nu }F^{\mu \nu }`$ in the Pagels–Tomboulis model or $`\varphi `$ in the dilaton model. In particular, in (18) $`\sigma (\varphi )=\varphi ^{\delta 1}`$ plays the same role as $`ϵ(F_{\mu \nu }F^{\mu \nu })=(F_{\mu \nu }F^{\mu \nu })^{\delta 1}`$ in (6) (see e.g. , ).

On the other hand, the Lagrangian (18) appears in the natural way as a part of the topological generalization of the $`(2+1)`$ dilaton–Maxwell–Einstein theory . This theory has been treated as the toy model of the quantum gravitation. There have been found exact solutions describing the formation of a black hole by collapsing matter. The Hawking radiation can be also described in the frame of this model. The particular form of $`\sigma `$ function is motivated by the string theory and usually reads

$$\sigma =e^{a\varphi },$$

where $`a`$ is a dimensionless constant. However, some other forms of $`\sigma `$ have been also under consideration .
The equations of motion are as follows

$$_\mu (\sigma F^{\mu \nu })+\frac{m}{2}ϵ^{\nu \mu \rho }F_{\mu \rho }=0$$
(19)
and

$$_\mu ^\mu \varphi +\frac{1}{4}\sigma ^{}F_{\mu \nu }F^{\mu \nu }=0,$$
(20)
where prime denotes the differentiation with respect to the scalar field. It is easy to notice that the solution of the equation (19) has self–dual-like form

$$A_\mu =\frac{\sigma (\varphi )}{2m}ϵ^{\mu \nu \rho }F_{\nu \rho }.$$
(21)
The corresponding massive Chern–Simons-like Lagrangian is found to be

$$L_{mass}=\frac{m^2}{2}\frac{1}{\sigma (\varphi )}f_\mu f^\mu \frac{m}{2}ϵ^{\mu \nu \rho }f_\mu _\nu f_\rho +\frac{1}{2}(_\mu \varphi )^2.$$
(22)
The pertinent field equations read

$$f_\mu =\frac{1}{2m}\sigma (\varphi )ϵ^{\mu \nu \rho }f_{\nu \rho }$$
(23)
and

$$_\mu ^\mu \varphi +\frac{m^2}{2}\frac{\sigma ^{}}{\sigma ^2}f_\mu f^\mu =0.$$
(24)
It is immediately seen that the self–dual equation (21) for the massive Chern–Simons–dilaton model (22) is just the equation of motion. Moreover, using (23) one eliminates the field $`f_\mu `$ from the second field equation. After that equation (24) takes the from

$$_\mu ^\mu \varphi +\frac{1}{4}\sigma ^{}f_{\mu \nu }f^{\mu \nu }=0.$$
(25)
As we have expected both Lagrangian (18) and (22) give the same equation of motion. Additionally we see mutual duality of these models. The strong coupling sector of the one theory is interchanged with the weak coupling sector in the other one.
At least at the theoretical level one can consider a model where the dielectric function depends on $`U(1)`$ gauge invariant $`F_{\mu \nu }F^{\mu \nu }`$ as well as on the scalar function $`\varphi `$:

$$L=\frac{\sigma }{4}(F_{\mu \nu }F^{\mu \nu })^\delta +\frac{m}{4}ϵ^{\mu \nu \rho }A_\mu F_{\nu \rho }+\frac{1}{2}(_\mu \varphi )^2.$$
(26)
We see that the Pagels–Tomboulis and the dilaton model are included in this Lagrangian and can be derived in the particular limits. It is easy to check that the corresponding generalized self-dual equation has the form

$$A_\mu =\frac{\delta \sigma (\varphi )}{2m}ϵ^{\mu \nu \rho }F_{\nu \rho }(F_{\sigma \lambda }F^{\sigma \lambda })^{\delta 1},$$
(27)
whereas the massive Chern–Simons-like Lagrangian

$$L_{mass}=A\sigma ^{\frac{1}{12\delta }}(f_\mu f^\mu )^{\frac{\delta }{2\delta 1}}\frac{D\delta }{2\delta 1}ϵ^{\mu \nu \rho }f_\mu _\nu f_\rho +\frac{1}{2}(_\mu \varphi )^2.$$
(28)
Here the constants read

$$\frac{D}{A}=\left(\frac{\delta 2^\delta }{2m}\right)^{\frac{1}{1+2\delta }},A\left(\frac{D}{A}\right)^{2\delta }=2^{\delta 2}(2\delta 1)$$
(29)
## 3 Conclusions

In the present paper we have considered the (2+1) Pagels–Tomboulis electrodynamics with topological term. The generalized version of the self-dual equations and the corresponding massive Chern–Simons-like Lagrangian have been found. Moreover, we have proved that both models can be derived from the generalized master equation (16).

The dual structure has been also obtained in case of the (2+1) topological dilaton–Maxwell model. There are two equivalent Lagrangians (18) and (22) consisting of scalar field and $`U(1)`$ field. It seems to be interesting that the strong coupling regime in the first theory is related to the weak coupling sector in the second. The non–perturbative effects in one model can be reformulated as the perturbative effects in the other one and solved applying standard methods. Knowing that $`(2+1)`$ topological dilaton–Maxwell model plays an important role in studying $`(2+1)`$ gravity we believe that this feature can give us possibility to find some new gravitational solutions for the modified model. It is quite remarkable that the dual structure can be found not only in $`U(1)`$ gauge models. Field theories containing additional degrees of freedom (here the scalar field) possess the dual formulation as well. The problem whether such a dual structure is observed in case of more complicated additional field is still unsolved and requires separate studies.

Similar duality has been observed in the combined Pagels–Tomboulis–dilaton model.

There are two obvious directions in which the present work can be continued. First of all, as it was mentioned before, the full $`(2+1)`$ topological dilaton–Maxwell–Einstein theory should be considered. Secondly, because of the fact that the Pagels–Tomboulis Lagrangian is mostly considered in its non–Abelian version it seems to be important to analyze the non–Abelian generalization of the results obtained here. Then the topological term takes the form of the well-known $`SU(2)`$ Chern–Simons invariant. Very interesting, new results, concerning the standard $`\delta =1`$ case, have been recently obtained .

We would like to thank Professor H. Arodź for many helpful comments and suggestions. This work was supported in part by the ESF programme COSLAB.


text:
# Entropy and correlations in a fluid of hard spherocylinders: The onset of nematic and smectic order

## 1 Introduction

A systematic approach to the study of the relation between configurational entropy, spatial correlations and local ordering in a fluid of elongated particles was recently outlined in , where the Authors used the theoretical framework that had been originally introduced by Giaquinta and Giunta in order to identify the “hidden” signature of freezing in the structural properties of a homogeneous and isotropic fluid of hard spheres . Their approach was based on the well known multi-particle correlation expansion of the statistical entropy, first established for a finite system by H. S. Green  and later generalized to an infinite open system by R. E. Nettleton and M. S. Green :

$$s_{\mathrm{ex}}=\underset{n=2}{\overset{\mathrm{}}{}}s_n,$$
(1)
where $`s_{\mathrm{ex}}`$ is the excess entropy per particle in units of the Boltzmann constant and the “$`n`$-body entropies” ($`s_n`$) are obtained from the integrated contribution of spatial correlations between $`n`$-tuples of particles. Note that the one-body term coincides with the entropy of the corresponding ideal gas. The pair entropy of a homogeneous and isotropic fluid of nonspherical molecules can be written as :

$$s_2(\rho )=\frac{1}{2}\frac{\rho }{\mathrm{\Omega }^2}\{g(r,\omega ^2)\mathrm{ln}[g(r,\omega ^2)]g(r,\omega ^2)+1\}d𝐫d\omega ^2,$$
(2)
where $`g(r,\omega ^2)`$ is the pair distribution function (PDF) which depends on the relative separation $`r`$ between a pair of molecules and on the set of Euler angles $`\omega ^2[\omega _1,\omega _2]`$ that specify the absolute orientations of the two particles in the laboratory reference frame. The quantity $`\mathrm{\Omega }`$ represents the integral over the Euler angles of one molecule ($`\mathrm{\Omega }=4\pi `$ for linear molecules), while $`\rho `$ is the particle number density.

The approach originally set up by Giaquinta and Giunta focused on the properties of the so-called residual multi-particle entropy (RMPE):

$$\mathrm{\Delta }ss_{\mathrm{ex}}s_2.$$
(3)
The quantity $`\mathrm{\Delta }s`$ includes, by definition, the re-summed contributions of all correlations involving more than two particles . This quantity, despite its minor quantitative relevance in the overall entropy balance, is far from being irrelevant in that it conceals significant indications on the statistical thermodynamics of the fluid that are intimately related to the role played by high-order density correlations in the system. The noticeable feature exhibited by the RMPE, as compared to the pair entropy (a negative-definite quantity), is its non-monotonic behavior. In fact, $`\mathrm{\Delta }s\left(\rho \right)`$ starts decreasing for increasing densities until the function attains a minimum beyond which it undergoes a sharp increase up to positive values. This behavior may come out, at first glance, somewhat unexpected in that one would probably surmise that, in analogy with the monotonic behavior of the two-body term $`s_2`$, the growth of higher-order density correlations that is induced by a further compression of the system should throughout contribute to a contraction of the configurational states that are accessible to the system for smaller and smaller volumes, as is actually the case from low to intermediate densities. Instead, one observes a “slowing down”, for increasing pressures, in the reduction rate of the average number of states with respect to the non-interacting system in an equivalent thermodynamic condition: in fact, the positive cumulative contribution of multiparticle correlations to the entropic balance moderately damps the systematic drop that is caused by the dominant pair term. This effect is suggestive of the emergence of a new structural condition in the system. More specifically, it indicates that multiparticle correlations have started to build up some type of ordering, on a local scale, as a result of compelling entropic constraints. The associated signature is the vanishing of the RMPE: a posteriori, it is found to herald in a very sensitive way the occurrence - in a proximate range of densities and/or temperatures - of a phase transition of the fully disordered fluid into a more structured phase. By now, the reliability of such a one-phase ordering criterion has been extensively documented for a variety of model fluids , also in two dimensions .

With specific reference to a fluid of hard spherocylinders, i.e., cylinders of length $`L`$ and diameter $`D`$ capped at both ends with two hemispheres, preliminary evidence was reported in  on the RMPE indication concerning the isotropic-nematic (I-N) transition. In the case of simple fluids composed of spherical particles a number of one-phase criteria have been introduced in the past with the aim of locating the transition from the liquid to the solid phase without resorting to the knowledge of the free energy of the two coexisting phases . However, no such simple criteria are available for nematic fluids. In this respect, the zero-RMPE criterion stands as, perhaps, a unique exception in that it can be extended in a straightforward way to fluids composed of elongated particles to deal with the transition from the homogeneous and isotropic fluid to a liquid-crystalline phase.

Since the seminal work of Onsager , the model of hard spherocylinders has been diffusely investigated, notwithstanding its simplicity, in order to study excluded-volume effects in real liquid crystals. In fact, hard spherocylinders exhibit – depending on the value assumed by the aspect ratio $`L/D`$ – a surprising variety of mesophases . In  constant-pressure Monte Carlo simulations were carried out for $`L/D=5`$ only, a case where the disordered fluid undergoes, under compression, a first-order transition to a partially ordered nematic phase. In this paper we have extended the above calculations to lower values of the aspect ratio in the range $`3L/D5`$, thus encompassing a region where the homogeneous and isotropic fluid undergoes a transition to a fully ordered solid (S) phase as well as to the smectic-A (SmA) phase, a layered orientationally ordered phase characterized by a one-dimensional density modulation along the direction $`𝐧`$ of the molecular alignment . We have carried out simulations also in the limit of very elongated particles, specifically for $`L/D=20`$, in order to analyze the behavior of the RMPE in a regime where the I-N transition point can be determined, asymptotically, in an exact way . This is also the range of aspect ratios relevant for the modelling of monodisperse aqueous suspensions of rodlike particles like the tobacco mosaic virus, a plant virus which shows an isotropic-nematic transition as well as a smectic phase at higher concentrations .

The paper is organized as follows: The theoretical framework and the numerical simulation technique, as applied to the case of cylindrical molecules with head-tail symmetry, are described in Sects. 2 and 3, respectively. The results are presented in Sect. 4 while Sect. 5 is devoted to concluding remarks.

## 2 Theory

In order to evaluate the RMPE from Eq. (3), one needs to calculate the excess and pair entropies of the fluid. The former quantity can be obtained by integrating the equation of state (EoS) along a thermodynamic path:

$$s_{\mathrm{ex}}(\rho )=s_{\mathrm{ex}}(\overline{\rho })_{\overline{\rho }}^\rho \left[\frac{\beta P}{\rho ^{}}1\right]\frac{\mathrm{d}\rho ^{}}{\rho ^{}}.$$
(4)
In Eq. (4) $`P`$ is the pressure, $`\beta `$ is the inverse temperature in units of the Boltzmann constant, and $`\overline{\rho }`$ is the density of a suitably chosen reference state. The EoS of the fluid was obtained through a Monte Carlo sampling of the system at different pressures, while the quantity $`s_{\mathrm{ex}}(\overline{\rho })`$ was calculated using the Widom test-particle insertion method  at low enough densities.

As for the pair entropy, this quantity was obtained, according to Eq. (2), after integration of the PDF which, in turn, was decoupled in the form :

$$g(r,\omega ^2)=g(r)g(\omega ^2|r),$$
(5)
where $`g(r)`$ is the radial distribution function of the molecular centers of mass that is obtained after integrating the full PDF over the set of Euler angles, while $`g(\omega ^2|r)`$ represents the conditional distribution function, normalized to $`\mathrm{\Omega }^2`$, for the relative orientation of a pair of molecules whose centers of mass lie at a distance $`r`$. Using Eq. (5), the pair entropy was separated into the sum of a translational ($`s_2^{\mathrm{tr}}`$) and an orientational part ($`s_2^{\mathrm{or}}`$), after sorting out an additional excluded-volume contribution which arises in Eq. (2) from the integration over space regions where $`g(r,\omega ^2)=0`$:

$$s_2=B_2\rho +s_2^{\mathrm{tr}}+s_2^{\mathrm{or}}.$$
(6)
In Eq. (6), $`B_2`$ is the second virial coefficient of hard spherocylinders:

$$B_2=\frac{2}{3}\pi D^3+\pi D^2L+\frac{\pi }{4}DL^2.$$
(7)
The translational contribution is formally analogous to the pair entropy of a simple fluid with no rotational degrees of freedom:

$$s_2^{\mathrm{tr}}=\frac{1}{2}\rho [g(r)\mathrm{ln}g(r)g(r)+1]d𝐫,$$
(8)
where the integration is carried out over non-overlapping regions. As for the orientational term, one finds:

$$s_2^{\mathrm{or}}=\rho g(r)S^{\mathrm{or}}(r)d𝐫,$$
(9)
where

$$S^{\mathrm{or}}(r)=\frac{1}{2\mathrm{\Omega }^2}g(\omega ^2|r)\mathrm{ln}[g(\omega ^2|r)]d\omega ^2.$$
(10)
Even for uniaxial molecules, the computation of the full orientational correlation function $`g(\omega ^2|r)`$ and its subsequent integration is a formidable task. In this specific case there are only four independent degrees of freedom which can be fixed by providing, e.g., the relative intermolecular distance $`r`$ and three angles . Without loss of generality, we can hold the center of mass of, say, particle $`1`$ fixed at the origin of the laboratory coordinate system and let its molecular axis $`𝐞_\mathrm{𝟏}`$ lie along the $`z`$-axis. Then, the position and orientation of particle $`2`$ can be unambiguously determined by specifying, for instance, two polar coordinates of its center of mass, i.e., the distance $`r`$ and the angle $`\vartheta `$ formed by the intermolecular axis with the $`z`$-axis, and the Euler angles $`\theta `$ and $`\varphi `$ of the $`𝐞_\mathrm{𝟐}`$ axis (the “twist” angle, $`\chi `$, is redundant for uniaxial molecules). In order to simplify the whole scheme, we neglected the dependence of $`g(\omega ^2|r)`$ on $`\vartheta `$ and $`\varphi `$, thus focusing on the information associated with the angle representing the relative orientation of the two molecular axes, $`\theta =\mathrm{arccos}(𝐞_\mathrm{𝟏}𝐞_\mathrm{𝟐})`$. Indeed, this is the critical parameter that should be monitored in order to assess the onset of either nematic or smectic order in the fluid. The contracted orientational distribution function $`g(\theta |r)`$ is normalized in such a way that:

$$\frac{1}{2}_0^\pi g(\theta |r)\mathrm{sin}\theta \mathrm{d}\theta =1$$
(11)
We do not expect that such a simplification may heavily bias the estimate of the weight associated with orientational correlations in the homogeneous and isotropic phase. Indeed, the quantity we are ultimately interested in is just an integral measure that can help to assess the relative balance between the positional and angular contributions that intervene in the configurational entropy.

## 3 Simulation

We performed Monte Carlo (MC) simulations of hard spherocylinders at constant pressure. This choice is rather common for systems composed of non-spherical hard-core particles for which it may be difficult to calculate the equation of state through the contact value of the PDF, as is usually done in a constant-volume simulation. Furthermore, density fluctuations are more naturally accommodated in a constant-pressure simulation . The number of particles, that were enclosed in a cubic box with periodic boundary conditions, typically ranged between $`500`$ ($`L/D=3.2,5`$) and $`800`$ ($`L/D=3`$), with an intermediate value of $`672`$ particles for $`L/D=4`$. A larger sample composed of $`1500`$ particles was used for more elongated particles with $`L/D=20`$.

A perfectly ordered, low-density lattice arrangement was the starting configuration. Then, the system was allowed to equilibrate, initially along a constant-volume MC path. A sequence of states was then generated at constant pressure, starting from an equilibrated isotropic configuration. We carried out rather extended simulations, as compared with those currently reported in the literature, especially in proximity of the transition threshold. In fact, after an equilibration period of typically $`10^5`$ to $`10^6`$ MC cycles, simulation data were obtained by generating chains consisting of $`5\times 10^5`$ to $`5\times 10^6`$ MC cycles, depending on the pressure. A MC cycle consisted of an attempt of changing, sequentially, both the position and the orientation of each molecule, followed by an attempt of changing the volume of the sample. During such a procedure, each molecule was first displaced from its original position, by moving at random its center of mass within a cube. The molecule was then re-oriented within a cone centered about the molecular axis. The overall acceptance probability for the combined move was adjusted to about 50%. The isotropic change of the simulation box was obtained by varying at random the box side $`L`$. Finally, the maximum displacement allowed was set so as to achieve an average acceptance probability for volume changes of $`50`$%. For hard-core molecules, the usual Metropolis acceptance criterion reduces to a check of particle overlaps after each Monte Carlo move. In this regard, a simple and efficient algorithm can be used for spherocylinders . During the cumulation runs, we monitored the average density and built histograms for the translational and orientational distribution functions, respectively; equilibrium averages and standard deviations were computed by dividing such runs into 5 to 10 independent blocks. In the following, we shall refer to the volume packing fraction $`\eta =\rho V_{\mathrm{hsc}}`$, where $`V_{\mathrm{hsc}}=(\pi /4)D^2L+(\pi /6)D^3`$ is the volume occupied by one spherocylinder, and to the reduced pressure $`P^{}=\beta PV_{\mathrm{hsc}}`$. We sampled the radial distribution function $`g(r)`$ at intervals of $`0.1D`$, while the orientational distribution $`g(\theta |r)`$ was calculated with a grid spacing of $`\mathrm{\Delta }\theta =5^{}`$.

We investigated the phase diagram of the model up to the threshold of either the nematic or the smectic phase. The onset of liquid-crystalline order was monitored through the nematic order parameter:

$$S=\frac{1}{N}\underset{i=1}{\overset{N}{}}\frac{3\mathrm{cos}^2\psi _i1}{2},$$
(12)
where $`\psi _i`$ is the angle formed by the molecular axis of the $`i`$-th molecule $`𝐞_i`$ (the sum running over all particles in the system). The director $`𝐧`$ defines the alignment direction attained, on average, by the molecules. Since this direction is not known a priori, the order parameter is usually determined by diagonalizing the traceless, symmetric, second-rank tensor $`𝐐`$ that is defined in terms of the molecular axes as:

$$𝐐=\frac{1}{N}\underset{i=1}{\overset{N}{}}\frac{3𝐞_i𝐞_i𝐈}{2},$$
(13)
where $`𝐈`$ is the unit tensor. The nematic order parameter is then obtained as the largest eigenvalue, and the director as the corresponding eigenvector . The value attained by $`S`$ is close to zero in the isotropic phase and tends to one in a highly ordered phase. Across the ordering transition, both the density and the order parameter show a finite jump. However, such discontinuities, that are associated with a first-order phase transition, are in certain cases so small that a closer investigation of the correlation functions or a direct observation of the arrangement of the molecules in the sample may be necessary on the thermodynamic edge of both the nematic and smectic phase.

As already anticipated, we used Widom’s insertion method  to obtain independent numerical estimates of the excess entropy at low densities, $`s_{\mathrm{ex}}(\overline{\rho })`$, to be used in Eq. (4). The Widom technique provides a simple scheme for calculating the excess chemical potential, $`\mu _{\mathrm{ex}}`$, of not too dense a liquid via the calculation of the average Boltzmann factor associated with the (never accepted) random insertion of an additional particle in an $`N`$-particle system. The excess entropy can then be obtained through the thermodynamic equation:

$$s_{\mathrm{ex}}=\beta \mu _{\mathrm{ex}}+\frac{\beta P}{\rho }1$$
(14)
Depending on the density and the elongation of the spherocylinders, 50 to 200 trial insertions per MC step were typically needed in order to obtain a reliable estimate of $`\mu _{\mathrm{ex}}`$. The use of this technique at small but finite densities avoids the otherwise necessary extrapolation to the ideal gas limit, as a reference state for the integration contemplated in Eq. (4). This latter procedure was adopted in , where some spurious fluctuations of the orientational distribution function as well as some difficulties associated with the simulation in the highly dilute regime were registered.

As sketched in Fig. 1, the values obtained for $`s_{\mathrm{ex}}`$ using Widom’s insertion method are quite stable in all the cases we have examined: the thermodynamic potential relaxes almost immediately, with small fluctuations about the average value. No significant drifts were observed during simulations as long as $`10^5`$ MC steps. The simulation parameters and the results for the relevant properties of the fluid at low densities were collected for various elongations in Table 1.

## 4 Results and discussion

### 4.1 Phase behavior for $`3L/D5`$

In this subsection we shall focus on the phase behavior of the model in a range of parameters where, for increasing values of the aspect ratio, the disordered fluid undergoes a transition to either a solid, a smectic or a nematic phase. We investigated the model for shape anisotropies $`L/D=3,3.2,4,`$ and $`5`$. For $`L/D=3`$, the fluid freezes into a crystalline phase. An I-SmA phase transition is observed over a range of larger aspect ratios bounded by an isotropic-smectic-solid (I-SmA-S) triple point ($`L/D=3.1`$) and by an I-N-SmA triple point ($`L/D=3.7`$), respectively. For even larger anisotropies, the disordered fluid forms, under compression, a nematic phase .

The reliability of the present results for the EoS and for the nematic order parameter can be appraised through Fig. 2 where the above quantities were plotted as a function of the packing fraction for $`L/D=3.2`$ and $`5`$. The comparison with the simulation data reported by McGrother and co-workers  shows that a system with $`500`$ particles is fairly adequate for evaluating the basic thermodynamic properties of the fluid. The agreement turned out to be equally good along the disordered branch also for $`L/D=3`$ and $`4`$, up to the transition point.

We now turn to a discussion of the properties of the model for $`L/D=5`$, a case where the isotropic fluid undergoes a rather weak first-order transition to a thermodynamically stable nematic phase at about $`45\%`$ of the close-packing density, a value corresponding to an absolute packing fraction of $`0.4`$ . No specific feature indicating the transition edge is apparent either in the equation of state or in the order parameter (see Fig. 2). A rather modest degree of positional order shows up in the spatial profile of the radial distribution function that was plotted in Fig. 3 for increasing pressures, all the way up to the transition threshold. Actually, for moderately small packing fractions, the local density around one generic spherocylinder is significantly reduced, with respect to the homogeneous value taken at large distances, for interparticle separations lower than $`3\frac{1}{2}`$ molecular diameters, a distance which corresponds to the minimum contact separation between two orthogonal spherocylinders.

Retrospectively, this local “depletion” effect is more easily understood if one looks at the orientational distribution function (see Fig. 4): the almost flat profile of $`g(\theta |r)`$ for $`r>3.5D`$, when plotted as a function of $`\theta `$, implies that orthogonal geometries in the relative spatial arrangement of two spherocylinders are equally probable as parallel configurations are. The steric hindrance produced, on average, by such orthogonal (or almost orthogonal) particles sensitively reduces the probability of finding other molecules at shorter distances from the central one. Upon further compressing the fluid, the value of $`g(\theta |r)`$ for aligned-particles geometries ($`\theta =0,\pi `$) steadily increases while different geometries become, at the same time, rarer and rarer. This is apparent from the progressive and systematic reduction of $`g(\theta |r)`$, for short and intermediate molecular separations, over a wide range of angles centered about $`\pi /2`$. Correspondingly, the radial distribution function becomes more and more structured at short distances as is distinctly shown in Fig. 3 by the building up of a first coordination shell formed by particles lying almost at close contact with the central one.

The excess entropy of the fluid was resolved in Fig. 5 in terms of the contributions associated with pair and more-than-two-particle correlations, respectively (see Eq. (3)). The behavior of the RMPE is similar to that exhibited by the same quantity in a variety of other model systems, composed of spherical particles, across an ordering transition such as the freezing of a fluid  or the phase separation of a binary mixture . In particular, this quantity vanishes for a value of the packing fraction ($`\eta _0`$) which falls precisely on top of the currently estimated I-N phase transition point (see Table 2 where we summarized the predictions of the entropy-based criterion for the presently investigated values of the aspect ratio). We note that the current RMPE estimate sensitively improves on that formerly given in  where the values reported for the pair entropy turned out to be affected by a systematic computational error. However, no significant morphological change resulted, a posteriori, in both the pair entropy and in the RMPE. We also recall that the Authors had shown in  that the pair entropy changes with the size of the sample, for a given density, in a tiny but systematic way, the zero-RMPE density shifting towards moderately larger values. The RMPE inverts its trend (from decreasing to increasing) in the density region ($`\eta 0.36`$) corresponding to a more extended structuring of the fluid at short distances (see Fig. 3). To be specific, we refer to the growing of a local nucleus of (mostly) aligned particles that is signalled by the emergence of a secondary maximum in the radial distribution function at a relative distance twice as large as that corresponding to the first coordination shell.

Figure 5 also shows the pair entropy of the fluid resolved, according to Eq. (6), into the sum of a (spatially independent) excluded-volume term ($`B_2\rho `$) plus two more contributions arising from translational and orientational correlations, respectively. As expected, it is $`s_2^{\mathrm{or}}`$ that drives the rather sharp increase of $`\mathrm{\Delta }s(\eta )`$ just beyond the minimum. Vice versa, the contribution associated with positional correlations, $`s_2^{\mathrm{tr}}`$, is very small all over the fluid range. The function which, upon integration (see Eq. (9)), yields the quantity $`s_2^{\mathrm{or}}`$ is shown, for increasing densities, in the right part of Fig. 3. The value of the corresponding integral is negative and keeps close to zero at low and intermediate densities (see Fig. 5). For packing fractions larger than $`0.3`$, $`s_2^{\mathrm{or}}`$ starts decreasing more and more rapidly and eventually overcomes (in absolute value) the excluded-volume term. As seen from Fig. 5, the fingerprint of the ordering of the fluid is manifest in the persistence of angular correlations up to intermediate and long distances.

Considerations similar to those developed above for $`L/D=5`$ apply also to the $`L/D=3.2`$ case, even if it is a smectic phase that is now formed by the isotropic fluid. However, the basic underlying mechanism which drives the first-order I-SmA transition is analogous to that exploited in the nematic case. Obviously, the denser isotropic fluid looks more structured than for $`L/D=5`$ (see Fig. 6). Furthermore, at the transition point angular correlations show a very slow spatial decay. We also note that in this case the lower molecular asymmetry modifies the scale of interparticle distances in the average density profile. Thus, the effect associated with the structuring of the second coordination shell, which we already commented upon for $`L/D=5`$, is less resolved since the corresponding distance falls very close to the position of the lone weak maximum, located at a distance $`r/D=1+\frac{1}{2}(L/D)=2.6`$, that is present in the radial distribution function at low densities. A shoulder, rather than a peak, emerges at $`r/D2.4`$, again in a density range corresponding to the position of the minimum ($`\eta 0.47`$) attained by the RMPE (see Fig. 7).

In general, the ordering thresholds detected through the vanishing of the RMPE correlate very well with the corresponding transition point (see Table 2), whatever the nature of the higher-density phase coexisting with the isotropic fluid. The evidence discussed so far justifies the claim that the RMPE of spherocylinders monitors the leading microscopic process which drives the phase transition in all such cases, i.e., the aligning of spherocylinders along a common direction. As such, the vanishing of this quantity presumably portends the density threshold beyond which the nematic ordering may possibly emerge in the system, regardless of other concurrent structural phenomena like those which may ultimately lead to the formation of a more ordered macroscopic state, be it smectic or crystalline, instead of a pure nematic phase. An indication consistent with this thesis that is, perhaps, not accidental (yet to be considered with due caution because of the numerical uncertainty arising from the computational error which affects, at least, the third significant figure) is offered by the apparently greater accuracy of the predictions given by the RMPE-based criterion for $`L/D=4`$ and $`5`$ (see Table 2), viz., in those cases where the stable coexisting phase is a truly nematic fluid. In the other two cases investigated, i.e., when either a solid or a smectic phase is formed, the criterion just overshoots the target, locating the internal threshold for the ordering of the fluid at a slightly higher density.

### 4.2 The Onsager regime

As the aspect ratio increases, the I-N transition point moves to lower and lower densities. In the Onsager limit of infinitely long rods ($`L/D\mathrm{}`$), a fluid of hard spherocylinders undergoes a first-order phase transition to a nematic phase for $`B_2\rho =3.29`$ . However, the phase behavior characteristic of the Onsager regime qualitatively sets in for shape anisotropies even less than $`L/D=20`$, even if for such values of the aspect ratio the basic assumption made by Onsager that all virial coefficients of order higher than two can be neglected is not yet satisfied . In fact, the contribution of the third virial term to the free energy, evaluated for $`L/D=20`$ at the transition density, turns out to be still comparable to the contribution of the second virial term .

We carried out simulations for $`L/D=20`$. In passing, we recall that this value mimics the typical size of the tobacco mosaic virus, whose particles have a practically rigid rod shape of $`1518`$ nm diameter and $`300`$ nm length . For such large values of the aspect ratio, the simulation of a fluid of hard spherocylinders dictates more severe constraints on the size of the simulation box which should be large enough to accommodate at least two rod lengths, so as to avoid multiple overlaps between a molecule and the periodic images of another particle . The number of particles chosen ($`N=1500`$) is sufficient to ensure that the condition mentioned above is fulfilled in the (relatively low) density range where the disordered phase is thermodynamically stable. The reduced pressure and the nematic order parameter are shown in Fig. 8. The isotropic liquid phase is mechanically stable up to a reduced pressure $`P^{}=0.92`$: in this regime the system shows, for simulations as long as $`2.5\times 10^6`$ MC cycles, no significant fluctuations about the average values of the packing fraction ($`\eta =0.145`$) and of the nematic order parameter ($`S=0.058`$), respectively. Upon further compressing the system up to $`P^{}=0.93`$, we observed, after about $`1.5\times 10^6`$ MC cycles, a spontaneous and rapid transformation into a nematic phase which, at equilibrium, settled down at a packing fraction $`\eta =0.182`$ and was characterized by an order parameter $`S=0.862`$. The resulting “boundaries” are slightly shifted toward higher densities if compared with the direct estimates reported in , i.e., $`\eta _{\mathrm{iso}}=0.139`$ or $`0.137`$, and $`\eta _{\mathrm{nem}}=0.171`$ or 0.172, according to whether the Gibbs-Duhem integration or a Gibbs-ensemble technique was used. Exploratory runs performed by decompressing the system from the ordered phase distinctly show an hysteresis, the fluid remaining almost nematic for pressures as low as $`P^{}0.75`$. We calculated the pressure also using the “decoupling approximation” between the translational and orientational degrees of freedom originally introduced by Parsons . In this approximation a system of rods is mapped onto a system of spheres interacting with an effective orientation-dependent potential. As already observed by McGrother and co-workers for the shorter elongation regime $`3.2L/D5`$ that was analyzed in , the resulting EoS turns out to be fairly accurate in the isotropic phase up to the transition point, and definitely better than the prediction based on the scaled-particle-theory approach exploited by Boublik . However, it should be noted that the latter approach is based on a one-parameter approximation for the third and fourth virial coefficients which cannot be expected to yield accurate results for large elongations . A better agreement with the simulation data is obtained with a closely related description that was proposed by Nezbeda : this approximation is based on an empirical fit of the virial coefficients, especially tailored on the available results for hard spherocylinders. All the above approximations for the EoS were reported, for a comparison, in Fig. 8: note that the simulation data are closely bracketed by the Parsons and Nezbeda approximations, respectively.

Radial correlations are shown in Fig. 9 together with the function whose space integral yields $`s_2^{\mathrm{or}}`$. All over the liquid density range, the radial distribution function is practically structureless apart from the correlation hole at short distances (see Fig. 9). As a result, the translational contribution to the pair entropy keeps close to zero all over the explored density range (see Fig. 10). The same is also true for the orientational contribution for packing fractions less than about $`0.15`$. It thus follows that the pair entropy of the isotropic fluid is substantially equal to the excluded-volume term $`B_2\rho `$, as is actually assumed in the original Onsager theory. At variance with the positional term, the angular contribution is responsible, together with the excluded-volume term, of the vanishing of the RMPE. Just beyond the transition point, $`s_2^{\mathrm{or}}`$ blows up and definitely overcomes the excluded-volume term (see Fig. 10). The resulting RMPE shows the typical behavior already observed for smaller aspect ratios. Also in this case, the zero-RMPE threshold is in very good agreement with the I-N transition point estimates given in  (see Table 2). We also reported in Fig. 10 the Parsons and Nezbeda analytical estimates for the excess entropy. As already pointed out for the EoS, both approximations turn out to predict fairly well, almost with the same degree of accuracy, also the excess entropy of the fluid.

As seen from Figs. 57 and 10, the overall importance of the cumulative contribution of higher-order density correlations to the excess entropy decreases with increasing shape anisotropies. This is clearly a consequence of the progressive confinement of the isotropic phase to lower and lower densities. In this regard, we just observe that the value attained by the RMPE at its minimum drops from $`45\%`$ of the excess entropy for $`L/D=3.2`$ to $`18\%`$ for $`L/D=20`$. This behavior is consistent with the numerical findings on the virial expansion cited above and with the asymptotic trend predicted by Onsager as $`L/D\mathrm{}`$. Note, however, that at low densities the ratio $`\mathrm{\Delta }s/s_{\mathrm{ex}}`$ moderately increases with $`L/D`$ for a given packing fraction. Actually, longer and thinner particles give rise to more extended multiparticle correlations which trigger the ordering of the fluid at lower and lower densities. Beyond the zero of the RMPE, where the nematic phase is thermodynamically stable, the present data monitor de facto a system in a metastable, macroscopically isotropic condition whose proper description lies beyond the standard Onsager theory.

## 5 Concluding remarks

In this paper we have analyzed the contributions to the “pair entropy” $`s_2`$ of hard spherocylinders of length $`L`$ and diameter $`D`$ that are associated with excluded-volume, translational and angular correlations, with particular emphasis on the thermodynamic behavior exhibited by the above quantities on approaching the phase transition from the low-density fully disordered phase to a partially ordered phase at higher densities. An elucidating synthesis of the results obtained for $`s_2`$ through an intensive Monte Carlo sampling of the model is offered by Fig. 11 where we plotted the three contributions cited above, each of them being calculated in the state corresponding to the vanishing of the residual multi-particle entropy (RMPE) for an assigned value of $`L/D`$. The RMPE is a quantity that gauges the cumulative weight of spatial correlations involving more than two particles in the configurational entropy of the fluid. Figure 11 neatly indicates the relative importance of the three contributions in the overall entropic balance: for very small asymmetries, the translational term, $`s_2^{\mathrm{tr}}`$, prevails (in absolute value) while being comparable with the excluded-volume contribution, $`B_2\rho `$ (note that the data for $`L/D=0`$ do obviously refer to the hard-sphere case ). For increasing values of the aspect ratio the angular term, $`s_2^{\mathrm{or}}`$, acquires more and more importance: in fact, an interpolation of the available data shows that the three contributions reach the same magnitude for $`L/D0.4`$. Actually, it is in this range of values (more precisely, for $`L/D0.35\pm 0.05`$ ) that the “rotator phase” (i.e., the plastic crystal) disappears in the phase diagram of hard spherocylinders, and is replaced at high densities by an orientationally ordered, crystal phase. As seen from Fig. 11, in the range $`0.4L/D5`$ the ordering of the fluid is mainly controlled by angular correlations. In fact, the translational contribution rapidly tends to smaller and smaller values and practically vanishes for $`L/D>5`$. Also $`s_2^{\mathrm{or}}`$ asymptotically tends to zero in this range of increasing asymmetries but, as seen from Fig. 11, the decay of this quantity is much slower than that shown by its translational counterpart. Correspondingly, the excluded-volume term becomes the dominant contribution to the configurational entropy of the fluid. Note that its value for $`L/D=20`$ ($`3.45`$) is already very close to the Onsager limit ($`3.29`$).

As far as the quality of the “predictions” offered by the zero-RMPE criterion are concerned, the agreement with the properly defined thermodynamic thresholds is impressive for all the asymmetries that have been investigated. Indeed, the vanishing of the RMPE monitors, in a very sensitive and reliable way, the ordering of the homogeneous and isotropic fluid into a more ordered phase be it nematic, smectic or solid. However, we remark that such a close quantitative correspondence should not be necessarily and systematically expected a priori. In fact, the zero of $`\mathrm{\Delta }s`$ needs not coincide with the thermodynamic edge of the disordered phase that is properly located through the comparison of the free energies of the two coexisting phases. Actually, the RMPE conveys a type of information that is intermediate between the fully macroscopic level and the underlying microscopic description of the system. The interpretation of such a simply accessible information (and, more specifically, of its change of sign) as an intrinsic signature of the incipient ordering of the fluid appears to be quite firmly established on the basis of an ample and coherent evidence that has, by now, emerged in a variety of continuum and lattice model fluids . The present analysis of the “fine structure” of the configurational entropy of hard spherocylinders further corroborates the sensitivity of the RMPE to local ordering phenomena which may even turn out into a rather weak first-order phase transition. We believe that this one-phase entropic criterion can be conveniently generalized to account for more than one phase transition, leading the system to increasing levels of self-organization. An attempt in this direction has been recently done by Cuetos and coworkers whose results seem to indicate the existence of a jump in the translational part of the pair entropy as well as in its rate of change across the nematic-smectic transition . However, this evidence was not considered conclusive because of the limited size of the simulation box. We are also currently investigating this point with promising preliminary results.

## Acknowledgments

We would like to thank Professor Bruno Martinez-Haya for useful discussions and for pointing a numerical inconsistency out in a previously published article. D. C. gratefully acknowledges the hospitality and advice of Professor M. P. Allen during a visit to the University of Bristol.

## Tables

## Figures


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# Comment on ‘Equilibrium crystal shape of the Potts model at the first-order transition point’

## References