# Equilibrium size of large ring molecules

## 1 Introduction

The effects of topology on the equilibrium properties of polymer systems is important both experimentally and theoretically to the understanding of polymeric materials. Many experimental systems, for example as polymer networks, possess non-trivial topology. Furthermore DNA is often in the form of a ring and possesses a well defined and non-trivial topology. This fact has important biological implications. Topological effects arise because a polymer chain cannot cross itself and is therefore confined to a fixed topological class that depends on its initial configuration. However the effects of topology are, in theory, very hard to understand. The simplest example is that of the ring polymer. Even when it is in the state of a “trivial” knot, that is the same topological class as a circle, its statistical properties have not as yet been well understood. This is because there are an infinite number of invariants that characterize a knot and so evaluating, or even writing down, the partition function is a daunting task. Questions about this system, such as how radius of gyration $`R_g`$ scales with chain length $`N`$, have not been answered with any certainty. The effects of topology on the size of a simple ring has been conjectured to give the same scaling exponent $`R_gN^\nu `$, as excluded volume chains. It is not clear that $`\nu `$ should be identical to that of the self avoiding chain. Topological effects may induce effective power law interactions between monomers in the ring. In this paper, we wish to analyze how topology alters the fractal dimension of a polymer ring.

To simulate polymers, lattice models have often been employed because in many circumstances they are more efficient and easier to implement than off-lattice models. However a large class of lattice models with local dynamics have been proven to be strongly non-ergodicsokal. Even if an ergodic model is usedquake some of the subtle effects of topology that we wish to examine here can be masked by this kind of model. To avoid segments crossing, which would violate topology, lattice models add in a hard core repulsion. This makes analysis of the results difficult because this repulsive potential must also be taken into account. The same can be said for many off-lattice models that include repulsive potentials between the monomers of the ring. Again this has the problem of masking delicate topological effects making results difficult to interpret.

Therefore it would seem worthwhile to explore an off-lattice model whose interactions are purely topological. The idea is to isolate topological effects to gain some understanding as to how they effect statistical properties.

To achieve this goal we explore topological effects numerically using an efficient off-lattice algorithm which has no excluded volume. The chain is a phantom chain, except that it is not allowed to cross itself and therefore can explore only one topological class. As mentioned above, this differs from other work in this area where excluded volume was also present. An efficient long range algorithm is developed that allows the exploration of rings up to $`2048`$ links. In addition, the chain is more flexible than chains on a cubic lattice which as we will see is important in light of the results that were obtained.

What was found is rather surprising. We did find that phantom ring polymers confined to the “trivial knot” are swollen with respect to phantom linear chains. But even with these very flexible chains, the effect of topology is rather weak, and rings must be longer than $`500`$ links before the scaling exponent $`\nu `$ appears to reach that of a self avoiding walk (SAW).

## 2 The Model

The model is illustrated in figure 1. A chain in three dimensions of $`N`$ links, all of equal length, is constructed so as to have the topology of a simple ring. All configurations are of equal energy, however moves must not be allowed to alter the topological class. That is, the chain is not allowed to cross itself.

To investigate the dynamics of small chains, moves were chosen that were local, involving rotations of two adjacent links. Moves of this type are illustrated in figure 1, where links initially adjacent to A are moved to locations shown by the dashed lines by B. The relaxation time with such moves is slightly greater than $`N^2`$ which is prohibitively long for chain lengths in the thousands. Therefore a long range algorithm was used instead.

A long range move is illustrated in the same figure. It is a variation of a pivot algorithm. To construct a new conformation, the algorithm attempts to rotate the chain about some axis. Two points C and D are chosen randomly from the backbone of the chain and the line going through C and D is defined to be the axis of rotation. An angle is chosen randomly between $`90`$ and $`90`$ degrees and all chain segments between C and D are rigidly rotated about this axis. If the ring is found to cross itself as chain segments are being rotated, the move is rejected, otherwise it is accepted.

These long range moves are repeated millions of times and the radius of gyration was averaged.

The simulation was tested by starting two rings in a locked configuration and checking to see that they never became unlocked. This test was performed for over $`10^8`$ cycles and always remained locked. The simulation was further tested by taking a long ring of length 512, after it had moved many million cycles, and turning on a repulsive coulomb potential. It was always found that the ring would swell up into what could clearly be seen as being a circle, in other words a trivial knot. This contrasted with what happened when a deliberately knotted ring was swollen. There the final configuration was not circular.

The simulation was checked by allowing the ring to cross itself by turning off the checking algorithm. In such a case it is easy to show that $`R_g^2=N/4`$, when $`N>>1`$. The results found agreed with this value within statistical error. With the crossing constraint enforced, the radii of gyration were always larger than this value.

## 3 Results

The radius of gyration defined as

$$R_g^2\frac{2}{N}\underset{i=0}{\overset{N/21}{}}|𝐫_{i+N/2}𝐫_i|^2$$
(1)   
was examined by averaging over millions of iterations. Here $`𝐫_𝐢`$ is the vector position of the ith monomer, and N is the total number of links in the ring.

Figure 2 shows the $`R_g^2`$ as a function of chain length. The best fit to this line gives an exponent of $`1.11\pm 0.03`$. However the best fit for the last two data points at $`N=1024`$ and $`N=2048`$ is an exponent of $`1.17`$ close to the result $`1.175`$ found for an SAW in three dimensions. Because this only involves two data points, the up turn is not statistically significant so we now further analyze this possibility by probing the internal structure of the rings.

The self similarity of these rings was examined by means of the correlation function

$$g(s)\frac{1}{Ns}\underset{i=0}{\overset{Ns1}{}}|𝐫_{i+s}𝐫_i|^2$$
(2)   
Figure 3 examines how this scales with chain length by writing $`g(s)`$ in the scaling form

$$g(s)=N^\nu f_N(2s/N)$$
(3)   
The function $`f_N(x)`$ should become independent of $`N`$ for large enough $`N`$. In fig 3, we plot $`f_N(x)g(s)/N^\nu `$ as a function of $`x2s/N`$. This is done for three different chain lengths, $`N=`$ $`512`$, $`1024`$, and $`2048`$. $`\nu `$ was chosen to be $`1.17`$. Note that only the two longest chain lengths overlap. In order to get the $`512`$ link ring to overlap with $`N=2048`$ , a smaller value, $`\nu =1.11`$ must be chosen. This suggests that the rings of length $`512`$ are not long enough to be in the asymptotic scaling regime.

## 4 Discussion

The results above confirm the prediction that $`\nu `$ for a polymer ring in a trivial knot, is swollen compared to an ideal chain. What is surprising is that the length of chain needed to clearly see its asymptotic fractal dimension are in the thousands of links. This contrasts with a self avoiding walk, where $`\nu `$ can be calculated from chain lengths in the teens to quite high accuracy.

Fairly compelling arguments have been given to why $`\nu _{ring}`$ for a trivial ring should be greater than or equal to $`\nu _{SAW}`$ for a linear SAW. It is still an open question as to whether $`\nu _{ring}`$ is actually greater than $`\nu _{SAW}`$. There is no answer to this that is available at present. However if the ring is trapped between to parallel plates, then this is amenable to a fairly convincing analytical argument. It is argued here that when the separation between the plates is very small, so that the walk is almost two-dimensional, that the exponent must be less than or equal to $`\nu `$ for an SAW in two dimensions. This taken with the argument that $`\nu _{ring}\nu _{SAW}`$, which carries over to this case also, we can conclude that $`\nu _{ring}=\nu _{SAW}`$.

If the separation between the two walls is much less than the length of a link, then the chain is essentially confined to a two dimensional x-y plane. However besides the coordinates of the monomers we also must keep track, in a crossing between two links, of which one lies on top. If we want the ring to preserve the initial topology of a trivial knot, some configurations where the chain crosses itself in the x-y plane must be excluded. Essentially the only configurations that are allowed are those of a flattened trivial knot. Therefore the phase-space of all configurations are the coordinates in the x-y plane, and the type of crossing of which there are two possibilities.

If in addition to the topological constraint, we introduce a fictitious repulsive potential between links in the chain, it seems highly plausible that this can only increase the average radius of gyration of this system. In the limit of complete excluded volume, no crossing is allowed, and this system is identical to the usual self avoiding ring. This is because complete excluded volume implies that there is no crossing allowed at all, and this by itself enforces the topological constraint. Therefore the radius of gyration of the ring without the repulsive potential should be less than or equal to that of a two dimensional SAW.

In three dimensions the numerical results presented here are consistent with an exponent less than or equal to that of an SAW. However one cannot exclude the possibility that at even longer chain lengths, a ring becomes more swollen than a linear SAW. Until a better theoretical understanding of knots has been achieved, it is not possible to exclude this possibility.

It is surprising that scaling behavior has not yet reached asymptotic behavior for chains of length $`512`$ as the model we have used allows for the formation of nontrivial knotted chains even for rings of $`6`$ monomers. However this work is consistent with enumeration of knot types for random phantom rings where the mean number steps needed to observe a nontrivial knot was of order hundreds of steps.

From an experimental view point, the rings analyzed here are large but easily achievable experimentally. A linear chain in good solvent could be synthesized with functional end-groups that chemically bond in good solvent. This should create a rings that are predominantly trivial knots. By changing solvent conditions to those of theta solvent for linear chains, one should observe that these rings are still swollen, albeit far less so than a linear chain in good solvent.

Ring polymers in other situations, are conjectured to have many interesting properties. For example, a melt of rings, and this is the subject of active investigation. It might be useful to apply the model described here, to these other systems.

## 5 Acknowledgements

This work is supported by NSF grant number DMR-9419362 and acknowledgment is made to the Donors of the Petroleum Research Fund, administered by the American Chemical Society for partial support of this research.