# Topological effects in ring polymers (II): Influence of persistence length

## I Introduction

Unconcatenated and unknotted rings in their melt are relatively compact. This was found in recent computational studies and was expected on theoretical grounds. Qualitatively the squeezing of the rings was attributed to the topological constraints (see Fig. 1 (a)) . This is in line with much older observations showing that dilute rings repel each other much more strongly than their linear chain counterparts due to the entropy loss associated with the unconcatenation constraint preventing the two rings to thread each other. While the usual excluded volume interaction is screened out at high chain overlap (i.e., if the ring size $`R`$ is larger than the size $`\xi `$ of the excluded volume blob) , topological interactions are expected to dominate the conformational properties if the number of overlapping rings $`pR^3\varphi /N`$ ($`N`$ being the chain mass, $`\varphi `$ the monomer density) becomes high enough.

In a simple Flory-like argument Cates and Deutsch (CD) argued that the number of degrees of freedom lost for a typical ring due to its topological interactions with neighbouring rings increases like $`p^\alpha `$ where $`\alpha `$ is an unknown exponent. This free energy term, which favors decreasing the ring size, has to be balanced by the entropy penalty for squashing a ring. To be specific, this penalty was assumed to be the same as for a Gaussian chain. Adding these contributions and minimising over $`RN^\nu `$ yields the Flory exponent $`\nu =(\alpha +1)/(3\alpha +2)`$. The simplest possible estimate for $`\alpha `$ is to say that that roughly one degree of freedom is lost for each of the $`p`$ neighbours which the ring is prevented from threading, i.e. $`\alpha =1`$ and hence $`\nu =2/5`$. This is very close to the value $`\nu 0.39`$ found by us in our previous study . Note that the overlap number $`pN^{1/5}`$ increases extremely weakly and that the only intrinsic length scale in the CD picture is the ring size $`R`$ itself (possibly renormalised in terms of excluded volume blobs of size $`\xi `$). Again this was found to be qualitatively in good agreement with the simulations reported in our first paper . From the CD picture one expects a similar density crossover scaling for rings as for linear chains: The ring size $`R(\varphi )`$ reduced by the ring size $`R_0`$ of the dilute reference ring should scale with $`\varphi /\varphi ^{}`$ where $`\varphi ^{}N/R_0^3`$ is the crossover density. Having focused in ref.  on flexible rings at one fixed density we were unable to verify this implicit scaling assumption of the CD picture.

A different picture comes from the extensive studies on (isolated) ring polymers in gels (see Fig. 1 (b)), often modelled by so-called lattice animals (LA), depicted in Fig. 1 (c) . If the ring size $`R`$ becomes larger than the typical distance $`d_t`$ between the fixed topological obstacles (represented as squares in the figure) the rings are forced to retrace their paths and the fractal dimension $`d_f=1/\nu `$ becomes that of a strongly branched object. The question is now if it is possible to use this well-understood model via a standard mean-field argument also for strongly overlapping systems of rings in their own melt. Are the surrounding rings able to generate (in a self-consistent manner) around a reference ring a fixed mesh of topological obstacles? And if so, is $`d_tR`$ — then LA and CD picture would be indistinguishable from the scaling point of view — or does it introduce an additional ring length independent scale? In the latter case, obviously, the above mentioned density crossover scaling would not work. (However, one can strictly only expect this LA picture to hold in the high entanglement limit.) In any case, there is a catch: While increasing $`pb^3N^{3\nu 1}`$, $`b`$ being the persistence length, the effective exponent $`\nu (p)`$ is supposed to drop down to $`1/3`$ (and even down to $`\nu =1/4`$ for an ideal Gaussian LA within an intermediate range of ring sizes $`N`$) . Hence, the LA picture might not be self-consistent as already stressed in ref. . It is crucially the prefactor $`b^3`$ (and not the inefficient $`N^{3\nu (p)1}`$) which allows the simulator to control the overlap. (This assumes that the persistence length only weakly affects the hypothetical length $`d_t`$ which has to be checked a posteriori.).

This is the route we have taken in this study to test the scaling predictions (rather than the variation in density $`\varphi `$ which we plan to investigate in a subsequent study). Indeed, the persistence length $`b`$ turns out to be a very efficient way to vary the overlap number $`p`$ (additional computational overhead and reduced diffusion constants taken into account) compared to the ring mass (which we have however increased from $`N=512`$ to $`N=1024`$). This allows us to more severely put a test on the scaling predictions of the CD scenario than we were able in our previous study . In contrast to that work, the new evidence presented here shows the emergence of (at least) one further length scale alongside $`R`$ which we identify with $`d_t`$. Tentatively, our data are consistent with a broad crossover towards the LA picture in the limit of high chain overlap which is attained by increasing $`b`$ so that the chains become more extended (though more compact in the scaling sense of smaller $`\nu `$). A typical semi-flexible coil at higher overlap is presented in Fig. 2 on the right.

Of course, the CD and LA pictures are not necessarily contradictory in that they might provide useful heuristic descriptions in different overlap limits. In the computationally important regime (depending on $`b`$) where the rings expel successfully neighbouring chains and form relatively dense coils, the mean-field assumption of the LA approach has to break down. A typical chain for low overlap is shown Fig. 2 on the left. The CD picture is a priori a good candidate to describe this regime where overlap $`p`$ and topological interactions are weak. A possible choice for the unknown CD exponent in this regime is the limiting case $`\alpha 0`$ and, hence, $`\nu 1/2`$, i.e. the topological constraints mainly contribute logarithmic corrections to a closed  Gaussian chains of blobs. Evidence for this (justifying a posteriori the squeezing term used by CD) is presented below.

Our paper is arranged as follows: In the next section II we give a short synopsis of the model and simulation technique used. To understand the special effects linked to the unconcatenation constraint we need reference date at the same chain and persistence length to compare with. This is provided in section III where we review some properties of dilute semi-flexible ring polymers. In the subsequent section IV we investigate the statistics of ring polymers in their melt as a function of the stiffness, comparing them with dilute rings and dense linear chains from ref. . (Note that in most figures we compare features discussed subsequently in section III and IV.) Possible scaling scenarios are discussed and a detailed analysis of the local fractal dimension is presented. The following section V presents briefly our first results on the dynamics of semi-flexible ring polymers. We conclude with a summary of our results.

## II Algorithm and Parameters

As in our previous study we investigate the properties of unknotted and unconcatenated rings in the framework of the bond fluctuation model (BFM). Many static and dynamic properties of linear chains are known for this computationally efficient, coarse grained lattice model. A small number of chemical repeat units is mapped onto a lattice monomer such that the relevant characteristics of polymers – excluded volume and connectivity – are retained. Each monomer blocks a unit cell of the three dimensional cubic lattice from further occupancy. Adjacent monomers along a polymer are connected via one of 108 allowed bond vectors of lengths $`2,\sqrt{5},\sqrt{6},3`$ and $`\sqrt{10}`$. Here and in the following all spatial distances are measured in units of the lattice spacing. This set of bonds allows for 87 different bond angles and, hence, results in a good approximation to chains in continuous space. The bond vectors are chosen such that the local excluded volume interactions prevent the rings from crossing each other during their motion. This conservation of the topology ensures that the rings remain neither knotted with themselves nor concatenated with one another during the course of the simulation. We evolve the ring conformations via random local monomer displacements.

As explained in the Introduction, a crucial parameter is the overlap number $`p`$, which increases only very weakly with $`N`$, but much more strongly with the persistence length. In order to tune the persistence length, we impose a simple intramolecular potential which favours straight bond angles: $`E(\mathrm{\Theta })=\sigma \mathrm{cos}(\mathrm{\Theta })`$. Here $`\mathrm{\Theta }`$ denotes the complementary angle between two successive bonds and $`\sigma `$ the dimensionless energy scale (setting $`k_BT=1`$). This potential has been used and investigated in various studies on linear polymer chains at filling fraction $`\varphi =0.5`$ of occupied lattice sites . This is of importance because it is reasonable to assume that on short length scales (for long enough chains) neither ring closure nor topological constraints are pertinent. This statement will be corroborated later in section IV when we discuss the local ring structure (Fig. 6). Note for now that other local quantities like the mean bond length $`l`$, $`\mathrm{cos}(\mathrm{\Theta })`$ (i.e. the mean stiffness energy per monomer) or the acceptance rate $`A`$ are identical for rings and their linear counterparts. Hence, one expects to find the same local rigidity $`b(\sigma )`$ for rings as for linear chains where $`b=b_e^L`$ is easily obtained from the mean-square end-to-end vector $`R_e^2`$ and the known Flory exponent of linear chains. See Tab. I and Tab. II for the dilute ($`\varphi =0`$) and the dense limit ($`\varphi =0.5`$) respectively. The systems containing dilute rings and linear chains have been simulated for reasons of comparison. Not surprisingly the quantities featured in Tab. I and Tab. II depend somewhat on the volume fraction . Note that at the density $`\varphi =0.5`$ of occupied lattice sites, many static and dynamic features of molten linear polymer materials are reproduced by the BFM. For example, the single chain conformations obey Gaussian statistics down to the screening length $`\xi (\sigma =0)6`$ of the excluded volume interaction obtained by the static structure factor .

We have restricted ourselves to values $`\sigma 3`$ because we found tentative evidence for the onset of a nematic order at values $`\sigma 4`$. Due to the lower conformational entropy rings tend to order nematically at lower stiffnesses than linear molecules. (For linear chains an isotropic to nematic transition is found close to $`\sigma 6`$ .) Moreover, increasing the stiffness also decrease the number of statistically independent segments, and we want to keep finite $`N`$ effects low, even for small ring lengths.

The algorithm described above has been implemented on a massively parallel CRAY T3E computer. Using a 2 dimensional geometric decomposition of the simulation grid of linear extension $`L=128`$, we employ 64 T3E processors. The simulations involve about $`\mathrm{40\hspace{0.33em}000}`$ hours of single processor CPU time.

As shown in Tab. III, this allows us to investigate ring systems with 131072 monomers and chain masses up to $`N=1024`$. The data for flexible rings have been used as starting configurations for simulations at higher persistence length. In most cases rings diffused at least a spatial distance of their radius of gyration before any conformational data were collected. The simulation runs were extended up to five times the relaxation time for sampling the ring conformations. Note that we could not meet this stringent criterion for the semi-flexible ($`\sigma >0`$) systems at our largest mass $`N=1024`$. The resulting data appear to be time independent, and we presume them to be equilibrated, but they have not diffused over a radius of gyration. These three data points ($`\sigma =1,2`$ and $`3`$) have to be taken with care.

As can be deduced from Tab. III a relatively small increase in persistence length is a very effective way to increase the overlap number $`pR_e^3/N`$. To give some numbers, increasing the stiffness parameter $`\sigma `$ from $`0`$ to $`3`$ amounts in increasing $`p`$ by a factor 3 for $`N=256`$ (seen in Fig. 2) and by a factor 5 for $`N=512`$. To achieve a similar effect by tuning the contour length requires an increase by two, respectively three, orders of magnitude .

## III Dilute rings revisited

As a reference for the subsequent section on strongly overlapping rings (where the unconcatenation constraint matters) we briefly revisit some properties of flexible and semi-flexible dilute rings and their linear counterparts. Basically, the remaining unknottedness constraint and the requirement of ring closure do not matter: Dilute rings behave broadly like linear chains.

The simplest quantity to characterise the chain structure as a function of the stiffness parameter $`\sigma `$ is the overall chain size versus chain length $`N`$. The size of the rings is measured first with the usual mean-square radius of gyration $`R_g^2`$. As a second measure, we sample the mean-square distance $`R_n^2=(\stackrel{}{R}_i\stackrel{}{R}_{i+n})^2`$ (averaged over all monomers $`i`$) between pairs of monomers that are $`n`$ monomers apart along the contour. In particular we define for rings the mean-square ring diameter $`R_e^2=R_n^2|_{n=N/2}`$. (For the linear chains $`R_e^2=R_n^2|_{n=N}`$ denotes the usual mean-square end-to-end distance.) In Fig. 3 the diameter $`R_e=R_e^2^{1/2}`$ for flexible and semi-flexible dilute rings is plotted versus $`N`$. Not included are the linear counterparts of same $`N`$ and $`\sigma `$. (But see Fig. 4.) The data are well fitted for all the persistence lengths considered by $`R_e=b_eN^\nu `$ with the classical Flory exponent $`\nu =\nu _03/5`$ . The effective bond length $`b_e`$ encodes the persistence length effect. It is tabulated for linear chains (”L”) and rings (”R”) in table I. Similar fits have also be performed for the radius of gyration. We find, independent of chain size and persistence length, the following relations: $`b_e^L/b_e^R1.89`$, $`b_g^L/b_e^L\sqrt{6}`$ and $`b_e^R/b_g^R1.79`$. Note that in fitting we have disregarded the three smallest masses $`N=16,32`$ and $`64`$ to minimize finite size effects. We have checked for (the remaining) finite size effects (not shown): The (negative) curvature in the data points is surprisingly weak and similar for linear chains and rings. It is slightly stronger for the radius of gyration than for the diameter which probes larger distances. While we cannot rule out that the asymptotic exponents of the ring chains are slightly different from their linear counterparts, for all practical purposes of relevance here we may conclude that neither the ring-closure nor the non-selfknottedness constraint are pertinent.

We are now in the position to rescale the effects of the persistence length for both linear chains and rings by estimating for the linear chain the number $`g_k`$ of correlated monomers along the chain and the associated Kuhn length $`k=lg_k`$ ($`l`$ being the measured mean length of the BFM bond). Rewriting $`R_e=b_eN^\nu =k(N/g_k)^\nu `$ yields $`g_k=(b_e/l)^{1/(1\nu )}`$ and $`k=l(b_e/l)^{1/(1\nu )}`$. Obviously this scaling-based definition of $`k`$ and $`g_k`$ is arbitrary to within prefactors of order one. The proposed rescaling works successfully for dilute linear chains and rings as shown in Fig. 4. Here we have plotted the reduced diameters $`u=R_e/k`$ versus the number of statistical segments $`v=N/g_k`$. A similar figure was obtained for the radius of gyration (not shown). Note that only a part of the linear chain configurations used to characterise the stiffness effects for dilute systems are included in the figure.

In Fig. 5 we show the bond-bond correlation function $`<\stackrel{}{e}_i\stackrel{}{e}_{i+n}>`$, where $`\stackrel{}{e}_i`$ denotes one of the bond vectors of monomer $`i`$ (say the “right” one in a given list). Only values for rings are included (the values for linear chains being identical for long enough chains). As it should, the bond-bond correlation functions for different persistence lengths collapse onto a single scaling curve, when plotted versus $`n/g_k`$ (not shown). Note that this scaling and the (supposed) exponential decay is sometimes preferred to define the number of correlated monomers $`g_k`$ and the persistence length $`k`$ rather than our definition based on the measured effective bond length $`b`$ and the well-known (and for rings confirmed) Flory exponent. However, the correlation function for dilute chains (both linear and rings) does certainly not decrease as a pure exponential (not shown). This is due to (non-universal) short range packing effects and (more importantly) to long range excluded volume correlations. In addition to this we prefer our method for statistical reasons.

Additional information about the local structure of the flexible and semi-flexible rings comes from the structure factor $`S(q)`$ which is of direct experimental relevance. The slopes of the structure factor in $`\mathrm{log}\mathrm{log}`$ coordinates define the differential fractal dimension $`d_f(q)=d\mathrm{log}(S(q))/d\mathrm{log}(q)`$. The general shape of $`S(q)`$ was discussed in ref. . We present here only $`d_f(q)`$ which contains all the information. It is equivalent in the limit of long chains ($`q0`$, $`qR_g1`$) to the inverse of the Flory exponent $`\nu `$. Fig. 6(a) shows $`d_f(q)`$ for dilute rings (thin symbols) of mass $`N=1024`$ plotted versus $`\delta r=2\pi /q`$. For large distances the rings are well described by the classical Guinier expansion $`S(q)N\left(1(R_gq)^2/3\right)`$ (not shown); hence $`d_f(qR_g0)0`$. For small distances $`\delta rl`$ one finds the usual spurious Bragg-peak of the structure factor  due to local packing effects giving rise to negative $`d_f`$-values. We note a weak $`\sigma `$-dependence due BFM related lattice effects: A slightly different set of bond vectors is preferred. This is in line with the fact that also the mean bond vector varies weakly with persistence length as shown in Tab. I. In between both limits we find a broad plateau for the flexible rings with $`d_f=1/\nu _01.7`$ (upper horizontal line) due to the excluded volume interactions. Semi-flexible rings show, as expected from linear chains, a shoulder at about $`d_f=1`$ (upper horizontal line) due to the local rigidity of the rings. Note that the curves for linear dilute chains (not included) are very similar. The only qualitative difference is the “hump” between the plateau and the Guinier regime. It is due partially to the ring closure as one can easily see by calculating the static structure factor for a Gaussian ring (solid line).

## IV Conformational properties of dense rings

### A Compact, but strongly overlapping rings

While dilute rings essentially behave like their linear counterparts, this becomes very different for unconcatenated rings in the melt. This is shown in the dramatic decrease of the chain size of rings (full symbols) in Fig. 3 as compared with dilute reference rings (open symbols). Certainly, linear chain sizes also decrease with increasing density due to the screening of the excluded volume correlations , but to nowhere near this extent, as Fig. 4 illustrates. Moreover, the slopes of $`R_e`$ versus $`v=N/g_k`$ decrease strongly with persistence length. (See Tab. II.) For flexible rings ($`\sigma =0`$) the data points (for $`N=128`$ to $`N=1024`$) are fitted by an (effective) exponent $`\nu =0.4`$. For our stiffest rings we observe $`\nu (\sigma =3)1/3`$. This last result is indeed consistent with the compact LA scaling behaviour predicted for rings at high enough overlap $`p`$.

These results are also in agreement with the density distribution of a ring around its center of mass, shown for rings in Fig. 7. We see that for flexible rings (main figure) the overlap $`p`$ must be very small; nearly all monomers from neighbouring rings are expelled. From the Flory exponent $`\nu 0.4`$ measured above one expects the density inside the ring to decrease as $`\rho N^{0.2}`$. This is confirmed. In the inset we present the corresponding plot for semi-flexible rings ($`\sigma =3`$). Since the effective Flory exponent is $`\nu =1/3`$ we expect the density inside the ring to be independent of the ring size. The ring length independence of the density is observed for $`N\stackrel{>}{}128`$ for $`\sigma =2`$ (not shown) and $`N\stackrel{>}{}64`$ for $`\sigma =3`$. This supports the idea that the LA regime is reached earlier for stiffer rings. Though rings in this regime show compact scaling ($`\nu 1/3`$) the asymptotically constant density $`\rho `$ is fairly small. Thus the density of other rings in the correlation hole of a given ring is larger for stiff than for flexible rings (Fig. 7). This holds for the ring sizes studied; it does not exclude similar strong overlap behaviour for flexible, but much larger rings.

### B First evidences for additional length scale

We have to stress, however, that the above exponents are only effective exponents. The curves are strongly (negatively) curved as one can easily visualise by plotting $`R/N^{1/3}`$ versus $`N`$ (not shown). Alternatively, one can characterise this curvature via the differential Flory exponent $`\nu (N)`$ defined from the increase between chain length $`N`$ and $`2N`$ . This reveals (not shown) that $`\nu (N)`$ decreases continuously from $`\nu 1/2`$, i.e. nearly Gaussian behaviour, for smaller rings down to the slopes indicated in Fig. 3 for the largest masses we were able to simulate. In our previous study  we have attributed the observed curvature to classical finite-size effects which also appear for linear chains. That is, we have not attributed them to topological effects, but excluded volume interactions visible due to the finite number of blobs. If one admits this as the only physical origin of the curvature (excluding, e.g., additional length scales) it is indeed reasonable to attempt to obtain the asymptotic exponent by classical finite-size extrapolation method. In this method, the local slope $`\nu (N)`$ (obtained from the diameter and the radius of gyration) is plotted versus the reduced blob size $`\xi /R`$ where $`R`$ is itself given in a self-consistent manner by the asymptotic behaviour. This works generally well for linear polymers. Proceeding along these lines we obtained an asymptotic exponent of $`\nu 0.4`$ (which we now obtain directly after including $`N=1024`$). This value happened to coincide with the CD picture ($`\alpha =1`$ ) which made us perhaps more confident than we should have been (in ref.) of having characterised the asymptotic behaviour.

The excluded volume effects (and their screening) do certainly contribute to the general crossover scenario. This is shown below when we discuss the structure factor (Fig. 6). But a danger remains that we may have missed additional physics, in the form of an additional length scale (not included in the simple CD picture), which controls the behavior of molten rings.

Thus one of the key claims made in ref.  was that the only relevant length scale in dense rings is the chain size itself. This was shown in various scaling plots, e.g., of the reduced mean ring “area” $`|a|/R_g^2=const`$. The area $`a`$ is defined as a signed quantity (the component in that direction of the vector area of a ring) that vanishes for any configuration in which the ring exactly retraces its own steps. Qualitatively, one expects that a ring which is only very weakly threaded by the surrounding rings has a very small area. This should hold in particular while we approach the LA limit. The reduced area $`|a|/R_g^2`$ has been (log-linear) plotted in Fig. 8 versus ring mass $`N`$ for dilute rings (empty symbols) and rings in the melt (full symbols) of different flexibility. For (long enough) dilute rings the ratio is indeed chain length (and persistence length) independent. For the dense limit however, we now find evidence for (logarithmic) corrections to the expected CD scaling (plateau). The reduced area decreases systematically as a function of mass — this is in contrast to what was deduced from a (linear-linear) plot in ref. . Note that the ratio decreases also with respect to $`\sigma `$: stiffer rings are likely to get less threaded by other rings. This is consistent with the LA picture where stiffer (and hence larger) rings are forced to retrace their own steps in a network of fixed obstacles.

### C Failure of classical scaling analysis without additional length scale

More stringent tests for the CD picture are posed by the following two scaling analyses which try to allow for a varying persistence length under the assumption of no new additional length scale for topological interactions. They are presented in Fig. 4 and in the inset of Fig. 9.

In the first we replot the reduced ring size $`u=R_e/k`$ versus the number of statistical units $`v=N/g_k`$ as we did in Section III for dilute rings. The values of $`k`$ and $`g_k`$ used in the Fig. 4 for the dense linear chains and rings are the same as for the dilute systems . The difference to the behaviour of linear chains is striking: The ring data for different $`\sigma `$-lines diverges while the linear chain data clearly collapses (on the expected slope $`\nu =0.5`$). This is a physically unsound result; flexibility-dependent universality classes for rings are difficult to accept.

The second scaling test is the “classic” $`u=R(\sigma ,\varphi =0.5)/R_0`$ versus $`v=\varphi /\varphi ^{}N/R_0^3`$ mentioned in the Introduction . This is shown in the inset of Fig. 9. Both ring diameter (full symbols) and radius of gyration (empty symbols) at $`\varphi =0.5`$ have been included. As reference chain size $`R_0`$ we used the measured radius of gyration for a dilute ring of given $`\sigma `$. Again, the scaling attempt fails to account for data of more than one chain stiffness.

For the moment we may conclude that there is clear evidence for one or more additional length scales. At this point, we still do not know how this hypothetical length scale $`d_t`$ depends on ring and persistence lengths, nor do we know what physics it represents: however, since it arises for rings and not for linear chains, we can presume a topological origin.

### D Evidence for a chain length independent length $`d_t`$

Another striking effect which we are able to see due to the persistence length variation is shown in Fig. 5 for the bond-bond correlation function of dense rings. As before for dilute chains this correlation function becomes chain length independent for the large masses indicated in the figure. For flexible rings the correlation function drops down slightly below zero within three monomers and approaches then zero from below. When the persistence length is increased a most remarkable negative correlation becomes visible indicating that the polymer is likely to fold back after 10 monomers for ($`\sigma =3`$). Needless to say that the correlation function for dilute rings does not show anything faintly similar. The position and the depth of this anti-correlation dip increases with $`\sigma `$. We stress that the position and the shape of the dip are chain length independent. If this effect has something to do with the additional length scale $`d_t`$ mentioned above, as we believe, this is a piece of evidence for its chain length independence.

### E A new scaling scenario

This observation forms the basis for the next scaling proposal attempted in Fig. 9. We assume here that there is one additional, mass independent length scale $`d_t`$. Hence, the associated number $`g_t`$ of monomers between the topological obstacles is also mass independent, but depends on the local conformational properties. These are complicated as will be revealed below (see Fig. 6 and Fig. 10). However, as we have observed above (Fig. 3), short rings are reasonable approximated by Gaussian statistics and we may write $`g_t=g_k\left(d_t/k\right)^{1/\nu _1}`$, where $`\nu _1`$ is some effective exponent close to $`1/2`$ characterising the (messy) statistics at distances $`k\delta rd_t`$. We want to plot $`u=R/d_t`$ versus $`N/g_t`$ where $`R`$ denotes either the diameter (full symbols) or the radius of gyration (empty symbols). We still need to fix the persistence length dependence of $`d_t`$. For simplicity, we suppose that $`d_t`$ is only weakly affected by $`\sigma `$ and set arbitrarily $`d_t=1`$, i.e., we neglect any stiffness dependence of $`d_t`$ itself. Hence, $`g_t1/g_k`$ and $`v=Ng_k`$. This assumes that the effect of $`\sigma `$ is to increase $`R/d_t`$ (allowing the asymptotic regime to be accessed for smaller $`N`$) by increasing $`R`$ at (nearly) constant $`d_t`$. This idea is very much the opposite of what we tried in Fig. 4 where we had $`v=N/g_k`$ and stiffer chains with fewer statistical units were considered as being effectively “shorter”. As shown in Fig. 9 this simple new proposal is successful although a weak dependence of $`d_t`$ on $`\sigma `$ cannot be ruled out. Moreover, it is self-consistent: The local statistics is indeed well described by the Gaussian behaviour $`\nu _11/2`$. This might be interpreted as the $`\alpha 0`$ limit of the CD proposal. The data collapse over two orders of magnitude in $`v`$ justifies a posteriori the neglect of a stiffness dependence of $`d_t`$. At large distances data points for different persistence lengths fall together on one slope of $`\nu _2=1/3`$ which is consistent with the LA picture. Note the later crossover of the radius of gyration onto the $`\nu _2`$-slope. This might be related to the fact that $`R_g`$ probes smaller distances.

The above proposal may be in principle generalised to incorporate excluded volume effects on intermediate scales $`k\delta r\xi `$ where the statistics is governed by the exponent $`\nu _0=0.59`$ for dilute rings. Note that the strong dependence of $`\xi `$ on the persistence length is checked by the small difference between $`\nu _0`$ and $`\nu _1`$. (We plan to consider this problem in a subsequent study on density effects .) This offers an effective simplification for the molten chains ($`\varphi =0.5`$) of interest in this study: Both length scales $`\xi `$ and $`k`$ are of same order and we are not able to separate the effects anyway as we are going to show now.

### F Local conformational properties: Structure factor

So far we have considered mainly global properties like the ring diameter $`R_e`$ or the ring area. We wish now to characterise the local conformational properties by measuring the single chain structure factor $`S(q)`$ and the mean-square length $`R_n^2`$, both introduced in Sec. III, and the differential fractal dimensions $`d_f(q)`$ associated with both quantities. We will first consider the fractal dimension obtained from $`S(q)`$ as presented in Fig. 6 and then compare this in Sec. IV F below) with $`d_f`$ obtained from $`R_n^2`$ and shown in Fig. 10.

The differential fractal dimension for our longest ($`N=1024`$) rings in the melt ($`\varphi =0.5`$) is depicted in Fig. 6(a) and compared with their dilute counterparts. The Bragg peak at $`\delta rl`$ is much more pronounced than for the dilute chains (not fully shown). We note again small, but distinct $`\sigma `$-dependent packing effects. Not surprisingly, at very large distances the structure is again well described by the Guinier expansion (see section III) and $`d_f(q)`$ vanishes smoothly.

Obviously one wants to understand the behaviour between the (featureless and trivial) Guinier and the (non-universal) Bragg part. To stress this regime we have plotted in Fig. 6(b) the differential fractal dimension $`d_f(q)`$ versus $`\delta r=2\pi /q`$ chopping off distances $`\delta r<l`$ and the Guinier part. Data are for flexible ($`\sigma =0`$) and semi-flexible ($`\sigma =3`$) rings and linear chains in the melt. For small distances where $`d_f<1`$ the data for all $`d_f`$ are very similar. (Note the small $`\sigma `$-dependent packing effects mentioned above.) At $`d_f(\delta r4)=1`$ the semi-flexible systems branch off the much steeper line for flexible chains (top line). This applies also to the data for $`\sigma =1`$ and $`\sigma =2`$ (not shown). We stress that the difference between different $`\sigma `$ is gradual and that systems of flexible rings do not constitute a singular limit. Because of the small blob size (i.e., the very strong interactions with the surrounding rings) we are unable to separate rigidity and excluded volume effects: Semi-flexible rings do not show the “shoulder” at $`d_f1`$ we saw for dilute rings (dotted line in Fig. 6(a)).

At these small distances, smaller than the blob size $`\xi `$ , linear chains behave exactly like their ring counterparts of the same flexibility. This proves, as assumed above, that on small scales the $`\sigma `$-effects are the same for both architectures and justifies the use of the persistence length $`b`$ (and the associated values $`g_k`$ and $`k`$) obtained from linear chains. It also shows that it was natural to attempt in ref.  a finite-size scheme in terms of the correlation hole, at least when one assumes the CD picture to hold, i.e. $`R`$ being the only length scale.

However, the rescaling in Fig. 4 did not work for molten rings (in contrast to linear chains). This is due to effects caused by the ring closure and topology which intervene at larger distances $`\delta r\xi `$ (and in particularly at $`\delta rd_t`$): The fractal dimension $`d_f`$ for rings continues to rise while the linear chains become roughly Gaussian, i.e. $`d_f2`$ . The more flexible the rings, the more this increase becomes suppressed (see the flexible chains of mass $`N>256`$ in Fig. 6(b)). This gives the more rigid systems a chance to catch up (in $`d_f(q)`$) the more flexible ones — and this after having consumed fewer monomers on short scales.

The above discussion is only valid if the chains are actually large enough i.e. $`\delta rR_g`$ or $`S(q)N`$, to fall on the asymptotic ($`\sigma `$-dependent) curves. The closure constraint (rather than the topology) forces smaller rings (e.g., $`N=64`$ in Fig. 6(b))), to form rather dense globules of blobs.

For (asymptotically) long rings there are now two possible scenarios: Either all the $`\sigma `$-lines merge again at large enough distances or they become parallel. (We reject crossing of the $`d_f(\sigma )`$-lines as unphysical.) Unfortunately we are at present unable to decide unambiguously between these two. We believe it however more likely that all the lines eventually merge and that the asymptotic properties of ring polymers are independent of the persistence length $`b`$ . Hence, for large distances $`\delta r>\delta r^{}(\sigma )`$ the evolution of $`d_f(\delta r)`$ becomes again independent of $`\sigma `$. It is tempting in view of the scaling in Fig. 9 to set $`\delta r^{}=d_t`$ .

### G Local conformational properties: Contour distance $`R_n`$

We consider finally the average distance $`R_n=(\stackrel{}{R}_i\stackrel{}{R}_{i+n})^2^{1/2}`$ between the ends of a ring contour segment of length $`n`$. Similarly to the discussion above for $`S(q)`$ we define a differential fractal dimension $`1/d_f=d\mathrm{log}(R_n)/d\mathrm{log}(n)`$. Note that $`S(q)`$ and $`R_n^2`$ are not just simply Fourier transforms to each other. They contain different information: the $`S(q=2\pi /R_n)`$ monomers of the reference ring within a volume of radius $`R_n`$ around an arbitrary monomer of the same ring comprise also monomers far away the ring contour, i.e. much larger than $`n`$. This contribution is certainly small for linear chains (hence $`S(q)n`$ ), but gets more and more important while the rings become more compact (with increasing $`\sigma `$ and $`N`$).

We have plotted $`R_n`$ in the main part of Fig. 10 versus $`nN/2`$ for various ring lengths mass as indicated in the figure. Both flexible ($`\sigma =0`$) and semi-flexible ($`\sigma =3`$) are included. The lines of the stiffer rings are stronger curved. For $`nN/2`$ all curves collapse on a chain length independent (but $`\sigma `$ dependent) master curve. Obviously, in the limit of $`nN/2`$ the ring closure forces $`R_n`$ to level off towards $`R_e`$, i.e. $`1/d_f`$ has to vanish. The inset shows the differential fractal dimension $`d_f`$ for our longest rings $`N=1024`$ for three different persistence lengths. Indeed, $`d_f`$ for small $`n`$ increases with $`\sigma `$. For short flexible rings the fractal dimension takes more or less the Gaussian value. Consistent with Fig. 6 we are unable to separate clearly the different length scales and observe broad crossover lines. As mentioned above, $`d_f`$ has trivially to diverge for $`nN/2`$ and data points $`n>N/4`$ are influenced by this upper cut-off. However, we again see that stiffer chains show more compact scaling than flexible ones. Qualitatively, the $`\sigma =3`$-curve is even consistent with the $`d_f=4`$-window predicted for Gaussian LA .

In brief, the advantage to use stiff chains is due to an additional length scale $`d_tN^0`$. Flexible chains, very compact on short length scales (see the snapshot on the left of Fig. 2), “waste” there a large number $`g_t`$ of monomers. Systems with $`Ng_t`$ (that is, $`R_gd_t`$) feature only one characteristic size, their own size, and show CD scaling (with $`\alpha =0`$). Semi-flexible chains, however, using less monomers on short distances below $`d_t`$ can explore larger distances and become more compact in the scaling sense: They do this by having a lower ceiling on the local density $`\rho `$ of a single ring, thereby enhancing the topological interaction with their neighbours (thus increasing $`d_f`$).

## V Dynamics of rings in the melt

The differences in the ring statistics should strongly influence their dynamic behaviour. But as pointed out in ref. , there is some experimental evidence that the dynamics of rings are similar to their linear counterparts, at least up to the largest molecular masses that can readily be obtained. Our simulation data, presented below, confirms this.

We characterise the dynamics by measuring three different mean-square displacement functions describing the motion of monomers $`g_1(t)=[𝐑_n(t)𝐑_n(0)]^2`$ in the laboratory frame, the motion of monomers in the center-of-mass frame of a given ring $`g_2(t)=[𝐑_n(t)𝐑_{c.m.}(t)𝐑_n(0)+𝐑_{c.m.}(0)]^2`$, and the motion of the center of mass itself $`g_3(t)=[𝐑_{c.m.}(t)𝐑_{c.m.}(0)]^2`$. As shown in Fig.11, the mean square displacements for flexible rings collapse onto chain length independent master curves when the mean square displacements are rescaled by the radius of gyration $`R_g^2`$, and the time by the characteristic relaxation time $`R_g^2/D_N`$. Here $`D_N`$ is the diffusion coefficient (presented in Fig. 12) obtained from the asymptotic behaviour of the center of mass motion $`g_3(t)/t`$ (bold line of slope 1 on the right).

Closer inspection shows, however, that the collapse is not perfect. This is in agreement to what was observed by Brown and Szamel . In any case, this scaling is not born out for the semi-flexible ($`\sigma =3`$) systems of mass $`N=128`$ depicted in Fig. 11. This does not come as a surprise in view of what we have described above in section IV about the scaling of conformational properties. It is worth noting than in inspection of the differential slope of the motion of monomers $`g_1(t)`$ (not shown) shows (a small, but distinct) region with slope 0.32 instead of the classical Rouse-like anomalous diffusion exponent $`1/2`$.

In Fig.12 we present the self-diffusion constant of linear chains (empty symbols) and rings as a function of their size $`N`$. The circles correspond to isolated swollen chains. The diffusion constant is the same for linear chains and rings. It scales like $`D_N1/N`$. Our Monte Carlo simulations do not of course incorporate hydrodynamic interactions and the dynamics is expected to be Rouse-like . The squares correspond to flexible chains in the melt $`\varphi =0.5`$. It is important to note that rings are always faster than their linear counterpart of same mass. As shown in the figure, the diffusion coefficient are well fitted by (effective) power laws: $`D_NN^{1.22}`$ for rings and $`D_NN^{1.5}`$ for linear chains. As was emphasised in ref. both linear chains and rings scale with the size of their correlation hole $`D_NR^3`$. The diamonds in Fig.12 display the results of semi-flexible rings ($`\sigma =3`$) at melt density $`\varphi =0.5`$. The dependence of the diffusion constant for the larger ring sizes studied is stronger than for flexible chains and obeys the apparent relation $`D_NN^{1.68}`$. This is roughly consistent with the data of Brown and Szamel who found $`DN^{1.54}`$ for large flexible rings . Both sets of simulation data are likely to be affected by crossover effects.

This observation is in accord with theoretical calculations, which calculate the diffusion constant of rings via the motion of kinks along the contour. This diffusion of kinks along the molecules is also the dominant relaxation mechanism in the reptation of linear chains. In this sense, the dynamics of (more and more entangled) rings is the analog of reptation in melts of linear molecules. We do not find any signature of arm retraction in the motion of ring polymers. The latter would result in an exponential decrease of the diffusion with ring size like in star polymers .

In the (suspected) LA limit, the ring conformations should possess an hierarchical structure. Studying the motion of a single ring in a network of (explicitly) fixed obstacles, Obukov et al. suggested that the outer arms of a LA can rearrange much faster than the inner structure . This results in a broad range of relaxation times. We investigated this by monitoring the distribution of mean square displacements of monomers for flexible rings ($`N=256`$ and $`\sigma =0`$) and semi-flexible ones ($`N=256`$ and $`\sigma =3`$) after a time interval $`\mathrm{\Delta }t\mathrm{2.3\hspace{0.33em}10}^5`$ MCS. This corresponds to a time scale which is shorter than the diffusion time $`D_N/R_g^2`$ of the ring. Note that both curves correspond to roughly the same time period and the same mean value of the monomer displacement. The center of mass diffusion constant differs, however, by an order of magnitude. Hence, the major difference in the dynamic behaviour does not stem from a difference in the local dynamics (e.g. a slight decrease of the acceptance ratio of the Monte Carlo moves due to the additional bond angle potential), but reflects the interplay between conformations/topology and the dynamics. Notably, the monomer mean square displacements for flexible rings are Gaussian distributed, while the distribution of semi-flexible systems is non-Gaussian. This is consistent with simulations of rings in a network of fixed obstacles .

From these different probes of the ring dynamics we conclude that the dynamics for flexible and semi-flexible chains are qualitatively different, at least for the chain lengths we were able to probe. There appears to be clear evidence for the occurrence of a second length and time scale for our semi-flexible chains (which have $`Rd_t`$), but not for our flexible ones (which have $`Rd_t`$). Qualitatively we conclude again that stiffer rings are closer to the LA limit than their flexible counterparts. However, even for the largest ring size and stiffness our data are still affected by the small number of arms and we expect pronounced finite size effects to the asymptotic behaviour for large rings in the melt. An investigation of the dynamics of even larger rings ($`N>256`$) is unfortunately beyond our computational facilities at present.

## VI Conclusions

In summary, we have presented extensive Monte Carlo simulations of semi-dilute solutions and melts of flexible and semi-flexible ring polymers. The rings are neither knotted with themselves nor concatenated with each other.

In order to have a reference with systems where the non-linkage constraint does not play a rôle we have briefly considered dilute solutions of rings. They appear to be extremely similar to their linear counterparts, both with respect to statical and dynamical properties. The (remaining) topological unknottedness constraint seems not to be pertinent , at least not for the chains sizes ($`N=1024`$) we have considered here. The ring extension scales like $`RN^\nu `$ with $`\nu 0.59`$. This was also made evident from the study of the differential fractal dimension $`d_f(q)`$ obtained from the static structure factor $`S(q)`$. Dilute rings do not differ from linear chains with regard to the influence of finite persistence length (at least for large enough rings). The dynamics is Rouse-like $`D_NN^1`$, because our Monte Carlo simulations ignore hydrodynamical interactions (“free draining limit”). In short, from the practical point of view topology is irrelevant.

This is dramatically different in the high density limit ($`\varphi =0.5`$) with strongly overlapping entangled rings where topological constraints tend to squeeze the rings into relatively compact objects. We have varied the stiffness of the rings so as to tune the overlap between different rings. Due to the rather compact structure of the molecules in the melt, increasing the stiffness is much more efficient than increasing the ring size. Essentially, stiffer chains “waste” less monomers on short distances and have more monomers left to meander through the topological constraints imposed by neighbouring rings. Indeed the effective Flory exponent $`\nu (N)`$ obtained from the high chain length behaviour of chain diameter and radius of gyration shows a strong effect with regard to the persistence length, decreasing from $`\nu 0.4`$ for flexible chains ($`\sigma =0`$) to $`\nu 1/3`$ for our stiffest systems ($`\sigma =3`$). Chain stiffness allows a reduction in $`\nu `$ to more “compact” values by increasing (at a given $`\nu `$) the overlap parameter $`pb^3N^{3\nu 1}`$.

Rings with topological constraints do not follow the classical one parameter scaling with $`\varphi /\varphi ^{}`$ for linear chains where the size of the (dilute) chain of mass $`N`$ and stiffness $`\sigma `$ sets the only relevant length scale . This is in disagreement to the fundamental assumption of the CD picture. In order to scale the chain length $`R=R(N,\sigma )`$ we were forced to assume an additional chain length independent length scale $`d_tg_t^{\nu _1}`$. Supposing a weak $`\sigma `$-dependence of $`d_t`$ and choosing $`\nu _1`$ self-consistently this yields a satisfactory data collapse and $`\nu _11/2`$ as demonstrated in Fig. 9. For small chains, $`Rd_t`$, the topological interactions are weak. The rings resemble their linear counterparts and behave effectively like closed Gaussian chains of blobs. This regime is consistent with the $`\alpha 0`$ limit of the CD scenario, i.e. due to the non-linkage constraint the free energy of a reference ring increases only like $`\mathrm{log}(p)`$. Rings larger than $`d_t`$ appear to be governed by the topological interactions and are more compact (in the scaling sense of smaller $`\nu `$). They are well characterised by an effective Flory exponent $`\nu _2=1/3`$. This scaling scenario is broadly consistent with the concept of lattice animals (LA) within a network of topological obstacles created in a self-consistent manner by surrounding rings. These LA appear to be made of locally Gaussian chain pairs at short distances.

Our (more ambitious) discussion of the differential fractal dimension $`d_f`$ (obtained from the static structure factor $`S(q)`$ and/or the spatial distance $`R_n(n)`$ between a contour segment of length $`n`$) reveals very rich and broad crossover effects: excluded volume $`\xi `$ versus persistence length $`k`$, excluded volume versus ring closure, ring size $`R`$ versus topological length scale $`d_t`$. As shown in Fig. 6 and Fig. 10, it is not possible to separate the different length scales unambiguously and to disentangle their physics . In view of the (restricted) range of parameters ($`N1024,\sigma 3,\varphi =0.5`$) we are able to simulate, this does not come as a surprise. Much more surprising is the success and the simplicity of the scaling scenario of Fig. 9 for the global chain $`R`$ size described in the paragraph above. There, all the intricate short range physics was cast in one effective exponent $`\nu _1`$ for all chain and persistence lengths. It just turns out that the Gaussian value $`\nu _1=1/2`$ (i.e. $`\alpha 0`$) fits particular well the data. Similarly, while $`\nu _2=1/3`$ is certainly the asymptotic value, this does not exclude the possiblity of an intermediate window with $`\nu _2=1/4`$. Indeed the differential fractal dimensions for our largest and stiffest configurations clearly exceed $`d_f=3`$. This is in favour of an ultra-compact transient which should then eventually become evident also in the ring sizes for even larger chain lengths $`N`$ than we are at present able to simulate.

Additional evidence for the crossover to a strongly entangled regime characterised by an additional length scale $`d_t`$ comes from our brief investigation of the ring dynamics. The scaled time dependence of the monomer displacements differs from the master curve in the non-entangled regime, and the monomer displacements at times smaller than the relaxation time are non-Gaussian distributed as expected for LA . The diffusion constant for chains in the melt scales like $`D_NN^{1.22}`$ for flexible chains. This decrease to $`D_NN^{1.68}`$ for semi-flexible systems ($`\sigma =3`$). Again these exponents are presumably only effective values due to a broad crossover between unentangled and entangled regime. The similarity of the dynamics of melts of rings and linear chains suggests that our observations for rings might also be pertinent to the dynamics of linear chains. Indeed, it is tempting to relate the topological constraints which lead to the lattice animal behavior for rings to the entanglements in linear chains. While the topological interactions do not influence the static conformations of linear chains, however, rings offer the additional possibility to investigate the effect of topology in the static behavior.

In any case, our simulation data cover only the onset of LA behaviour and our estimates for the scaling functions of the conformational statistics and the dynamics are likely to be subjected to corrections due to the very small number of arms. In future we plan to corroborate further the discussion of the dynamical properties (increasing the number of statistical segments) and to investigate the static and dynamical scaling properties with regard to the monomer density $`\varphi `$ .

### Acknowledgement

M.M. has benefitted from interesting discussion with W. Paul, K. Binder, and K.S. Schweizer. He thanks EPCC for very kind hospitality and financial support during his stay as a TRACS visitor and J.-C. Desplat for visualisations of the ring conformations (Fig. 2). A generous grant of CPU time on the CRAY T3E computers at the EPCC in Edinburgh and the HLR Stuttgart as well as partial financial support by the DFG under grant Bi314-17 are gratefully acknowledged. J.P.W. acknowledges stimulating discussions with S.P. Obukov which triggered this study. Moreover he is indebted to him for Russian driving lessons in California. Finally he would like to thank C. Gay and J.-L. Barrat for detailed comments concerning the topological constraints.