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# On High-Energy Behavior of Cross Sections in Theories with Large Extra Dimensions

## Abstract

We discuss the high-energy behavior of cross sections in theories with large extra dimensions and low-scale quantum gravity, addressing two particular issues: (i) the tension of the D-branes, and (ii) bounds on the cross section and their relation to approximations in the mode sum over Kaluza-Klein-graviton exchanges.

Theories with large compact dimensions and an associated low scale characterizing quantum gravity have been the subject of intensive study recently (a few references are given in ). In Ref.  we analyzed some of the phenomenological aspects of such theories, including the high-energy behavior of cross sections for reactions involving graviton exchange. Assuming that there are $`n`$ large compact dimensions of size $`r_n`$, and denoting the scale of quantum gravity in the $`(4+n)`$-dimensional space as $`M_{4+n}\stackrel{>}{}M_s`$ (where $`M_s`$ is the string mass scale in an underlying string theory), one finds the relation

$$M_{Pl}^2=(r_n)^n(M_{4+n})^{2+n}$$
(1)
where $`M_{Pl}=G_N^{1/2}=1.2\times 10^{19}`$ GeV is the Planck mass, obtained from the measured Newton constant $`G_N`$. Thus, in these theories, the largeness of $`M_{Pl}`$ is seen to be a consequence of the largeness of the compact dimensions, and the underlying short-distance Planck mass, $`M_{4+n}`$ can actually be much less than $`M_{Pl}`$. At large distances $`r>>r_n`$ (here for simplicity we assume the same compactification radius for all of the $`n`$ compact dimensions), the gravitational force $`Fr^2`$, while for $`r<<r_n`$, this changes to $`Fr^{(2+n)}`$. It is a striking fact that there is a vast extrapolation of 31 orders of magnitude between the smallest scale of 0.2 mm to which Newton’s law has been tested  and the scale that has conventionally been regarded as being characteristic of quantum gravity, namely the Planck length, $`L_{Pl}=1/M_{Pl}10^{33}`$ cm, and it is quite possible that new phenomena could occur in these 31 decades that would significantly modify the nature of gravity. It therefore instructive to explore how drastically one can change the conventional scenario in which both gauge and gravitational interactions occur in four-dimensional spacetime up to energies comparable to the Planck mass. String/brane theory involves extra dimensions and, especially in Type I constructions, naturally lead to models in which open strings end on Dp branes , so that the standard-model gauge and matter fields propagate on these branes, while closed strings (gravitons) propagate in the “bulk” between the branes.

In these types of models, gravitational scattering is strongly altered by the presence of a large number of Kaluza-Klein (KK) modes for the graviton. To an observer in the usual four-dimensional space, the massless graviton is replaced by a set of KK modes, of which the lowest is the massless graviton itself, but the others are massive. The mass of a KK graviton mode is

$$\mu _{\mathrm{}_1,\mathrm{},\mathrm{}_n}=\left(\underset{i=1}{\overset{n}{}}\mathrm{}_i^2\right)^{1/2}r_n^1$$
(2)
where the mode numbers are $`\mathrm{}_j`$ and the indices $`j=1,2,..n`$ run over the number of extra compactified dimensions. The couplings of all of these KK states to other particles have the same Lorentz structure as the coupling of the graviton. These KK-graviton modes have the effect of changing the strength of gravitational scattering from its naive value $`G_N=M_{Pl}^2`$ to a level not much less than regular weak strength, if the underlying quantum gravity scale $`M_s`$ is not much greater than the electroweak scale, $`M_{ew}250`$ GeV. This can be seen because in calculating the rate for such a scattering process, one multiplies the squared coupling $`M_{Pl}^2`$ by a factor incorporating the multiplicity of the various KK modes that are exchanged. Since this factor is $`(s^{1/2}r_n)^n`$, where $`s^{1/2}`$ is the center-of-mass energy, when one substitutes the expression for $`r_n`$ from eq. (1), the factor of $`1/M_{Pl}^2`$ is exactly cancelled, and the final product is $`s^{n/2}/M_{4+n}^{n+2}`$. Thus, from a four-dimensional viewpoint, although the KK-gravitons are coupled extremely weakly, this is compensated by their very large multiplicity, so that their net effect involves in the denominator a mass scale of order $`M_{4+n}`$ .

In Ref.  we carried out estimates of the effects of the exchange of the KK-graviton modes to $`22`$ gravitational scattering processes. In the theories of interest here, as $`\sqrt{s}`$ becomes comparable to the string scale, $`M_s`$, one changes over from a field theory (with effects of D-branes included) to a fully stringlike picture, so that $`M_s`$ serves as an upper cutoff to the low-energy effective field theory in which the calculation is performed. Accordingly, one imposes an upper cutoff

$$\mathrm{}_i<\mathrm{}_{max}=M_sr_n$$
(3)
on the sums over KK modes, which thus run over the range

$$\mathrm{}_i=0,\pm 1,\mathrm{},\pm \mathrm{}_{max}\mathrm{for}i=1,\mathrm{},n$$
(4)
The value of $`\mathrm{}_{max}=M_sr_n`$ is very large; for example, for $`n=2`$, for $`M_s30`$ TeV, one has $`\mathrm{}_{max}=M_sr_24\times 10^{14}`$.

In  we studied several approaches to estimating the high-energy behavior of the 2-2 gravitational scattering cross section and chose an eikonal approximation that automatically produced a unitary result for this cross section. Our result was (see eq. (2.35) in Ref. )

$$\sigma (s)=\frac{4\pi s}{M_{4+n}^4}$$
(5)
where $`s`$ is the center of mass energy squared. It was emphasized that because of the universal nature of the gravitational coupling, this applies to any 2-2 scattering process, independent of particle type.

One application of this result is to ultra-high energy (UHE) neutrinos with energies ranging from $`10^{15}`$ eV to $`10^{20}`$ eV and beyond. Neutrinos in these energy regions can be produced in several ways, including (i) from active galactic nuclei; (ii) as decay products of the pions produced by the reaction $`p+\gamma _{CMB}N+\pi `$, where $`\gamma _{CMB}`$ denotes a photon in the cosmic microwave background radiation; (iii) via analogous reactions in which the protons scatter off of the radiation field of a source such as a gamma-ray burster; and (iv) via decays of Z bosons produced resonantly from antineutrinos scattering on relic neutrinos . From our estimates, in conjunction with standard-model calculations of ultra-high energy $`\nu p`$ and $`\overline{\nu }p`$ total scattering cross sections , we concluded that in theories with large compactification radii and low-scale quantum gravity, it is possible for gravitational scattering to make a non-negligible contribution to these cross sections. This could also affect the opacity of the earth to ultra-high energy neutrinos. Indeed, from standard-model calculations, it is known that at energies $`E\stackrel{>}{}10^{15}`$ eV, the interaction length for (anti)neutrinos is smaller than the diameter of the earth, and for $`E\stackrel{>}{}10^{18}`$ eV, the earth is opaque to (anti)neutrinos , so that the highest-energy (anti)neutrinos would be expected to arrive at a detector from the upward hemisphere, while those coming upward and thus traversing more of the earth are commensurately more highly absorbed enroute. If, indeed, new gravitational contributions to ultra-high energy $`\nu p`$ and $`\overline{\nu }p`$ scattering are significant, this would be important for currently operating large detectors like AMANDA and BAIKAL, and the next-generation detectors like AUGER, NESTOR, ANTARES, ICECUBE, etc. .

It is of continuing interest to investigate further what predictions an assumed underlying string theory of quantum gravity could make concerning models having extra dimensions whose compactification radii are large. Unfortunately, at the present stage of understanding, one cannot derive the compactification process ab initio or reliably calculate the compactification radii. Another property is the tension of the Dp branes  that serve as the $`p`$-dimensional spaces, forming $`(p+1)`$-dimensional world-volumes, in which the standard-model fields propagate, while gravitons propagate in the higher-dimensional “bulk” extending outside of these Dp branes. This tension (more precisely, energy per unit $`p`$-dimensional spatial volume of the D-brane) $`\tau _p`$ is given by

$$\tau _p=\frac{1}{g_s(2\pi )^p(\alpha ^{})^{(p+1)/2}}$$
(6)
where $`\alpha ^{}=M_s^^2`$ is the Regge slope, which sets the scale of the string mass $`M_s`$ and is related to the string tension $`T`$ according to $`T=1/(2\pi \alpha ^{})`$. Because of the inverse dependence on the string coupling $`g_s`$, the D-brane tension, where one can calculate it reliably using perturbative string theory (i.e., for small $`g_s`$), satisfies $`\tau _p>>(M_s)^{p+1}`$. More generally, since nonperturbative effects can be important, one expects that $`\tau _p`$ is at least of order $`(M_s)^{p+1}`$. In turn, this determines the rigidity of the D-branes; for large tension, recoil effects accompanying KK-graviton emission are negligibly small. It follows that KK-graviton recoil effects are negligible up to the energy $`EM_s`$ at which the low energy pointlike effective field theory methods used in phenomenological studies  cease to apply and must be supplanted by full string-theoretic calculations. Consequently, in most analyses , recoil effects are usually dropped. Indeed, even if one takes a moderately strong string coupling $`g_sO(1)`$, $`\tau _p`$ would still be of order $`(M_s)^{p+1}`$. In the exceptional case where one assumes that $`\tau _p<<(M_s)^{p+1}`$, the recoil effects would suppress KK-graviton emission and hence various cross sections involving these .

Our eikonal approximation used for calculating the KK-graviton 2-2 scattering cross section automatically yields a unitary result, and, indeed, this is one reason that we relied upon this method for our estimate . As we noted in , the Froissart bound does not apply to KK-graviton scattering, because this bound assumes that the lightest particle exchanged in the $`t`$-channel has a finite mass, but this is not the case for reactions involving KK-graviton exchange, since the lowest-mass particle is the usual massless graviton. Indeed, if one lets $`m_{min}`$ be the lowest-mass particle exchanged in the $`t`$-channel and $`s_0`$ be a reference value for the center of mass energy squared, then the Froissart bound is

$$\sigma <\frac{4\pi }{m_{min}^2}\mathrm{ln}^2(s/s_0)$$
(7)
Thus, clearly, there is no bound if $`m_{min}=0`$, as is the case here.

Since the enhanced size of the cross sections involving KK-graviton exchange comes from the large multiplicity of KK modes, one might inquire what sort of result one would get by making an approximation in which one excludes the single massless graviton from the sum over KK modes. Recall that these modes are indexed by the $`n`$ additional KK momenta $`k_i=\mathrm{}_i/r_n`$ where $`\mathrm{}_i`$ and the graviton itself has $`\mathrm{}_i=0`$ for $`i=1,\mathrm{},n`$. In this case there is a finite, though very small, gap, $`m_{min}=1/r_n`$. In  we concentrated on the case $`n=2`$, so let us take this again here for definiteness; in this case, $`r_2=M_{Pl}/M_6^2`$. The Froissart bound then allows (neglecting the logs) $`\sigma =4\pi /m_{min}^2=4\pi r_2^2`$. This is exactly the value of our linearly rising cross section (5) at $`s=M_{Pl}^2`$. In this case there are just four KK-graviton exchanges that are characterized by the minimum nonzero mass, namely, for $`n=2`$, $`k_\lambda =(\pm 1/r_2,0),(0,\pm 1/r_2)`$. The strength of the partial wave amplitude $`s/M_{Pl}^2`$ of each exchange is order unity at this value $`s=M_{Pl}^2`$, thereby allowing for the saturation (up to logs) of the Froissart bound.

Consider next some lower energy $`s=M_{Pl}^2/N^2`$. The relevant KK modes are the $`O(N^2)`$ modes satisfying the condition $`k_1^2+k_2^2<(N/r_2)^2`$, i.e. the modes that have squared masses smaller than $`(N/r_n)^2`$. In this case the Froissart bound allows cross sections $`\sigma =4\pi r_2^2/N^2`$, again in agreement with our eq. (5). Furthermore the reduction of each individual exchange amplitude by the factor $`s/M_{Pl}^2=1/N^2`$ is compensated by the multiplicity of the relevant $`N^2`$ KK-graviton exchanges, so that again we have a total resultant amplitude of order unity and hence saturation of the Froissart bound . Of course for the true cross section, one cannot exclude the contribution of the massless graviton, which, as noted, means that the conventional Froissart bound does not apply to this cross section. In passing, we note that in Ref.  an attempt to analyze the high-energy behavior due to KK-graviton was made, and seemed to give a somewhat weaker growth of the cross section than in (5). We have traced the reason for this; instead of the $`t`$-dependence $`1/(t\mu _{\mathrm{}_1,\mathrm{}\mathrm{}_n}^2)`$ appropriate for the exchange of the KK-graviton mode with extra-dimensional momenta $`(\mathrm{}_1/r_n,\mathrm{},\mathrm{}_n/r_n)`$, Ref.  used an ad hoc exponential form. As the derivation of the Froissart bound clearly shows, it is the $`t`$-dependence (equivalently, the dependence on the impact parameter, $`b`$) that matters and not the initial $`s^\nu `$ behavior of the Born amplitude that, even for $`\nu 2`$, is removed by unitarization in systems with finite range interactions.

S. N. would like to thank the Israeli Academy for Fundamental Research for a grant. The research of R. S. was partially supported by the NSF grant PHY-97-22101. S. N. thanks the Yang Institute for Theoretical Physics at SUNY Stony Brook and the physics department, UCLA, and R. S. thanks Tel Aviv University for hospitality during visits when part of this paper was written.


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# Tube Models for Rubber-Elastic Systems

## I Introduction

Polymer networks  are the basic structural element of systems as different as tire rubber and gels and have a wide range of technical and biological applications. From a macroscopic point of view, rubber-like materials have very distinct visco- and thermoelastic properties.  They reversibly sustain elongations of up to 1000% with small strain elastic moduli which are four or five orders of magnitude smaller than for other solids. Maybe even more unusual are the thermoelastic properties discovered by Gough and Joule in the 19th century: when heated, a piece of rubber under a constant load contracts, and, conversely, heat is released during stretching. This implies that the stress induced by a deformation is mostly due to a decrease in entropy. The microscopic, statistical mechanical origin of this entropy change remained obscure until the discovery of polymeric molecules and their high degree of conformational flexibility in the 1930s. In a melt of identical chains polymers adopt random coil conformations  with mean-square end-to-end distances proportional to their length, $`\stackrel{}{r}^2N`$. A simple statistical mechanical argument, which only takes the connectivity of the chains into account, then suggests that flexible polymers react to forces on their ends as linear, entropic springs. The spring constant, $`k=\frac{3k_BT}{\stackrel{}{r}^2}`$, is proportional to the temperature. Treating a piece of rubber as a random network of non-interacting entropic springs (the phantom model ) qualitatively explains the observed behavior, including — to a first approximation — the shape of the measured stress-strain curves.

In spite of more than sixty years of growing qualitative understanding, a rigorous statistical mechanical treatment of polymer networks remains a challenge to the present day. Similar to spin glasses,  the main difficulty is the presence of quenched disorder over which thermodynamic variables need to be averaged. In the case of polymer networks,  the vulcanization process leads to a simultaneous quench of two different kinds of disorder: (i) a random connectivity due to the introduction of chemical crosslinks and (ii) a random topology due to the formation of closed loops and the mutual impenetrability of the polymer backbones. Since for instantaneous crosslinking monomer-monomer contacts and entanglements become quenched with a probability proportional to their occurrence in the melt, ensemble averages of static expectation values for the chain structure etc. are not affected by the vulcanization as long as the system remains in its state of preparation.

For a given connectivity the phantom model Hamiltonian for non-interacting polymer chains formally takes a simple quadratic form,  so that one can at least formulate theories which take the random connectivity of the networks fully into account.  The situation is less clear for entanglements or topological constraints, since they do not enter the Hamiltonian as such, but divide phase space into accessible and inaccessible regions. In simple cases, entanglements can be characterized by topological invariants from mathematical knot theory.  However, attempts to formulate topological theories of rubber elasticity (for references see ) encounter serious difficulties. Most theories therefore omit such a detailed description in favor of a mean-field ansatz where the different parts of the network are thought to move in a deformation-dependent elastic matrix which exerts restoring forces towards some rest positions. These restoring forces may be due to chemical crosslinks which localize random paths through the network in space  or to entanglements. The classical theories of rubber elasticity  assume that entanglements act only on the crosslinks or junction points, while the tube models  stress the importance of the topological constraints acting along the contour of strands exceeding a minimum “entanglement length”, $`N_e`$. Originally devised for polymer networks, the tube concept is particularly successful in explaining the extremely long relaxation times in non-crosslinked polymer melts as the result of a one-dimensional, curvilinear diffusion called reptation  of linear chains of length $`NN_e`$ within and finally out of their original tubes. Over the last decade computer simulations  and experiments  have finally also collected mounting evidence for the importance and correctness of the tube concept in the description of polymer networks.

More than thirty years after its introduction and in spite of its intuitivity and its success in providing a unified view on entangled polymer networks and melts,  there exists to date no complete solution of the Edwards tube model for polymer networks. Some of the open problems are apparent from a recent controversy on the interpretation of SANS data.  Such data constitute an important experimental test of the tube concept, since they contain information on the degree and deformation dependence of the confinement of the microscopic chain motion and therefore allow for a more detailed test of theories of rubber elasticity than rheological data.

On the theoretical side, the original approach of Warner and Edwards  used mathematically rather involved replica methods  to describe the localization of a long polymer chain in space due to crosslinking. The replica method allows for a very elegant, self-consistent introduction of constraining potentials, which confine individual polymer strands to random-walk like tubular regions in space while ensemble averages over all polymers remain identical to those of unconstrained chains. Later Heinrich and Straube  recalculated these results for a solely entangled system where they argued that there are qualitative differences between confinement due to entanglements and confinement due to crosslinking. In particular, they argued that the strength of the confining potential should vary affinely with the macroscopic strain, resulting in fluctuations perpendicular to the tube axis which vary only like the square root of the macroscopic strain.

Replica calculations provide limited insight into physical mechanism and make approximations which are difficult to control.  It is therefore interesting to note that Flory was able to solve the, in many respects similar, constrained-junction model  without using such methods. Recent refinements of the constrained-junction model such as the constrained-chain model  and the diffused-constrained model  have more or less converged to the (Heinrich and Straube) tube model, even though the term is not mentioned explicitly. Another variant of this model was recently solved by Rubinstein and Panyukov.  In particular, the authors illustrated how non-trivial, sub-affine deformations of the polymer strands result from an affinely deforming confining potential.

While tube models are usually formulated and discussed in real space, two other recent papers have pointed independently to considerable simplifications of the calculations in mode space. Read and McLeish  were able to rederive the Warner-Edwards result in a particularly simple and transparent manner by showing that a harmonic tube potential is diagonal in the Rouse modes of a linear chain. Complementary, one of the present authors introduced a general constrained mode model (CMM),  where confinement is modeled by deformation dependent linear forces coupled to (approximate) eigenmodes of the phantom network instead of a tube-like potential in real space. This model can easily be solved exactly and is particularly suited for the analysis of simulation data, where its parameters, the degrees of confinement for all considered modes, are directly measurable. Simulations of defect-free model polymer networks under strain analyzed in the framework of the CMM  provide evidence that it is indeed possible to predict macroscopic restoring forces and microscopic deformations from constrained fluctuation theories. In particular, the results support the choice of Flory,  Heinrich and Straube,  and Rubinstein and Panyukov  for the deformation dependence of the confining potential. In spite of this success, the CMM in its original form suffers from two important deficits: (i) due to the multitude of independent parameters it is completely useless for a comparison to experiment and (ii) apart from recovering the tube model on a scaling level, Ref.  remained fairly vague on the exact relation between the approximations made by the Edwards tube model and the CMM respectively.

In the present paper we show that the two models are, in fact, equivalent. The proof, presented in section II B is a generalization of the result by Read and McLeish to arbitrary connectivity. It provides the link between the considerations of Eichinger, Graessley,  Mark,  and others on the dynamics of (micro) phantom networks and the ideas of Edwards and Flory on the suppression of fluctuations due to entanglements. As a consequence, the CMM can be used to formally solve the Edwards tube model exactly, while in turn the independent parameters of the CMM are obtained as a function of a single parameter: the strength of the tube potential. Quite interestingly, it turns out that the entanglement contribution to the shear modulus depends on the connectivity of the network. In order to explore the consequences, we discuss in the second part the introduction of entanglement effects into the Warner-Edwards model, which represents the network as an ensemble of independent long paths comprising many strands. Besides recovering some results by Rubinstein and Panyukov for entanglement dominated systems, we also calculate the single chain structure factor for this controversial case.  Finally we propose a “double tube” model to describe systems where the confinement of the fluctuations due to crosslinks and due to entanglements is of similar importance and where both effects are treated within the same formalism.

## II Constrained fluctuations in networks of arbitrary connectivity

### A The Phantom Model

The Hamiltonian of the phantom model  is given by $`_{ph}=\frac{k}{2}_{i,j}^Mr_{ij}^2`$, where $`i,j`$ denotes a pair of nodes $`i,j1,\mathrm{},M`$ which are connected by a polymer chain acting as an entropic spring of strength $`k=\frac{3k_BT}{\stackrel{}{r}^2}`$, and $`\stackrel{}{r}_{ij}(t)=\stackrel{}{r}_i(t)\stackrel{}{r}_j(t)`$ the distance between them. In order to simplify the notation, we always assume that all elementary springs have the same strength $`k`$. The problem is most conveniently studied using periodic boundary conditions, which span the network over a fixed volume  and define the equilibrium position $`\stackrel{}{R}_i=(X_i,Y_i,Z_i)`$. A conformation of a network of harmonic springs can be analyzed in terms of either the bead positions $`\stackrel{}{r}_i(t)`$ or the deviations $`\stackrel{}{u}_i(t)`$ of the nodes from their equilibrium positions $`\stackrel{}{R}_i`$. In this representation, the Hamiltonian separates into two independent contributions from the equilibrium extensions of the springs and the fluctuations. For the following considerations it is useful to write fluctuations as a quadratic form.  Finally, we note that the problem separates in Cartesian coordinates $`\alpha =x,y,z`$ due to the linearity of the springs. In the following we simplify the notation by writing the equations only for one spatial dimension:

$$_{ph}=\frac{k}{2}\underset{i,j}{}X_{ij\alpha }^2+\frac{1}{2}\underset{¯}{u}^t\underset{¯}{\underset{¯}{K}}\underset{¯}{u}.$$
(1)
Here $`\underset{¯}{u}`$ denotes a $`M`$-dimensional vector with $`(\underset{¯}{u})_i(\stackrel{}{u}_i)_x`$. $`\underset{¯}{\underset{¯}{K}}`$ is the connectivity or Kirchhoff matrix whose diagonal elements $`(\underset{¯}{\underset{¯}{K}})_{ii}=f_ik`$ are given by the node’s functionality (e.g. a node which is part of a linear chain is connected to its two neighbors so that $`f_i=2`$ in contrast to a four-functional crosslink with $`f_i=4`$). The off-diagonal elements of the Kirchhoff matrix are given by $`(\underset{¯}{\underset{¯}{K}})_{ij}=k`$, if nodes $`i`$ and $`j`$ are connected and by $`(\underset{¯}{\underset{¯}{K}})_{ij}=0`$ otherwise. Furthermore, we have assumed that all network strands have the same length.

The fluctuations can be written as a sum over independent modes $`\underset{¯}{e}_p`$ which are the eigenvectors of the Kirchhoff matrix: $`\underset{¯}{\underset{¯}{K}}\underset{¯}{e}_p=k_p\underset{¯}{e}_p`$ where the $`\underset{¯}{e}_p`$ can be chosen to be orthonormal $`\underset{¯}{e}_p\underset{¯}{e}_p=\delta _{pp}`$. The transformation to the eigenvector representation $`\underset{¯}{\overset{~}{u}}=\underset{¯}{\underset{¯}{S}}\underset{¯}{u}`$ and back to the node representation $`\underset{¯}{u}=\underset{¯}{\underset{¯}{S}}^1\underset{¯}{\overset{~}{u}}`$ is mediated by a matrix $`\underset{¯}{\underset{¯}{S}}`$ whose column vectors correspond to the $`\underset{¯}{e}_p`$. By construction, $`\underset{¯}{\underset{¯}{S}}`$ is orthogonal with $`\underset{¯}{\underset{¯}{S}}^t=\underset{¯}{\underset{¯}{S}}^1`$. Furthermore, the Kirchhoff matrix is diagonal in the eigenvector representation $`(\underset{¯}{\underset{¯}{\overset{~}{K}}})_{pp}=(\underset{¯}{\underset{¯}{S}}^1\underset{¯}{\underset{¯}{K}}\underset{¯}{\underset{¯}{S}})_{pp}=k_p`$. The Hamiltonian then reduces to

$$_{ph}=\frac{k}{2}\underset{i,j}{}X_{ij}^2+\underset{p}{}\frac{k_p}{2}\stackrel{~}{u}_{p}^{}{}_{}{}^{2}.$$
(2)
Since the connectivity is the result of a random process, it is difficult to discuss the properties of the Kirchhoff matrix and the eigenmode spectrum in general.  The following simple argument  ignores these difficulties. The idea is to relate the mean square equilibrium distances $`X_{ij}^2`$ to the thermal fluctuations of the phantom network.

Consider the network strands before and after the formation of the network by end-linking. In the melt state, the typical mean square extension $`\stackrel{}{r}^2`$ is entirely due to thermal fluctuations, while $`\stackrel{}{r}=0`$. In the crosslinked state, the strands show reduced thermal fluctuations $`\stackrel{}{u}_{ij}^2`$ around quenched, non-vanishing mean extensions $`\stackrel{}{R}_{ij}^2`$. However, the ensemble average of the total extension $`\stackrel{}{R}_{ij}^2+\stackrel{}{u}_{ij}^2`$ is not affected by the end-linking procedure. The fluctuation contribution $`\stackrel{}{u}_{ij}^2`$ depends on the connectivity of the network and can be estimated using the equipartition theorem. The total thermal energy in the fluctuations, $`U_{fluc}`$, is given by $`\frac{3}{2}k_BT`$ times the number of modes and therefore $`U_{fluc}=\frac{3}{2}k_BTN_{nodes}=\frac{2}{f}\frac{3}{2}k_BTN_{strands}`$, where $`N_{nodes}`$ and $`N_{strands}`$ are the number of junction points and network strands, which are related by $`N_{strands}=\frac{f}{2}N_{nodes}`$ in an $`f`$-functional network. Equating the thermal energy per mode to $`\frac{k}{2}\stackrel{}{u}_{ij}^{}{}_{}{}^{2}`$, one obtains

$`\stackrel{}{u}_{ij}^2`$ $`=`$ $`{\displaystyle \frac{2}{f}}\stackrel{}{r}^2`$ (3)
$`\stackrel{}{R}_{ij}^2`$ $`=`$ $`\left(1{\displaystyle \frac{2}{f}}\right)\stackrel{}{r}^2.`$ (4)
Using these results, one can finally estimate the elastic properties of randomly cross- or endlinked phantom networks. Since the fluctuations are independent of size and shape of the network, they do not contribute to the elastic response. The equilibrium positions of the junction points, on the other hand, change affinely in the macroscopic strain. The elastic free energy density due to a volume-conserving, uni-axial elongation with $`\lambda _{||}=\lambda _{}^{1/2}=\lambda `$ is simply given by:

$`\mathrm{\Delta }F_{ph}(\lambda )`$ $`=`$ $`\left(\lambda ^2+{\displaystyle \frac{2}{\lambda }}3\right){\displaystyle \frac{R_{strand}^2}{\stackrel{}{r}^2}}\rho _{strand}`$ (5)
$`=`$ $`\left(\lambda ^2+{\displaystyle \frac{2}{\lambda }}3\right)\left(1{\displaystyle \frac{2}{f}}\right)\rho _{strand},`$ (6)
where $`\rho _{strand}`$ is the number density of elastically active strands. For incompressible materials such as rubber, the shear modulus is given by $`\frac{1}{3}`$ of the second derivative of the corresponding free energy density with respect to the strain parameter $`\lambda `$. In response to a finite strain, the system develops a normal tension $`\sigma _T`$:

$`G_{ph}`$ $`=`$ $`{\displaystyle \frac{1}{V}}{\displaystyle \frac{1}{3}}{\displaystyle \frac{d^2\mathrm{\Delta }F_{ph}(\lambda )}{d\lambda ^2}}|_{\lambda =1}`$ (7)
$`=`$ $`\left(1{\displaystyle \frac{2}{f}}\right)\rho _{strand}k_BT`$ (8)
$`\sigma _T`$ $`=`$ $`(\lambda ^2{\displaystyle \frac{1}{\lambda }})G_{ph}.`$ (9)
Experimentally observed stress-strain curves show deviations from eq 9. Usually the results are normalized to the classical prediction and plotted versus the inverse strain $`1/\lambda `$, since they often follow the semi-empirical Mooney-Rivlin form

$`{\displaystyle \frac{\sigma _T}{\lambda ^2\frac{1}{\lambda }}}`$ $``$ $`2C_1+{\displaystyle \frac{2C_2}{\lambda }}.`$ (10)
### B The Constraint Hamiltonian

Most theories introduce the entanglement effects as additional, single-node terms into the phantom model Hamiltonian, which constrain the movement of the monomers and junction points. The standard choice are anisotropic, harmonic springs of strength $`\stackrel{}{l}(\lambda )`$ between the nodes and points $`\stackrel{}{\xi }_i(\lambda )`$ which are fixed in space:

$$_{constr}=\underset{i}{}\frac{1}{2}\left(\stackrel{}{r}_i\stackrel{}{\xi }_i(\lambda )\right)^t\stackrel{}{l}(\lambda )\left(\stackrel{}{r}_i\stackrel{}{\xi }_i(\lambda )\right).$$
(11)
While all models assume that the tube position changes affinely with the macroscopic deformation,

$`\stackrel{}{\xi }_i(\lambda )=\stackrel{}{\lambda }\stackrel{}{\xi }_i(\lambda =1),`$ (12)
there are two different choices for the deformation dependence of the confining potential:

$`\stackrel{}{l}(\lambda )=\stackrel{}{l}(\lambda =1)`$ (13)
$`\stackrel{}{l}(\lambda )=\stackrel{}{\lambda }^2\stackrel{}{l}(\lambda =1).`$ (14)
Since this choice of $`_{constr}`$ leaves the different spatial dimensions uncoupled, we consider the problem again in one dimension and express $`_{constr}`$ in the eigenvector representation of the Kirchhoff matrix of the unconstrained network. Using $`\underset{¯}{v}(\lambda )=\underset{¯}{\xi _x}(\lambda )\underset{¯}{X}(\lambda )=\stackrel{}{\lambda }\underset{¯}{v}(\lambda =1)`$ one obtains

$$\begin{array}{cc}\hfill _{constr}& =\frac{l(\lambda )}{2}(\underset{¯}{u}\underset{¯}{v})^t(\underset{¯}{u}\underset{¯}{v})\hfill \\ & =\frac{l(\lambda )}{2}(\underset{¯}{\underset{¯}{S}}^1\underset{¯}{\overset{~}{u}}\underset{¯}{\underset{¯}{S}}^1\underset{¯}{\overset{~}{v}})^t(\underset{¯}{\underset{¯}{S}}^1\underset{¯}{\overset{~}{u}}\underset{¯}{\underset{¯}{S}}^1\underset{¯}{\overset{~}{v}})\hfill \\ & =\frac{l(\lambda )}{2}(\underset{¯}{\overset{~}{u}}\underset{¯}{\overset{~}{v}})^t\underset{¯}{\underset{¯}{S}}\underset{¯}{\underset{¯}{S}}^1(\underset{¯}{\overset{~}{u}}\underset{¯}{\overset{~}{v}})\hfill \\ & =\frac{l(\lambda )}{2}(\underset{¯}{\overset{~}{u}}\underset{¯}{\overset{~}{v}})^t(\underset{¯}{\overset{~}{u}}\underset{¯}{\overset{~}{v}})\hfill \\ & =\underset{p}{}\frac{l(\lambda )}{2}\left(\stackrel{~}{u}_p\stackrel{~}{v}_p\right)^2.\hfill \end{array}$$
(15)
Thus the introduction of the single node springs does not change the eigenvectors of the original Kirchhoff matrix. The derivation of eq 15, which is the Hamiltonian of the Constrained Mode Model (CMM),  is a central result of this work. It provides the link between the considerations of Eichinger,  Graessley,  Mark,  and others on the dynamics of (micro) phantom networks and the ideas of Edwards and Flory on the suppression of fluctuations due to entanglements.

### C Solution and Disorder Averages: The Constrained Mode Model (CMM)

Since the total Hamiltonian of the CMM

$$=_{ph}+_{constr}$$
(16)
is diagonal and quadratic in the modes, both the exact solution of the model for given $`\stackrel{}{v}_p`$ and the subsequent calculation of averages over the quenched Gaussian disorder in the $`\stackrel{}{v}_p`$ are extremely simple.  In the following we summarize the results and give general expressions for quantities of physical interest such as shear moduli, stress-strain relations, and microscopic deformations.

Consider an arbitrary mode $`\stackrel{}{u}_p`$ of the polymer network. Under the influence of the constraining potential, each Cartesian component $`\alpha `$ will fluctuate around a non-vanishing mean excitation $`\stackrel{}{U}_p`$ with

$$U_{p\alpha }(\lambda )=\frac{l_\alpha (\lambda )}{k_p+l_\alpha (\lambda )}v_{p\alpha }(\lambda ).$$
(17)
Using the notation $`\stackrel{}{\delta u}_p\stackrel{}{u}_p\stackrel{}{U}_p`$, the Hamiltonian for this mode reads

$$\begin{array}{cc}\hfill _{p\alpha }[v_{p\alpha }]=& \frac{k_p}{2}U_{p\alpha }^2(\lambda )+\frac{l_\alpha (\lambda )}{2}\left(U_{p\alpha }(\lambda )v_{p\alpha }(\lambda )\right)^2\hfill \\ & +\frac{l_\alpha (\lambda )+k_p}{2}\delta u_{p\alpha }^2.\hfill \end{array}$$
(18)
Expectation values are calculated by averaging over both the thermal and the static fluctuations, which are due to the quenched topological disorder:<sup>*</sup><sup>*</sup>*In order to simplify the notation, we use $`ll(\lambda =1)`$, $`v_{p\alpha }^2v_{p\alpha }^2(\lambda =1)`$ etc.

$$A_p(\lambda )=𝑑v_p𝑑\delta u_pA_p[v_p,\delta u_p]P(v_{p\alpha })P(\delta u_{p\alpha }).$$
(19)
Both distributions are Gaussian and their widths

$`\delta u_{p\alpha }^2(\lambda )`$ $`=`$ $`{\displaystyle \frac{k_BT}{k_p+l_\alpha (\lambda )}}`$ (20)
$`v_{p\alpha }^2`$ $`=`$ $`{\displaystyle \frac{k_p+l}{k_pl}}k_BT`$ (21)
follow from the Hamiltonian and the condition that the random introduction of topological constraints on the dynamics does not affect static expectation values in the state of preparation. In particular,

$$u_{p\alpha }^2=\delta u_{p\alpha }^2+U_{p\alpha }^2\frac{k_BT}{k_p}.$$
(22)
Eq 22 relates the strength $`l`$ of the confining potential to the width of $`P(v_{p\alpha })`$. The result, $`v_{p\alpha }^2=\frac{1}{\gamma _p}\frac{k_BT}{k_p}`$, $`U_{p\alpha }^2=\gamma _p\frac{k_BT}{k_p}`$, $`\delta u_{p\alpha }^2=(1\gamma _p)\frac{k_BT}{k_p}`$ can be expressed conveniently using a parameter

$$0\gamma _p\frac{l}{k_p+l}1,$$
(23)
which measures the degree of confinement of the modes. As a result, one obtains for the mean square static excitations:

$$U_{p\alpha }^2(\lambda )=\lambda _\alpha ^2\left(\frac{l_\alpha (\lambda )}{k_p+l_\alpha (\lambda )}\right)^2\frac{k_p+l}{l}\frac{k_BT}{k_p}.$$
(24)
Quantities of physical interest are typically sums over the eigenmodes of the Kirchhoff matrix. For example, the tube diameter is defined as the average width of the thermal fluctuations of the nodes:

$$d_{T\alpha }^2(\lambda )=\frac{1}{M}\underset{p}{}\delta u_{p\alpha }^2(\lambda ).$$
(25)
In particular,

$$d_{T\alpha }^2=\frac{k_BT}{Ml}\underset{p}{}\gamma _p.$$
(26)
More generally, distances between any two monomers $`r_{nm\alpha }=r_{n\alpha }r_{m\alpha }`$ in real space are given by

$$r_{nm\alpha }^2(\lambda )=\underset{p}{}u_{p\alpha }^2(\lambda )S_{p,nm}^2+\lambda _\alpha ^2R_{nm\alpha }^2.$$
(27)
For the discussion of the elastic properties of the different tube models it turns out to be useful to define the sum

$$g(\lambda )=\frac{k_BT}{V}\frac{1}{1\lambda _\alpha ^2}\underset{p}{}\left(\frac{u_{p\alpha }^2(\lambda )}{u_{p\alpha }^2}1\right).$$
(28)
Using eq 28 the confinement contribution to the normal tension  and the shear modulus can be written as

$`\sigma _T(\lambda )`$ $`=`$ $`{\displaystyle \frac{1}{V}}{\displaystyle \underset{p}{}}k_p\left(u_{p||}^2(\lambda )u_p^2(\lambda )\right)`$ (29)
$`=`$ $`\left(\lambda ^21\right)g(\lambda )+\left(1\lambda ^1\right)g(\lambda ^{1/2})`$ (30)
$`G_{constr}`$ $`=`$ $`g(1).`$ (31)
### D Model A: Deformation independent strength of the Confining Potential

In order to completely define the model, one needs to specify the deformation dependence of the confining potential. One plausible choice is

$$\stackrel{}{l}_A(\lambda )=\stackrel{}{l}_A(\lambda =1),$$
(32)
i.e. a confining potential whose strength is strain independent. The following discussion will make clear, that this choice leads to a situation which mathematically resembles the phantom model without constraints.

Using eq 32 the thermal fluctuations (and therefore also the tube diameter eq 26) are deformation independent and remain isotropic in strained systems. The mean excitations, on the other hand, vary affinely with the macroscopic strain. This leads to the following relation for the deformation dependence of the total excitation of the modes:

$$\frac{u_{p\alpha }^2(\lambda )}{u_{p\alpha }^2}=1+(\lambda _\alpha ^21)\frac{l_A}{k_p+l_A}.$$
(33)
Using eqs 28 to 31 one obtains via

$$g_A(\lambda )=\frac{k_BT}{V}\underset{p}{}\left(\frac{l_A}{k_p+l_A}\right).$$
(34)
a classical stress-strain relation:

$`\sigma _T(\lambda )`$ $`=`$ $`\left(\lambda ^2\lambda ^1\right)G_A`$ (35)
$`G_A`$ $`=`$ $`{\displaystyle \frac{k_BT}{V}}{\displaystyle \underset{p}{}}\gamma _p.`$ (36)
### E Model B: Affine deformation of the confining potential

The ansatz

$`\stackrel{}{l}_B(\lambda )=\stackrel{}{\lambda }^2\stackrel{}{l}_B(\lambda =1),`$ (37)
goes back to Ronca and Allegra  and was used by Flory, Heinrich and Straube  and Rubinstein and Panyukov.  It corresponds to affinely deforming cavities and leads to a more complex behavior including corrections to the classically predicted stress-strain behavior.

Using eq 37, the mean excitations of partially frozen modes as well as the thermal fluctuations, become deformation dependent. The total excitation of a mode is given by:

$$\frac{u_{p\alpha }^2(\lambda )}{u_{p\alpha }^2}=1+\left(\lambda _\alpha ^21\right)\left(\frac{l_B(\lambda )}{k_p+l_B(\lambda )}\right)^2.$$
(38)
Only in the limit of completely frozen modes, $`\gamma _p1`$, one finds affine deformations with $`u_{p\alpha }(\lambda )=\lambda _\alpha u_{p\alpha }(\lambda =1)`$.

Concerning the elastic properties, eq 28 takes the form

$$g_B(\lambda )=\frac{k_BT}{V}\underset{p}{}\left(\frac{l_B(\lambda )}{k_p+l_B(\lambda )}\right)^2.$$
(39)
while the the shear modulus can be written as

$`G_B`$ $`=`$ $`{\displaystyle \frac{k_BT}{V}}{\displaystyle \underset{p}{}}\gamma _p^2.`$ (40)
Note the different functional form of eqs 36 and 40. Since $`0\gamma 1`$, the contribution of confined modes to the elastic response is stronger in Model A than in Model B. Furthermore, within Model B the interplay between the network connectivity (represented by the eigenmode spectrum $`\{k_p\}`$ of the Kirchhoff matrix) and the confining potential $`l`$ is different for the shear modulus eq 40 and the tube diameter eq 26.

### F Model C: Simultaneous presence of both types of confinement

Finally, we can discuss a situation where confinement effects of type A and B are present simultaneously. Coupling each node to two extra springs $`l_A(\lambda )=l_A`$ and $`l_{B\alpha }(\lambda )=l_{B\alpha }/\lambda _\alpha ^2`$ leads to the following Hamiltonian in the eigenmode representation:

$$_p=\frac{k_p}{2}u_p^2+\frac{l_A}{2}(u_pv_{Ap}(\lambda ))^2+\frac{l_B(\lambda )}{2}(u_pv_{Bp}(\lambda ))^2.$$
(41)
Model A and Model B are recovered by setting $`l_A`$ respectively $`l_B`$ equal to zero. Furthermore we assume, that both types of confinement can be activated and deactivated independently. This requires,

$`v_{Ap}^2`$ $`=`$ $`{\displaystyle \frac{l_A+k_p}{l_Ak_p}}`$ (42)
$`v_{Bp}^2`$ $`=`$ $`{\displaystyle \frac{l_B+k_p}{l_Bk_p}}.`$ (43)
In the presence of both types of confinement, the mean excitation of the modes is given by

$`U_p^2(\lambda )`$ $`=`$ $`{\displaystyle \frac{l_A^2v_{Ap}^2(\lambda )+l_B^2(\lambda )v_{Bp}^2(\lambda )}{(l_A+l_B(\lambda )+k_p)^2}}`$ (44)
$`+`$ $`{\displaystyle \frac{2l_Al_B(\lambda )v_{Ap}v_{Bp}(\lambda )}{(l_A+l_B(\lambda )+k_p)^2}}`$ (45)
while the thermal fluctuations are reduced to

$$\delta u_p^2(\lambda )=\frac{k_BT}{l_A+l_B(\lambda )+k_p}.$$
(46)
Finally the condition that the simultaneous presence of both constraints does not affect ensemble averages in the state of preparation requires

$`v_{Ap}v_{Bp}`$ $`=`$ $`{\displaystyle \frac{k_BT}{k_p}}.`$ (47)
From eqs 42 to 47 one can calculate the deformation dependent total excitation of the modes:

$$\begin{array}{cc}\hfill \frac{u_p^2(\lambda )}{u_p^2}& =1+(\lambda ^21)(\frac{l_A}{k_p+l_A+\frac{l_B}{\lambda ^2}}\hfill \\ & +\frac{\frac{l_B}{\lambda ^2}\left(l_A+\frac{l_B}{\lambda ^2}\right)}{\left(k_p+l_A+\frac{l_B}{\lambda ^2}\right)^2}),\hfill \end{array}$$
(48)
so that

$$g_C(\lambda )=\frac{k_BT}{V}\underset{p}{}\left(\frac{l_A}{k_p+l_A+\frac{l_B}{\lambda ^2}}+\frac{\frac{l_B}{\lambda ^2}\left(l_A+\frac{l_B}{\lambda ^2}\right)}{\left(k_p+l_A+\frac{l_B}{\lambda ^2}\right)^2}\right).$$
(49)
In the present case, the shear modulus can be written as

$`G_C`$ $`=`$ $`{\displaystyle \frac{k_BT}{V}}{\displaystyle \underset{p}{}}{\displaystyle \frac{\gamma _{Ap}(1\gamma _{Bp})}{1\gamma _{Ap}\gamma _{Bp}}}`$ (51)
$`+{\displaystyle \frac{\gamma _{Bp}(1\gamma _{Ap})\left(\gamma _{Bp}(1\gamma _{Ap})+\gamma _{Ap}(1\gamma _{Bp})\right)}{\left(1\gamma _{Ap}\gamma _{Bp}\right)^2}}.`$
Note that the shear modulus is not simply the sum of the contributions from the A and B confinements. While eqs 36 and 40 are reproduced in the limits $`\gamma _{Bp}=0`$ and $`\gamma _{Ap}=0`$ respectively, eq 51 reflects the fact that a mode can never contribute more than $`k_BT`$ to the shear modulus. Thus, for $`\gamma _{Bp}=1`$ (respectively $`\gamma _{Ap}=1`$) the $`p`$th mode contributes this maximum amount independently of the value of $`\gamma _{Ap}`$ (respectively $`\gamma _{Bp}`$).

An important point, which holds for all three models, is that it is not possible to estimate the confinement contribution to the shear modulus from the knowledge of the absolute strength $`l_A,l_B`$ of the confining potentials alone. Required is rather the knowledge of the relative strengths $`\gamma _{Ap},\gamma _{Bp}`$ which in turn are functions of the network connectivity.

### G Discussion

It is not a priori clear, whether entanglement effects are more appropriately described by model A or model B. While model A has the benefit of simplicity, Ronca and Allegra proposed model B,  because it leads (on length scales beyond the tube diameter) to the conservation of intermolecular contacts under strain. Similar conclusions were drawn by Heinrich and Straube  and Rubinstein and Panyukov.  In the end, this problem will have to be resolved by a derivation of the tube model from more fundamental topological considerations. For the time being, an empirical approach seems to be the safest option. Fortunately, the evidence provided by experiments  and by simulations  points into the same direction.

Since details of the interpretation of the relevant experiments are still controversial (see Section III D 3), we concentrate on simulation results where the strain dependence of approximate eigenmodes of the phantom model was measured directly.  Figure 1 shows a comparison of data obtained for defect-free model polymer networks to the predictions eq 33 of Model A and eq 38 of Model B. The result is unanimous. We therefore believe eq 37 and Model B to be the appropriate choice for modeling confinement due to entanglements. The shear modulus of an entangled network should thus be given by:

$$G=G_{ph}+\frac{k_BT}{V}\underset{p}{}\gamma _p^2$$
(53)
where in contrast to Reference  the various $`\gamma _p`$ are no longer free parameters but depend through eq 23 on a single parameter: the strength $`l`$ of the confining potential, which is assumed to be homogeneous for all monomers. The difficulty of this formal solution of the generalized constrained fluctuation model for polymer networks is hidden in the use of the generalized Rouse modes of the phantom model, which are difficult to obtain for realistic connectivities.  A useful ansatz for end-linked networks is a separation into independent Flory-Einstein respectively Rouse modes for the crosslinks and network strands.  In fact, the simulation results presented in Figure 1 are based on such a decomposition.

For randomly crosslinked networks with a typically exponential strand length polydispersity, the separation into Flory-Einstein and single-chain Rouse modes ceases to be useful. In this case, we can think of two radically different strategies:

* To keep the network connectivity in the analysis. For example, there is no principle reason, why the methods presented by Sommer et al.  and Everaers  could not be combined, in order to investigate the strain dependence of constrained generalized Rouse modes in computer simulations. Note, however, that this completely destroys the self-averaging properties of the approximation used in Reference . Analytic progress in the evaluation of, for example, eq 40 for the entanglement contribution to the shear modulus requires information on the statistical properties of the eigenvalue spectra of networks generated by random crosslinking. To our knowledge, the only available results were obtained numerically by Shy and Eichinger.  Note, that model C is irrelevant, if one is able to carry out calculations with the proper network eigenmodes.
* To average out the connectivity effects in tube models for polymer networks.  In the second part of the paper, we will consider linear chains under the influence of two types of confinement: network connectivity and entanglements.

## III Tube Models

In SANS experiments of dense polymer melts, it is possible to measure single chain properties by deuterating part of the polymers. If such a system is first crosslinked into a network and subsequently subjected to a macroscopic strain, one can obtain information on the microscopic deformations of labeled random paths through the network. In order to interpret the results, they need to be compared to the predictions of theories of rubber elasticity. Unfortunately, for randomly crosslinked networks it is quite difficult to calculate the relevant structure factors even in the simplest cases.  Because the crosslink positions on different precursor chains should be uncorrelated, Warner and Edwards  had the idea to consider a tube model, where the crosslinking effect is “smeared out” along the chain. To model confinement due to crosslinking, they used (in our notation) Model A, since this ansatz reproduces the essential properties of phantom models (affine deformation of equilibrium positions and deformation independence of fluctuations). In contrast, Heinrich and Straube , and Rubinstein and Panyukov  treated confinement due to entanglements using Model B. Obviously, both effects are present simultaneously in polymer networks. In the following, we will develop the idea that in order to preserve the qualitatively different deformation dependence of the two types of confinement, they should be treated in a “double tube” model based on our Model C.

Before entering into a detailed discussion, we would like to point out a possible source of confusion related to the ambiguous use of the term “tube” in the literature (including the present paper). A real tube is a hollow, cylindrical object, suggesting that in the present context the term should be reserved for the confining potential described by quantities such as $`\stackrel{}{\xi }_i,\stackrel{}{v}_p,l`$. It is in this sense that we speak of an “affinely deforming tube”. However, a harmonic confining tube potential is a theoretical construction which is difficult to visualize. For example, in the continuum chain limit used below, the forces exerted “per monomer” become infinitely small corresponding to $`\stackrel{}{\xi }_i\mathrm{},l0`$. On the other hand, the term tube is often associated with the tube “contents”, i.e. the superposition of the accessible polymer configurations characterized via a locally smooth tube axis (the equilibrium positions $`\stackrel{}{U}_p`$) and a tube diameter $`d_T`$ (defined via the fluctuations $`\stackrel{}{\delta u}_p`$). This second definition refers to measurable quantities. Which kind of tube we are referring to, will hopefully always be clear from the context and the mathematical definition of the objects under discussion.

In the case of linear polymers, the phantom model reduces to the Rouse model with vanishing equilibrium positions $`\stackrel{}{R}_i0`$. As a consequence, there are no strain effects other than those caused by the confinement of thermal fluctuations. In particular, the “intrinsic” phantom modulus vanishes (see eq 5). Since the networks are modeled as superpositions of independent linear paths, we have to introduce confinement of type A in order to recover the phantom network shear modulus $`G_{ph}`$ in the absence of entanglements.

In the Rouse model the Kirchhoff matrix takes the simple tridiagonal form

$$\underset{¯}{\underset{¯}{K}}=k\left(\begin{array}{ccccccc}2& 1& 0& \mathrm{}& & & 0\\ 1& 2& 1& 0& \mathrm{}& \\ & & \mathrm{}& & & & \\ & & & & & & \\ & & & & & & \\ 0& \mathrm{}& & & & 1& 2\end{array}\right)$$
(54)
and, depending on the boundary conditions, is diagonalized by transforming to sin or cos modes using the transformation matrix

$$\underset{¯}{\underset{¯}{S}}=(S)_{jp}=\frac{1}{\sqrt{N}}\mathrm{exp}\left(\text{i}\pi \frac{jp}{N}\right).$$
(55)
The eigenvalues of the diagonalized Kirchhoff matrix $`(\underset{¯}{\underset{¯}{\overset{~}{K}}})_{pp}=(\underset{¯}{\underset{¯}{S}}^1\underset{¯}{\underset{¯}{K}}\underset{¯}{\underset{¯}{S}})_{pp}=k_p`$ are given by

$$k_p=4k\mathrm{sin}^2\left(\frac{p\pi }{2N}\right).$$
(56)
If we consider a path with given radius of gyration $`R_g^2`$, the basic spring constant is given by $`k=\frac{Nk_BT}{2R_g^2}`$. In the continuous chain limit ($`N\mathrm{}`$), sums over eigenmodes can be approximated by integrals. For example, one obtains from eq 26 an expression for the tube diameter

$`d_{T\alpha }^2`$ $`=`$ $`{\displaystyle \frac{1}{N}}{\displaystyle _0^N}𝑑p{\displaystyle \frac{1}{k_p+l}}`$ (57)
$`=`$ $`{\displaystyle \frac{k_BT}{\sqrt{l\left(4k+l\right)}}}{\displaystyle \frac{k_BT}{2\sqrt{lk}}}`$ (58)
which could be further simplified, since in this limit the springs representing a chain segment between two nodes are much stronger than the springs realizing the tube, i.e. $`kl`$.

For normally distributed internal distances $`\stackrel{}{r}_{xx^{}}`$ between points $`x=\frac{n}{N}`$, $`x^{}=\frac{m}{N}`$ on the chain contour the structure factor is given by

$$S(\stackrel{}{q},\lambda )=_{x=0}^1𝑑x_{x^{}=0}^1𝑑x^{}\mathrm{exp}\left(\frac{1}{2}\underset{\alpha =1}{\overset{3}{}}q_\alpha ^2r_{xx^{}\alpha }^2(\lambda )\right).$$
(59)
In the present case, eq 27 reduces to

$$r_{xx^{}\alpha }^2(\lambda )=\frac{1}{N}_{\mathrm{}}^{\mathrm{}}𝑑pu_{p\alpha }^2(\lambda )\left|e^{\text{i}\pi px}e^{\text{i}\pi px^{}}\right|^2.$$
(60)
In the undeformed state,

$$r_{xx^{}\alpha }^2(\lambda =1)=2R_g^2|xx^{}|$$
(61)
so that the structure factor is given by the Debye function:

$$S(\stackrel{}{q},\lambda =1)=\frac{2N}{q^4R_g^4}\left(\mathrm{exp}(q^2R_g^2)1+q^2R_g^2\right).$$
(62)
### A The Warner–Edwards Model

Warner and Edwards  used the replica method to calculate the conformational statistics of long paths through randomly crosslinked phantom networks. The basic idea was to represent the localization of the paths in space due to their integration into a network by a coarse-grained tube-like potential. Recently, it was shown by Read and McLeish  that the same result could be obtained along the lines of the following, much simpler calculation, where we evaluate Model A for linear polymers.

Evaluation of the integrals eqs 26 and 27 yields for the deformation independent tube diameter and the internal distances:

$`d_{TA\alpha }^2`$ $`=`$ $`{\displaystyle \frac{k_BT}{2\sqrt{kl_A}}}`$ (63)
$`{\displaystyle \frac{r_{xx^{}\alpha }^2(\lambda )}{2R_g^2}}`$ $`=`$ $`\lambda _\alpha ^2|xx^{}|`$ (64)
$`+`$ $`\left(1\lambda _\alpha ^2\right){\displaystyle \frac{d_{TA\alpha }^2}{R_g^2}}\left(1e^{\frac{R_g^2|xx^{}|}{d_{TA\alpha }^2}}\right),`$ (65)
We note that the latter equation can be rewritten in the form

$$\begin{array}{cc}\hfill \frac{r_{xx^{}\alpha }^2(\lambda )r_{xx^{}\alpha }^2(1)}{(\lambda _\alpha ^21)r_{xx^{}\alpha }^2(1)}& =f_A\left(\frac{R_g^2|xx^{}|}{d_{TA}^2}\right)\hfill \\ \hfill f_A(y)& =1+\frac{e^y1}{y}\hfill \end{array}$$
(66)
with a universal scaling function $`f_A(y)`$ which does not depend explicitly on the deformation. eq 66 measures the degree of affineness of deformations on different length scales. Locally, i.e. for distances inside the tube with $`R_g^2|xx^{}|d_T^2`$ corresponding to $`y1`$, the polymer remains undeformed. Thus $`lim_{y0}f(y)=0`$. Deformations become affine for $`R_g^2|xx^{}|d_T^2`$ and $`y1`$, where $`f(y)`$ tends to one.

Furthermore, one obtains for the shear modulus and the stress-strain relation

$`g_A(\lambda )`$ $`=`$ $`{\displaystyle \frac{\rho b^2\sqrt{kl_A}}{6}}=G_A`$ (67)
$`G_A`$ $`=`$ $`{\displaystyle \frac{1}{4}}{\displaystyle \frac{\rho b^2k_BT}{d_{TA}^2}}`$ (68)
$`\sigma _T(\lambda )`$ $`=`$ $`(\lambda ^2{\displaystyle \frac{1}{\lambda }})G_A.`$ (69)
so that the Mooney-Rivlin parameters are simply given by

$`2C_1`$ $`=`$ $`G_A`$ (70)
$`2C_2`$ $`=`$ $`0.`$ (71)
### B The Heinrich–Straube / Rubinstein–Panyukov-Model

Heinrich and Straube,  and Rubinstein and Panyukov  have carried out analogous considerations for Model B, i.e. an affinely deforming tube. The relation between the strength of the springs $`l_B`$ and the tube diameter in the unstrained state is identical to the previous case. However, the tube diameter now becomes deformation dependent:

$`d_{TB\alpha }^2(\lambda )`$ $`=`$ $`\lambda _\alpha {\displaystyle \frac{d_{TB}^2}{3}}.`$ (72)
Thus the typical width of the fluctuations changes only with the square root of the width of the confining potential. Using equations eqs 60 and 38, one obtains for the mean square internal distances:

$$\begin{array}{cc}\hfill \frac{r_{xx^{}\alpha }^2(\lambda )}{2R_g^2}& =\lambda _\alpha ^2|xx^{}|\hfill \\ & +\frac{1}{2}\left(\lambda _\alpha ^21\right)|xx^{}|e^{\frac{R_g^2|xx^{}|}{d_{TB\alpha }^2(\lambda )}}\hfill \\ & \frac{3}{2}\left(\lambda _\alpha ^21\right)\frac{d_{TB\alpha }^2(\lambda )}{R_g^2}\left(1e^{\frac{R_g^2|xx^{}|}{d_{TB\alpha }^2(\lambda )}}\right).\hfill \end{array}$$
(73)
Again, we can rewrite this result in terms of a universal scaling function for the degree of affineness of the polymer deformation:

$$\begin{array}{cc}\hfill \frac{r_{xx^{}\alpha }^2(\lambda )r_{xx^{}\alpha }^2(1)}{(\lambda _\alpha ^21)r_{xx^{}\alpha }^2(1)}& =f_B\left(\frac{R_g^2|xx^{}|}{d_{TB\alpha }^2(\lambda )}\right)\hfill \\ \hfill f_B(y)& =1+\frac{1}{2}e^y+\frac{3}{2}\frac{e^y1}{y}.\hfill \end{array}$$
(74)
Eq 74 shows that Straube’s conjecture  $`f_A(y)=f_B(y)`$ is incorrect. However, the two functions are qualitatively very similar.

For the shear modulus and the stress-strain relation we find

$`g_B(\lambda )`$ $`=`$ $`{\displaystyle \frac{1}{8}}{\displaystyle \frac{\rho b^2k_BT}{\lambda d_{TB}^2}}={\displaystyle \frac{G_B}{\lambda }}`$ (75)
$`G_B`$ $`=`$ $`{\displaystyle \frac{1}{8}}{\displaystyle \frac{\rho b^2k_BT}{d_{TB}^2}}`$ (76)
$`\sigma _T(\lambda )`$ $`=`$ $`\left(\sqrt{\lambda }{\displaystyle \frac{1}{\sqrt{\lambda }}}+\lambda {\displaystyle \frac{1}{\lambda }}\right)G_B`$ (77)
in agreement with Rubinstein and Panyukov.  In order to account for the network contribution to the shear modulus, these authors add the phantom network results to eqs 7677. This leads to the following relations for the Mooney-Rivlin parameters:

$`2C_1`$ $`=`$ $`G_{ph}+{\displaystyle \frac{1}{2}}G_B`$ (78)
$`2C_2`$ $`=`$ $`{\displaystyle \frac{1}{2}}G_B.`$ (79)
Note that eq 77 holds only for $`\lambda 1`$. For large compression or extension the approximation $`kl(\lambda )`$ breaks down and one regains the result of Heinrich and Straube:

$`\sigma _T(\lambda )`$ $`=`$ $`\left(\lambda {\displaystyle \frac{1}{\sqrt{\lambda }}}\right)G_B(\lambda 1,\lambda 1).`$ (80)
### C The “double tube” model

In the following we discuss a combination of two different constraints, one representing the network (Model A) and therefore deformation independent and the other representing the entanglements (Model B). Thus we use Model C to combine the Warner-Edwards model with the Heinrich-Straube/Rubinstein-Panyukov model.

Evaluating eq 26 one obtains for the tube diameter

$`{\displaystyle \frac{1}{d_{TC\alpha }^4(\lambda )}}`$ $`=`$ $`{\displaystyle \frac{1}{d_{TA\alpha }^4}}+{\displaystyle \frac{1}{d_{TB\alpha }^4(\lambda )}}.`$ (81)
The deformation dependent internal distances are given by:

$$\begin{array}{cc}\hfill \frac{r_{xx^{}\alpha }^2(\lambda )}{2R_g^2}& =\lambda _\alpha ^2|xx^{}|\hfill \\ & +\frac{1}{2}\left(\lambda _\alpha ^21\right)|xx^{}|\frac{d_{TC\alpha }^4(\lambda )}{d_{TB\alpha }^4(\lambda )}e^{\frac{R_g^2|xx^{}|}{d_{TC\alpha }^2(\lambda )}}\hfill \\ & \frac{3}{2}\left(\lambda _\alpha ^21\right)\frac{d_{TC\alpha }^2(\lambda )}{R_g^2}\left(1e^{\frac{R_g^2|xx^{}|}{d_{TC\alpha }^2(\lambda )}}\right)\hfill \\ & \frac{d_{TC\alpha }^4(\lambda )\left(d_{TA\alpha }^4+\frac{2}{3}d_{TB\alpha }^4(\lambda )\right)}{d_{TB\alpha }^4(\lambda )d_{TA\alpha }^4}.\hfill \end{array}$$
(82)
In this case, it is not possible to rewrite the result in terms of a universal scaling function, because the relative importance of the two types of confinement is deformation dependent. Introducing $`\mathrm{\Phi }(\lambda )=d_{TC\alpha }^4(\lambda )/d_{TB\alpha }^4(\lambda )`$, eq 82 can be rewritten as

$`{\displaystyle \frac{r_{xx^{}\alpha }^2(\lambda )r_{xx^{}\alpha }^2(1)}{(\lambda _\alpha ^21)r_{xx^{}\alpha }^2(1)}}({\displaystyle \frac{R_g^2|xx^{}|}{d_{TC\alpha }^2(\lambda )}},\mathrm{\Phi }(\lambda ))=`$ (84)
$`f_A\left(y\right)+\mathrm{\Phi }(\lambda )\left(f_B\left(y\right)f_A\left(y\right)\right).`$
For the elastic properties of the double tube model we find:

$`g_C(\lambda )`$ $`=`$ $`{\displaystyle \frac{2g_B^2(\lambda )+g_A^2}{\sqrt{4g_B^2(\lambda )+g_A^2}}}`$ (85)
$`\sigma _T(\lambda )`$ $`=`$ $`\left(\lambda ^21\right)g_C(\lambda )+\left(1\lambda ^1\right)g_C(\lambda ^{1/2}).`$ (86)
Again, eq 86 only holds for moderate strains. Shear modulus and the Mooney-Rivlin parameters are given by:

$`G_C`$ $`=`$ $`{\displaystyle \frac{2G_B^2+G_A^2}{\sqrt{4G_B^2+G_A^2}}}`$ (87)
$`2C_1`$ $`=`$ $`{\displaystyle \frac{G_A^4+6G_B^2G_A^2+4G_B^4}{\left(4G_B^2+G_A^2\right)^{3/2}}}`$ (88)
$`2C_2`$ $`=`$ $`{\displaystyle \frac{4G_B^4}{\left(4G_B^2+G_A^2\right)^{3/2}}}.`$ (89)
### D Comparison of the different tube models

In the following we compare the predictions of the different models for the microscopic deformations and the macroscopic elastic properties from two different points of view:

1. As a function of the network connectivity, i.e. the ratio of the average strand length $`N_c`$ between crosslinks to the melt entanglement length $`N_e`$. For this purpose, we identify $`G_A`$ with the shear modulus of the corresponding phantom network $`G_{ph}`$:

$`{\displaystyle \frac{1}{4}}{\displaystyle \frac{\rho b^2k_BT}{d_{TA}^2}}=G_A`$ $`=`$ $`G_{ph}=\left(1{\displaystyle \frac{2}{f}}\right){\displaystyle \frac{\rho k_BT}{N_c}}`$ (90)
$`d_{TA}^2`$ $`=`$ $`{\displaystyle \frac{f2}{4f}}b^2N_c`$ (91)
where we use $`f=4`$ for our plots. Similarly, we choose for $`G_B`$ a value of the order of the melt plateau modulus $`G_e`$:

$`{\displaystyle \frac{1}{8}}{\displaystyle \frac{\rho b^2k_BT}{d_{TB}^2}}=G_B`$ $`=`$ $`G_e={\displaystyle \frac{3}{4}}{\displaystyle \frac{\rho b^2k_BT}{N_e}}`$ (92)
$`d_{TB}^2`$ $`=`$ $`{\displaystyle \frac{1}{6}}b^2N_e.`$ (93)
2. Assuming that the system is characterized by a certain tube diameter $`d_{TC}`$ or shear modulus $`G_C`$, we discuss its response to a deformation as a function of the relative importance $`0\mathrm{\Phi }1`$ of the crosslink and the entanglement contribution to the confinement:

$`\mathrm{\Phi }`$ $`=`$ $`{\displaystyle \frac{d_{TC}^4}{d_{TB}^4}}`$ (94)
$`1\mathrm{\Phi }`$ $`=`$ $`{\displaystyle \frac{d_{TC}^4}{d_{TA}^4}}`$ (95)
where $`\mathrm{\Phi }`$ is of the order $`\left(1+\left(\frac{N_e}{N_c}\right)^2\right)^1`$ .

#### 1 Elastic properties

Figure 2 shows the shear modulus dependence on the ratio of the network strand length $`N_c`$ to the melt entanglement length $`N_e`$. As expected $`G_C`$ crosses over from $`G_{ph}`$ for short strands to $`G_e`$ in the limit of infinite strand length. For comparison we have also included the prediction of Rubinstein and Panyukov, $`G_{ph}+G_e`$. The shear moduli predicted by our ansatz are always smaller than this sum. In particular, we find $`G=G_{ph}`$ for $`N_cN_e`$. The physical reason is that in a highly crosslinked network the typical fluctuations are much smaller than the melt tube diameter. As a consequence, the network does not feel the additional confinement and the entanglements do not contribute to the elastic response. Figure 3 shows analogous results for the Mooney-Rivlin Parameters $`C_1`$ and $`C_2`$ again in comparison to the predictions of Rubinstein and Panyukov. Note, that $`C_2`$ is not predicted to be strand length independent.

Figure 4 shows the reduced force in the Mooney-Rivlin representation for different entanglement contributions $`\mathrm{\Phi }`$ to the confinement. For moderate elongations up to $`\lambda 2`$ the curves are well represented by the Mooney-Rivlin form. For a given shear modulus, $`C_1`$ and $`C_2`$ are a function of the entanglement contribution $`\mathrm{\Phi }`$ to the confinement:

$`2C_1`$ $`=`$ $`G_C\left(1{\displaystyle \frac{\mathrm{\Phi }^2}{42\mathrm{\Phi }}}\right)`$ (96)
$`2C_2`$ $`=`$ $`G_C{\displaystyle \frac{\mathrm{\Phi }^2}{42\mathrm{\Phi }}}.`$ (97)
#### 2 The tube diameter

Since eq 51 can be written in the form

$`G_C`$ $`=`$ $`{\displaystyle \frac{1}{8}}{\displaystyle \frac{\rho b^2k_BT}{d_{TC}^2}}\left(2\mathrm{\Phi }\right),`$ (98)
a plot of $`d_{TC}^2`$ versus $`N_e/N_c`$ looks very similar to Figure 2.

The deformation dependence of the tube diameter (Figure 5) takes the form:

$`{\displaystyle \frac{d_{TC\alpha }^4}{d_{TC\alpha }^4(\lambda )}}`$ $`=`$ $`\left(1\mathrm{\Phi }\right)+{\displaystyle \frac{\mathrm{\Phi }}{\lambda _\alpha ^2}}`$ (99)
$`\underset{\lambda \mathrm{}}{lim}{\displaystyle \frac{d_{TC||}(\lambda )}{d_{TC||}}}`$ $`=`$ $`\left(1\mathrm{\Phi }\right)^{1/4}`$ (100)
$`\underset{\lambda \mathrm{}}{lim}{\displaystyle \frac{d_{TC}(\lambda )}{d_{TC}}}`$ $`=`$ $`\left(\mathrm{\Phi }\lambda \right)^{1/4}.`$ (101)
In the parallel direction, the entanglement contribution to the confinement vanishes for large $`\lambda `$ so that $`lim_\lambda \mathrm{}d_{TC||}(\lambda )=d_{TA||}`$. On the other hand, the entanglements become relatively stronger in the perpendicular direction with $`lim_\lambda \mathrm{}d_{TC}(\lambda )=d_{TB}(\lambda )`$.

#### 3 Microscopic deformations and structure functions

Figure 6 compares the universal scaling functions of the Warner–Edwards and Heinrich-Straube/Rubinstein-Panyukov model defined by eqs 6674.

More important for the actual microscopic deformations than the difference between these two functions is the fact, that the distances are scaled with the deformation dependent tube diameter. As a consequence, deformations parallel to the elongation are smaller in Model B than in Model A, while the situation is reversed in the perpendicular direction. In the general case (eq 84 of Model C), the results are further complicated by the deformation dependent mixing of the two confinement effects. Nevertheless, eqs 6674, and 84 should be useful for the analysis of simulation data where real space distances are directly accessible.

Experimentally, the microscopic deformations can only be measured via small angle neutron scattering. Unfortunately, there seems to be no way to condense the structure functions eq 59 which result from eqs 6473, and 82 for different strains into a single master plot. Figures 7 and 8 show a comparison for three characteristic values of $`\lambda `$. Qualitatively, the results for the three models are quite similar. In particular, they do not predict Lozenge-like patterns for the two-dimensional structure functions as they were observed by Straube et al.  In particular, we agree with Read and McLeish  that the interpretation of Straube et al.  is based on an ad-hoc approximation in the calculation of structure functions from Model B. In principle, their alternative idea, to investigated the influence of dangling ends on the structure function within Model A and Model B,  can be easily extended to Model C. Judging from the small differences between the models (Figures 7 and 8) and the results in Ref. , this would probably allow to obtain an excellent fit of the data and to correctly account for the deformation dependence of the tube.  However, since the lozenge patterns were also observed in tri-block systems where only the central part of the chains was labeled,  dangling ends seem to be too simple an explanation. At present it is therefore unclear, if the lozenge patterns are a generic effect or if they are due to other artifacts such as chain scission.  Simulations  might help to clarify this point.

## IV Conclusion

In this paper we have presented theoretical considerations related to the entanglement problem in rubber-elastic polymer networks. More specifically, we have dealt with constrained fluctuation models in general and tube models in particular. The basic idea goes back to Edwards,  who argued that on a mean-field level different parts of the network behave, as if they were embedded in a deformation-dependent elastic matrix which exerts restoring forces towards some rest positions. In the first part of our paper, we were able to show that the generalized Rouse modes of the corresponding phantom network without entanglement remain eigenmodes in the presence of the elastic matrix. In fact, the derivation of eq 15, which is the Hamiltonian of the exactly solvable Constrained Mode Model (CMM),  provides a direct link between two diverging developments in the theory of polymer networks: the ideas of Edwards, Flory and others on the suppression of fluctuations due to entanglements and the considerations of Eichinger,  Graessley,  Mark,  and others on the dynamics of (micro) phantom networks. An almost trivial conclusion from our theory is the observation, that it is not possible to estimate the entanglement effects from the knowledge of the absolute strength of the confining potentials alone. Required is rather the knowledge of the relative strength which in turn is a function of the network connectivity eq 40.

Unfortunately, it is difficult to exploit our formally exact solution of the constrained fluctuation model for arbitrary connectivity, since it requires the eigenvalue spectrum of the Kirchhoff matrix for randomly crosslinked networks. In the second part of the paper we have therefore reexamined the idea of Heinrich and Straube  to introduce entanglement effects into the Warner-Edwards model  for linear, random paths through a polymer network, whose localization in space is modeled by a harmonic tube-like potential. In agreement with Heinrich and Straube,  and with Rubinstein and Panyukov  we have argued that in contrast to confinement due to crosslinking, confinement due to entanglements is deformation dependent. Our treatment of the tube model differs from previous attempts in that we explicitly consider the simultaneous presence of two different confining potentials. The effects are shown to be non-additive. From the solution of the generalized tube model we have obtained expressions for the microscopic deformations and macroscopic elastic properties which can be compared to experiments and simulations.

While we believe to have made some progress, we do not claim to have solved the entanglement problem itself. For example, it remains to be shown how the geometrical tube constraint arises as a consequence of the topological constraints on the polymer conformations. But even on the level of the tube model, we are guilty of (at least) two possibly important omissions: (i) we have neglected fluctuations in the local strength of the confining potential and (ii) we have suppressed the anisotropic character of the chain motion parallel and perpendicular to the tube. In the absence of more elaborate theories, computer simulations along the lines of Refs.  may present the best approach to a quantification of the importance of these effects.

### A Acknowlegements

The authors wish to thank K. Kremer, M. Pütz and T.A. Vilgis for helpful discussions. We are particularly grateful to E. Straube for repeated critical readings of our manuscript and for pointing out similarities between our considerations and those by Read and McLeish.