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# Ising Model on Networks with an Arbitrary Distribution of Connections

## Abstract

We find the exact critical temperature $`T_c`$ of the nearest-neighbor ferromagnetic Ising model on an ‘equilibrium’ random graph with an arbitrary degree distribution $`P(k)`$. We observe an anomalous behavior of the magnetization, magnetic susceptibility and specific heat, when $`P(k)`$ is fat-tailed, or, loosely speaking, when the fourth moment of the distribution diverges in infinite networks. When the second moment becomes divergent, $`T_c`$ approaches infinity, the phase transition is of infinite order, and size effect is anomalously strong.

05.10.-a, 05-40.-a, 05-50.+q, 87.18.Sn

The Ising model is one of the immortal themes in physics. It is a traditional starting point for the study of the effects of cooperative behavior. Networks with complex architecture display a spectrum of unique effects , and so they are an intriguing substrate. The simulation of the Ising model on a growing scale-free network  has demonstrated that it is extremely far from that on regular lattices and on ‘planar graphs’ .

In this Letter, we report our exact results and results, which, we believe, are asymptotically exact, for the thermodynamic properties of the Ising model on the basic construction for ‘equilibrium’ random networks. These networks are the undirected graphs, maximally random under the constraint that their degree distribution is a given one, $`P(k)`$. Here, degree is the number of connections of a vertex. Correlations between degrees of vertices in such graphs are absent. In graph theory, these networks are called ‘labelled random graphs with a given degree sequence’ or ‘the configuration model’ . The earlier interest was mainly in the percolation properties of complex networks and the spread of diseases on them , and most of the analytical results were obtained just for this basic construction (however, see Refs. , where the Berezinskii-Kosterlitz-Thouless percolation phase transition was studied in growing networks).

Our results demonstrate the strong effect of the fat tail of the degree distribution on the phase transition in the Ising model. The most connected vertices induce strong ferromagnetic correlations in their close neighborhoods at very large temperatures, and so their role is very important. Surprisingly, we observe very strong effects of these vertices, even when they, at first sight, must be insignificant, namely, when the first and the second moments of the degree distribution are still finite but the fourth moment already diverges ($`k^4\mathrm{}`$).

It is convenient to use the power-law degree distribution $`P(k)k^\gamma `$ for parametrization. Then, $`k^4`$ diverges for $`\gamma 5`$, $`k^3`$ diverges for $`\gamma 4`$, and $`k^2`$ is divergent for $`\gamma 3`$. When $`k^4<\mathrm{}`$, the phase transition is similar to that in the Ising model on high-dimension regular lattices. However, for $`\gamma <5`$ its nature is quite different. As $`\gamma `$ decreases and the role of the highly connected vertices turns to be more important, $`T_c`$ grows and the phase transition becomes more ‘continuous’. Below $`\gamma =4`$ it is of the higher order than the second in Ehrenfest’s terminology. Furthermore, at $`\gamma =3`$, $`T_c`$ approaches $`\mathrm{}`$, and the order of the phase transition is infinite.

When $`k^2`$ diverges ($`\gamma 3`$), the effect of the highly connected vertices is crucial. In the infinite network, long-range magnetic order is not destroyed by any temperature, and finite-size effect is very strong. Formally speaking, we develop a theory for the infinite networks, but it also allows us to describe finite-size effect. Our main results are presented in Tab. I.

Intuitive arguments.—The large networks that are studied in this paper have a tree-like ‘local structure’. When we start from a randomly chosen vertex, and add its first nearest neighbors, second, …, $`n`$-th with all their connections, the resulting sub-graph is almost surely a tree. Of course, in a finite size network, there is a boundary for $`n`$, above which loops appear in such a sub-graph.

Cooperative properties, which we study in the present Letter, are determined by this ‘local’ environment, where vertices have a quite different structure of connections than in the entire net. Interactions are transmitted through edges, from vertex to vertex. Hence, the following characteristic is crucial: the distribution of the number of connections of the nearest neighbor of a vertex. In the networks under consideration, it is $`kP(k)/k`$. Then, the nearest neighbors of a vertex have the average number of connections (the average degree) $`k^2/k`$, its second nearest neighbors have the same average degree, and so on. Notice that this value is greater than the average number of connections for the entire network $`k`$, and it is much greater than $`k`$ if $`k^2`$ is large. Therefore, we estimate the critical temperature of the Ising model on the network using the formula $`T_c/J=2/\mathrm{ln}[q/(q2)]`$ for the Ising model on a regular Cayley tree  with the coordination number $`q=k^2/k`$. The result is

$$\frac{J}{T_c}=\frac{1}{2}\mathrm{ln}\left(\frac{k^2}{k^22k}\right).$$
(1)
We will show below that this naive estimate is exact.

General solution.—Consider the Ising model on an a network with the Hamiltonian: $`=J_{ij}S_iS_jH_iS_i`$, where the first sum is over all edges of the graph, the second one is over all vertices, $`J>0`$ and $`H`$ are the energy of the ferromagnetic interaction and magnetic field, respectively. Hereafter, we set $`J=1`$. It is known that the regular Cayley tree is solved exactly by using recurrence relations . As networks under discussion have a local tree-like structure, we apply this method to the Ising model on such nets. Consider spin $`S_0`$ on a vertex $`0`$ with $`k_0`$ adjacent spins $`S_{1,i}`$, $`i=1,2\mathrm{}k_0`$. Due to the local tree-like structure this spin may be treated as a root of a tree. We introduce

$$g_{1,i}(S_0)=\underset{S_l=\pm 1}{}\mathrm{exp}[(\underset{lm}{}S_lS_m+S_0S_{1,i}+H\underset{l}{}S_l)/T],$$
(2)
where $`T`$ is temperature. The indices $`l`$ and $`m`$ run only over spins that belong to sub-trees with the root spin $`S_{1,i}`$, including $`S_{1,i}`$. Let $`x_{1,i}g_{1,i}()/g_{1,i}(+)`$, then the magnetic moment $`M`$ of the vertex $`0`$ is

$$M=(e^{2H/T}\underset{i=1}{\overset{k_0}{}}x_{1,i})/(e^{2H/T}+\underset{i=1}{\overset{k_0}{}}x_{1,i}).$$
(3)
The parameters $`x_{1,i}`$ describe the effects of the nearest neighbors on the spin $`S_0`$. In turn, $`x_{1,i}`$ are expressed in terms of parameters $`x_{2,l}=g_{2,l}()/g_{2,l}(+)`$, $`l=1,2\mathrm{}k_{1,i}`$, which describe effects of spins in the second shell on spins in the first shell, and so on. The following recurrence relation between $`x_{n,j}`$ and $`x_{n+1,l}`$ holds

$$x_{n,j}=y\left(\underset{l=1}{\overset{k_{n,j}1}{}}x_{n+1,l}\right),$$
(4)
where we introduce the function

$$y(x)=\frac{e^{(1+H)/T}+e^{(1H)/T}x}{e^{(1+H)/T}+e^{(1H)/T}x}.$$
(5)
If a spin $`S_{n+1,l}`$ is on a dead end, then $`x_{n+1,l}=1.`$ Note that at $`H>0`$, $`x_{n,l}1`$, while $`x_{n,l}1`$ for $`H<0`$. For $`H>0`$, it is convenient to introduce $`x_{n,l}=\mathrm{exp}(h_{n,l})`$. Here, at a given $`n`$, $`h_{n,l}`$ are positive and independent random parameters, which play the role of random effective fields acting on a spin in the $`n`$-th shell from neighboring spins in the $`n+1`$-th shell. Then, Eqs. (3) and (4) take the form

$`M`$ $`=`$ $`{\displaystyle \frac{e^{2H/T}\mathrm{exp}(_{l=1}^{k_0}h_{1,l})}{e^{2H/T}+\mathrm{exp}(_{l=1}^{k_0}h_{1,l})}}\text{,}`$ (6)
$`h_{n,j}`$ $`=`$ $`\mathrm{ln}\left\{y\left[\mathrm{exp}\left({\displaystyle \underset{l=1}{\overset{k_{n,j}1}{}}}h_{n+1,l}\right)\right]\right\}.`$ (7)
At dead ends we have $`h_{n+1,l}=0.`$ At $`H=0`$ in the paramagnetic phase $`h_{n,l}=0`$, while in the ordered phase $`h_{n,l}0.`$ Eqs. (6) and (7) determine the magnetization $`M`$ of a graph as a function of $`T`$ and $`H`$. We emphasize that these equations are valid for any tree-like graph.

While deriving the recurrence relations, we started from some spin $`S_0`$ and then made the recurrence steps along sub-trees. While solving the recurrence relations, we start from distant spins, i.e., from large $`n`$, and descend along sub-trees to the spin $`S_0`$. The recurrence steps Eq. (4) converges exponentially quickly. Therefore, we can set for the starting spins $`h0`$ . In the limit $`n\mathrm{}`$ the parameter $`h_{1,i}`$ is the fixed point of the recurrence steps. The thermodynamic behavior is determined by this fixed point, which is reached from the neighborhood of $`h=0`$.

Let us average the magnetization $`M`$ over the ensemble of random graphs with a degree distribution $`P(k)`$. Introducing the distribution function of $`h_{n,l}`$, $`\mathrm{\Psi }_n(h)=\delta (hh_{n,l}`$, and its Laplace transform $`\stackrel{~}{\mathrm{\Psi }}_n(s)=_0^{\mathrm{}}𝑑he^{sh}\mathrm{\Psi }_n(h)`$ we obtain from Eq. (6) the average magnetic moment

$$M=\underset{k}{}P(k)_0^{\mathrm{}}𝑑h\frac{e^{2H/T}e^h}{e^{2H/T}+e^h}_i\mathrm{}^i\mathrm{}\frac{ds}{2\pi i}e^{sh}\stackrel{~}{\mathrm{\Psi }}_1^k(s).$$
(8)
Here $`P(k)`$ is the probability that the vertex $`0`$ has $`k`$ connections. Equation (7) gives the recurrence relation between $`\stackrel{~}{\mathrm{\Psi }}_n(s)`$ and $`\stackrel{~}{\mathrm{\Psi }}_{n+1}(s)`$:

$$\stackrel{~}{\mathrm{\Psi }}_n(s)=\underset{k}{}\frac{P(k)k}{k}_0^{\mathrm{}}𝑑hy^s(e^h)_i\mathrm{}^i\mathrm{}\frac{ds^{}}{2\pi i}e^{s^{}h}\stackrel{~}{\mathrm{\Psi }}_{n+1}^{k1}(s^{})$$
(9)
with $`\stackrel{~}{\mathrm{\Psi }}_{n+1}(s)=1`$ at a dead end. Here $`P(k)k/k`$ is the probability that the the neighbor in the $`n+1`$th shell of a vertex from the $`n`$th shell has $`k`$ connections. We start from distant spins with $`\stackrel{~}{\mathrm{\Psi }}_{n+1}(s)1`$ and large $`n`$ and make recurrence steps toward smaller $`n`$ until we reach the fixed point. In the limit $`n\mathrm{}`$, the recurrence procedure converges to $`\stackrel{~}{\mathrm{\Psi }}(s)`$. The fixed point $`\stackrel{~}{\mathrm{\Psi }}(s)`$ is a solution of Eq. (9) in which $`\stackrel{~}{\mathrm{\Psi }}_n(s)`$ and $`\stackrel{~}{\mathrm{\Psi }}_{n+1}(s)`$ are replaced by $`\stackrel{~}{\mathrm{\Psi }}(s)`$. Then Eq. (8) with $`\stackrel{~}{\mathrm{\Psi }}_1(s)\stackrel{~}{\mathrm{\Psi }}(s)`$ gives the exact expression for $`M`$. At $`H=0`$ in the paramagnetic phase we have $`\stackrel{~}{\mathrm{\Psi }}(s)=1`$.

Let us find the exact critical temperature, $`T_c`$. Consider a starting function $`\stackrel{~}{\mathrm{\Psi }}_n(s)=\mathrm{exp}(s\delta )`$, where $`\delta `$ is small: $`0<\delta 1`$, $`s\delta 1`$. After the first $`m`$ recurrence steps, we obtain $`\stackrel{~}{\mathrm{\Psi }}_{nm}(s)=\mathrm{exp}(s\delta f^m)`$, where $`f=k(k1)k^1\mathrm{tanh}(1/T)`$. For $`f<1`$, the recurrence steps lead to the fixed point $`\stackrel{~}{\mathrm{\Psi }}(s)=1`$, which corresponds to the paramagnetic phase. $`f=1`$ at a certain temperature $`T_c`$ which satisfies the condition $`k(k1)k^1\mathrm{tanh}(1/T_c)=1`$, so that at $`T<T_c`$ we have $`f>1`$ and the recurrence steps lead away from the point $`\stackrel{~}{\mathrm{\Psi }}(s)=1`$. One sees that $`T_c`$ is given by Eq. (1). Thus, the estimate (1) is exact. This result is valid for any degree distribution with $`k^2<\mathrm{}`$. In this range, the average number of the second nearest neighbors is $`z_2=k^2k`$  ($`z_1k`$), so

$$\mathrm{tanh}\frac{1}{T_c}=\frac{z_1}{z_2}.$$
(10)
At zero temperature we find the solution $`\stackrel{~}{\mathrm{\Psi }}(s)=t_s+(1t_s)\delta _{s,0}`$, where $`\delta _{s,0}=1`$ at $`s=0`$ and $`\delta _{s,0}=0`$ at $`s0`$, $`t_s`$ is the smallest root of the equation $`t_s=_kP(k)k`$ $`t_s^{k1}`$. This solution gives $`M=1P(k)t_s^k`$, which is exactly the size of the giant connected component of the network. This result is evident. Indeed, only vertices in the giant connected component have non-zero spontaneous moment, which is equal to 1 at $`T=0`$.

Ansatz.—To study the critical behavior of thermodynamic quantities, we develop an ansatz in the spirit of the ‘effective medium’ approach. Notice that the right-hand sides of Eqs. (6) and (7) depend only on the sum of the independent and equivalent random variables $`h_{n,j}`$. So, let us use the following ansatz

$$\underset{l=1}{\overset{k}{}}h_{n,l}kh+𝒪(k^{1/2}),$$
(11)
where $`hh_{n,l}`$ is the average value of the ‘effective field’ acting on a spin. The larger $`k`$ the better this approximation. Therefore, the most ‘dangerous’ highly connected spins are taken into account in the best way. With this ansatz,

$$M=\underset{k}{}P(k)\frac{e^{2H/T}e^{kh}}{e^{2H/T}+e^{kh}}.$$
(12)
Applying the ansatz (11) to Eq. (7) yields

$$h=k^1\underset{k}{}P(k)k\mathrm{ln}y[e^{(k1)h}]G(h).$$
(13)
$`h`$ plays the role of the order parameter. At $`H=0`$, $`h=0`$ above $`T_c`$ and is non-zero below $`T_c`$.

Thermodynamic quantities.—Let us describe the critical behavior of the thermodynamic quantities of the Ising model on the infinite networks. For this, one must solve the equation of state (13) near $`T_c`$ at $`H=0`$.

The case $`k^4<\mathrm{}`$. The expansion of $`G(h)`$ over small $`h`$ has the form: $`G(h)=g_1h+g_3h^3+\mathrm{}`$. For brevity, we do not present exact expressions for the coefficients $`g_i`$. Substituting this expansion into Eq. (13) determines $`T_c`$ and the order parameter $`ha\tau ^{1/2}`$ as a function of the reduced temperature $`\tau =1T/T_c`$, where $`a=[12k(k1)^2/(kk(k1)^3T_c]^{1/2}`$. Note that the critical temperature $`T_c`$ that follows from our ansatz coincides with the exact result (1). At small $`h`$ and $`H=0`$ Eq. (12) gives the spontaneous moment $`Mka\tau ^{1/2}/2`$. The magnetic susceptibility can be calculated from Eq. (12), by differentiating over $`H`$ and then taking into account the dependence of $`h`$ on $`H`$ from Eq. (13). We obtain $`\chi (H=0)(k^3/(2k^2k(k2)))\tau ^1`$. At $`T>T_c`$ the susceptibility has the same behavior $`\chi (0)(T/T_c1)^1`$ but with the double prefactor.

In our ansatz, the average internal energy per spin, $`E=J_{ij}S_iS_j_T/N`$ (the average is thermodynamic and over the ensemble of graphs), at $`H=0`$ is

$`E`$ $`=`$ $`{\displaystyle \frac{1}{2}}k\mathrm{coth}(2/T)+`$ (15)
$`+{\displaystyle \frac{1}{2\mathrm{sinh}(2/T)}}{\displaystyle \underset{k}{}}P(k)k{\displaystyle \frac{e^h+e^{(k1)h}}{1+e^{kh}}}.`$
Substituting here $`ha\tau ^{1/2}`$, we find that the specific heat $`C=dE/dT`$ has a jump at $`T=T_c`$:

$$\mathrm{\Delta }C=k(k2)k^2a^2/(8k).$$
(16)
This jump disappears as $`k^4`$ approaches $`\mathrm{}`$. When $`k^4`$ diverges, we consider power-law degree distributions, $`P(k)k^\gamma `$.

The case $`\gamma =5`$. The divergence of $`k^4`$ leads to a logarithmic singularity of the function $`G(h)`$: $`G(h)=g_1h+g_3h^3\mathrm{ln}(1/h)+\mathrm{}`$. Solving Eq. (13) yields

$$h,M\tau ^{1/2}/(\mathrm{ln}\tau ^1)^{1/2},\text{ }\delta C1/\mathrm{ln}\tau ^1,\text{ }\chi \tau ^1$$
(17)
\[for any $`\gamma `$, we have $`\delta C(T>T_c)=0`$\]. Note that the critical behavior of $`\chi `$ is not changed.

The case $`3<\gamma <5`$. The function $`G(h)`$ has two leading terms: $`G(h)g_1h+g_3h^{\gamma 2}`$. Solving the equation of state (13) yields

$$h,M\tau ^{1/(\gamma 3)},\text{ }\delta C\tau ^{(5\gamma )/(\gamma 3)},\text{ }\chi \tau ^1.$$
(18)
Notice that for $`\gamma <5`$ critical exponents of the magnetization and specific heat differ from the standard ones. For $`\gamma >4`$, exponent $`\alpha `$ of the specific heat $`(\delta C\tau ^\alpha )`$ is above $`1`$. Hence the second derivative of the free energy over $`T`$ diverges at $`T_c`$. Therefore, the phase transition is of the second order in Ehrenfest’s classification. For $`\gamma <4`$, we have $`\alpha =(5\gamma )/(\gamma 3)<1`$ and the transition turns to be of a higher order. The order of the transition tends to infinity as $`\gamma 3`$. Nevertheless, for $`\gamma >3`$, the susceptibility obeys the Curie law.

The case $`\gamma =3`$. Here, $`k^2`$ diverges. Formally speaking, this leads to the infinite critical temperature for the infinite networks \[see Eq. (1)\]. In any finite network, $`k^2<\mathrm{}`$, and the critical temperature is finite, although it may be very high, $`T_ck^2/k`$ (see below). We consider temperatures, which are much less than this critical temperature, but where $`h1`$, so $`T1`$. Using, for brevity, the continuum approximation for the degree distribution, we obtain $`G(h)(kh/2T)\mathrm{ln}[2/(kh)]`$. Then,

$`h`$ $``$ $`(2/k)e^{2T/k},\text{ }Me^{2T/k},`$ (19)
$`\delta C`$ $``$ $`T^2e^{4T/k},\text{ }\chi T^1.`$ (20)
Without the continuum approximation, we have, instead of $`k`$ in the exponentials, a constant that is determined by the complete $`P(k)`$. Equation (20) describes the behavior of thermodynamic quantities at modest temperatures in the situation, where the phase transition is of infinite order and at ‘infinite temperature’. Notice the paramagnetic dependence $`\chi 1/T`$. Note that the temperature dependence $`M\mathrm{exp}[2T/k]`$ coincides with the result of the simulation  for the Barabási-Albert model ($`\gamma =3`$) \[see Fig. 1 (a) from this paper\].

The case $`2<\gamma <3`$. Again $`T_c`$ for large networks is very high. Using the expansion $`G(h)gh^{\gamma 2}/T`$, we find, in the range $`1TT_c`$, the following behavior

$$h,MT^{1/(3\gamma )},\delta CT^{(\gamma 1)/(3\gamma )},\chi T^1$$
(21)
\[compare with Eq. (20)\]. Notice that the susceptibility keeps the paramagnetic temperature dependence.

Finite-size effect.—Equation (1) shows that $`T_c`$ diverges when $`k^2\mathrm{}`$. In finite networks, $`k^2`$ is finite because of the finite-size cutoff of the degree distribution. In scale-free networks, it is estimated as $`k_{cut}k_0N^{1/(\gamma 1)}`$, where $`N`$ is the total number of vertices in a network, $`k_0`$ is a ‘minimal degree’ or the lower boundary of the power-law dependence, and $`kk_0(\gamma 1)/(\gamma 2)`$. Then, actually, repeating estimations from Ref.  (see more detailed discussions in Refs. ), we obtain

$`T_c{\displaystyle \frac{k\mathrm{ln}N}{4}}\text{at}\gamma =3,`$ (22)
$`T_c{\displaystyle \frac{(\gamma 2)^2}{(3\gamma )(\gamma 1)}}kN^{(3\gamma )/(\gamma 1)}\text{for}2<\gamma <3.`$ (23)
The first expression can be compared with the simulation  of the Ising model on the Barabási-Albert growing network ($`\gamma =3`$) with minimal degree $`k_0=5`$, so $`k=10`$. From Eq. (23) $`T_c2.5\mathrm{ln}N`$ follows. The simulation  yields $`T_c2.6\mathrm{ln}N3`$. Recall that our results were obtained for the completely uncorrelated network, and correlations in growing networks are extremely strong.

Discussion.—Our results may be compared with those for percolation on such networks  and the disease spread within them . Of course, the problems are distinct but one finds a great resemblance (the super-stability of long-range order when $`k^2\mathrm{}`$, phase transitions of higher order, etc.). All these anomalous features are determined by fat tails in the distributions of connections. Our final results were presented for uncorrelated networks. However, the quantitative agreement with the simulation  of correlated nets shows that they are applicable in much more general situations. Furthermore, our analytical results can be easily generalized.

S.N.D. thanks PRAXIS XXI (Portugal) for a research grant PRAXIS XXI/BCC/16418/98. S.N.D and J.F.F.M. were partially supported by the project POCTI/99/FIS/33141. A.G. acknowledges the support of the NATO program OUTREACH. We also thank A.N. Samukhin and D. Stauffer for useful discussions.

E-mail address: sdorogov@fc.up.pt
E-mail address: goltsev@pop.ioffe.rssi.ru
E-mail address: jfmendes@fc.up.pt


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# The coherent scattering function of the reptation model: simulations compared to theory.

## I Introduction

Dynamical properties of dense polymer systems like melts or dense solutions often are analyzed within the framework of the reptation model . Reptation is a specific mechanism for the motion of a single tagged chain through an environment of other chains. It is based on the idea that the background chains act as impenetrable obstacles which confine the motion of the tagged chain to a tube roughly defined by its present configuration. The local motion of the inner parts of the chain is restricted to the diffusion of little wiggles of ’spared length’ along the tube. Globally the motion is driven by the chain ends, where wiggles are created or destroyed. Creation of a wiggle shortens the tube by its spared length, destruction prolongs the tube in some randomly choosen direction. In the long run this motion of the chain ends leads to the complete destruction of the original tube and to large scale diffusion of the chain.

Formulated in more precise terms, the reptation model deals with the stochastic motion of a flexible chain embedded in a fixed environment of obstacles which form the edges of a regular lattice in three dimensional space. In this work we present results for the coherent structure function measured in an extensive simulation of this model. The measured coherent structure functions of the total chain and of internal subchains are compared to the results of our recent analytical evaluation  of the model. For the total chain there exist previous approximate theories based on reptation , which are included in the comparison. These theories do not treat the full dynamics of the model, but neglect so called ‘tube length fluctuations’. For typical chain lengths used in (computer- or physical-) experiments these fluctuations are known to yield important contributions, as has first been pointed out in Ref.  in the context of an analysis of the viscosity.

As mentioned above, results of the reptation model generally are used to analyze data for systems like polymer melts , where the surrounding of a given chain certainly is far from forming an ordered time independent lattice of obstacles. Clearly the surrounding chains slowly move away, which leads to ‘constraint release’ , an effect that becomes important  outside the limit of asymptotically long chains. Also disorder in the distribution of obstacles might lead to fluctuations in the local tube diameter, thus affecting the local mobility of spared length. In this work we omit all such effects of the environment and study the coherent structure function of the pure reptation model, as described above. This is a necessary prerequisite for an analysis aiming at the separation of the different effects present in a real melt.

To illustrate the problem we now briefly recall some typical results  of reptation, as established for very long chains. We concentrate on the motion of an internal segment, which from a theoretical point of view is the simplest quantity to discuss.

Simple as it is, the reptation scenario involves several time scales and leads to a rich phenomenology. It needs a microscopic time $`T_0`$ before the chain feels the existence of constraints due to its surrounding. Generally $`T_0`$ is taken as the Rouse time of a short subchain of $`N_e`$ segments: $`T_0N_e^2`$, where the ’entanglement length’ $`N_e`$ is choosen such that the coil diameter of the subchain is of the order of the diameter of the tube, which substitutes the surrounding chains. The second time scale $`T_2`$ is the relaxation time of the total chain in a fixed tube, i.e. the time a wiggle needs to diffuse over the whole chain. It depends on chain length $`N`$ as $`T_2T_0(N/N_e)^2N^2`$ and thus behaves as the relaxation time of a free chain in the Rouse model. The longest scale $`T_3`$ is the ’reptation time’. It measures the time which the motion of the chain ends needs to completely destroy the initial tube. In the limit of long chains the reptation model predicts  $`T_3(N/N_e)^3T_0`$.

For observables like the motion of individual segments the model yields asymptotic power laws, where the exponent depends on the time range. We here quote the results for the motion of the central segment $`j=N/2`$:

$$\overline{\left(𝐫_{N/2}(t)𝐫_{N/2}(0)\right)^2}\{\begin{array}{cc}t^{1/4};\hfill & T_0tT_2\hfill \\ (t/N)^{1/2};\hfill & T_2tT_3\hfill \\ t/N^2;\hfill & T_3t\hfill \end{array}$$
(1)
We use the bar to denote the dynamic average, i.e. the average over the motion of spared length. The pointed brackets stand for the average over all initial configurations.

Considerable effort has been invested to check these predictions in simulations of melts, but the outcome to date is not conclusive . The $`t^{1/2}`$-regime has never been properly identified. (Note that crossover from a region $`\overline{(𝐫_j(t)𝐫_j(0))^2}t^\alpha ,\alpha <\frac{1}{2}`$, to free diffusion easily can pretend the existence of a $`t^{1/2}`$-regime. What has to be demonstrated is the stability of this regime for a larger range of time and chain lengths.) Slowing down of segment motion in the range $`T_0<t<T_2`$ is observed , with an effective exponent somewhere between 1/4 and 1/2. Only for some related observable, measuring the motion of a central segment relative to the center of mass, a $`t^{1/4}`$-behavior seems to be established . Real experiments do not measure $`\overline{(𝐫_j(t)𝐫_j(0))^2}`$. However, a related quantity, the return-to-origin probability of a segment averaged over all segments, is measured in NMR-experiments. Here the equivalent to $`t^{1/4}`$-behavior has been found in Ref. , but Ref.  reports equivalent results only for motion through a crosslinked gel, where constraint release is suppressed. The corresponding melt shows quite different behavior.

Invoking tube length fluctuations and constraint release we qualitatively may interpret the observed deviations from the asymptotic reptation results as crossover behavior outside the region of asymptotic chain lengths. However, there exist other theories of melt dynamics, which are not based on the tube concept and describe many experiments as well . (See also the review .) It thus is conceivable that the basic assumptions of the reptation scenario do not hold. To get more insight into these problems, we clearly have to quantitatively evaluate the consequences of the pure reptation model, beyond asymptotic power laws.

In previous analytical work  we determined the motion of individual segments of the chain. Since our theory involves some approximations, we compared the results to simulations  of the Evans-Edwards model , which is an accurate implementation of the pure reptation model. In essence, both theory and simulations agreed in showing that the crossover among various asymptotic power law regions is very slow. The crossover regions are so broad that the asymptotic power laws can be identified only for very long chains. For example, using the Evans-Edwards model with the smallest possible tube diameter we could identify the $`t^{1/4}`$-law for the motion of the central segment only for chain lengths $`N160`$. This law is the easiest to observe, and our evaluation of the theory predicts that other asymptotic laws unambiguously can be identified only for much longer chains. This result is in line with the known slow crossover behavior of the reptation time , which is predicted to reach the asymptotic law $`T_3N^3`$ only for chain lengths far beyond present day experimental feasibilities. Still, for the motion of individual segments, the full crossover functions can be calculated, and our analytical results very well agree with our simulations. Furthermore, for shorter chains all our analytical and simulational results qualitatively are very similar to results of simulations of melts . In later work  we considered chain motion in a time independent, but disordered environment, where the disorder affects only the chain mobility but leaves the equilibrium distribution of chain configurations unchanged. We found that with such ’kinematic’ disorder reptation prevails, an observation which recently has been supported  by rigorous bounds on the diffusion coefficient. Since such kinematic disorder certainly is present in a melt, these results again support reptation as adequate theory of melt dynamics.

In contrast to the motion of individual segments the coherent structure function $`S_c(q,t;N),(q=|𝐪|`$ : scattering vector, $`t`$ : time), is well accessible in real experiments. It can be measured, for instance, by neutron scattering from a mixture of deuterated and hydrogenated chains. As mentioned above, approximate asymptotic forms for $`S_c(q,t;N)`$, based on reptation type theories, can be found in the literature . However, as for the motion of individual segments we can evaluate the full reptation theory for $`S_c(q,t;N)`$ also outside the asymptotic regime. As for individual segments, we then expect to see important preasymptotic or crossover effects. The evaluation of $`S_c(q,t;N)`$ including full reptational dynamics is somewhat complicated, and our theory in detail has been presented in Ref. . Here we compare the results to simulations of the Evans-Edwards model. We consider both the scattering from the total chain and from interior subchains. The latter is important to estimate the reliability of the theory, which can treat end-effects only in some approximation.

In Section 2 we discuss our simulations. Section 3 is devoted to a comparison with the expressions for $`S_c(q,t;N)`$ given by Doi and Edwards  or by de Gennes , respectively. In Section 4 we qualitatively describe our theory and give an empirical fit formula which reasonably well describes our quantitative results. The comparison between our theory and our Monte Carlo data is presented in Sect. 5. Section 6 contains our conclusions.

## II Simulations

### A The Evans-Edwards model

A very simple model for simulating reptation has been introduced by Evans and Edwards . The configuration $`\{𝐫_1,\mathrm{},𝐫_N\}`$ of the chain is taken as a random walk of $`N1`$ steps $`|𝐫_j𝐫_{j1}|=\mathrm{}_0`$ on a cubic lattice. The lattice spacing $`\mathrm{}_0`$ henceforth defines the unit of length. The obstacles are taken as the edges of the dual lattice. In the interior of the chain, the obstacles suppress any motion except for the motion of ‘hairpins’, i.e., configurations of three subsequent beads of type $`\{𝐫_{j1},𝐫_j,𝐫_{j+1}=𝐫_{j1}\}`$. In an elementary move the tip $`𝐫_j`$ of the hairpin with equal probability hops to any of the six neighbors of the site $`𝐫_{j1}=𝐫_{j+1}`$. The chain ends $`𝐫_1,𝐫_N`$ are free to hop between all neighbors of $`𝐫_2,𝐫_{N1}`$, respectively. Fig. 1 shows a sequence of internal configurations resulting from this dynamics. In our simulations we used the same implementation of the model as in our previous work , and we measured the coherent structure function defined as

$`S_c(q,t^{(MC)};N)`$ $`=`$ $`{\displaystyle \underset{j_1,j_2=1}{\overset{N}{}}}\overline{e^{i𝐪\left(𝐫_{j_1}(t^{(MC)})𝐫_{j_2}^{(0)}\right)}}`$ (2)
$`=`$ $`\overline{𝒞(𝐪,t^{(MC)})𝒞(𝐪,0)+𝒮(𝐪,t^{(MC)})𝒮(𝐪,0)}`$ (3)
where

$`𝒞(𝐪,t)`$ $`=`$ $`{\displaystyle \underset{j=1}{\overset{N}{}}}\mathrm{cos}(\mathrm{𝐪𝐫}_j(t))`$ (5)
$`𝒮(𝐪,t)`$ $`=`$ $`{\displaystyle \underset{j=1}{\overset{N}{}}}\mathrm{sin}(\mathrm{𝐪𝐫}_j(t)).`$ (6)
(The imaginary part $`𝒮(𝐪,t)𝒞(𝐪,0)𝒞(𝐪,t)𝒮(𝐪,0)`$ of $`S_c`$ is zero on average, of course.) To get more information on the internal motion, we also measured the coherent structure function $`S_c(q,t^{(MC)};M,N)`$ of the central subchain of length $`M`$, defined by restricting the summations in Eqs. (2.1), (2.2) to the interval $`[(NM)/2+1,(N+M)/2]`$. ¿From our previous work, we expect to see features characteristic of reptation for $`N100`$, and we therefore used chain lengths $`N=80,\mathrm{\hspace{0.33em}160},\mathrm{\hspace{0.33em}320}`$. Since for our model, the entanglement length is estimated as $`N_e3.7`$ (see Sect. 4.B), this yields values $`22N/N_e87`$. Similar values are extracted from many simulations or experiments on melts, so that our results should be relevant also for the interpretation of such data. Monte Carlo time $`t^{(MC)}`$ is measured in units of one attempted move per bead on average. We performed runs up to $`t_{\mathrm{max}}^{(MC)}=510^{10}`$, and we measured the structure function up to $`t^{(MC)}=4.510^9`$ using a moving time average.

### B Statistical accuracy

During a run, the longer chains do not diffuse very far, and data of a single run therefore are strongly correlated. To get reasonably accurate results we have to average over many independent runs. A priori, this poses a problem for larger momenta, $`qR_g1`$, where $`R_g`$ is the radius of gyration of the chain. It is easily checked that the reduced width of the distribution of the static structure function with increasing $`qR_g`$ rapidly tends to $`1`$. Indeed, in the limit $`N\mathrm{},q>0`$ fixed, the distribution of $`S_c(q,0;N)`$ approaches the exponential distribution. This suggests that $`10^4`$ runs are needed to reduce the statistical uncertainty to a few percent. This would pose no problems, if we just were interested in static properties. However, for the longer chains a single run extending to times well beyond the reptation time takes several hours on a standard work station. In measuring dynamic quantities the number of runs therefore inevitably is much smaller than needed for a precise determination of static quantities.

Fortunately it turns out that the dynamics essentially is decoupled from the static configuration. This is illustrated in Fig. 2, which shows results for $`S_c(q,t^{(MC)};N),q\mathrm{}_0=0.5,N=320`$, normalized to the exact static structure function $`S_0(q,N)`$ of the model, which easily is calculated analytically (see Sect. 2.D). Each curve in Fig. 2 a is averaged over $`10^3`$ independent short runs $`(t^{(MC)}10^5)`$, including the moving time average for each run. Clearly the scatter of $`S_c(q,0;N)`$ is consistent with the above discussion. It is larger than the temporal variation of the curves. However, plotting in Fig. 2 b the normalized time dependence $`[S_c(q,t^{(MC)};N)S_c(q,0;N)]/S_0(q,N)`$, we find that all curves nearly coincide. The global dynamics measured by the structure function, is not correlated with the static configuration, an observation which supports one of the basic assumptions of the reptation model. The reason behind that observation is easily understood. The mobility of the chain is governed by the number of hairpins which essentially is Gaussian distributed and fluctuates much less than the static structure function. Furthermore, except for rare events, viz. extremely stretched or extremely compact configurations, the number of hairpins is independent of the overall (tube-) conformation of the chain. With this insight, we take as basic data the difference $`S_c(q,t^{(MC)};N)S_c(q,0;N)`$ for each run. The error bars in our plots give twice the standard deviation of this difference. We always plot the normalized dynamic structure function defined as

$`\overline{S}_c(q,t^{(MC)};N)=1+{\displaystyle \frac{1}{S_0(q,N)}}`$ (8)
$`\left(S_c(q,t^{(MC)};N)S_c(q,0;N)\right)_{\text{averaged over runs}},`$
where $`S_0(q,N)`$ is the exact static structure function, not the measured average value of $`S_c(q,0;N)`$. Depending on the number of independent runs, these two quantities differ by $`0.16\%`$.

For reasons of computer memory, we performed runs with three different values of the maximal time $`t_{\mathrm{max}}^{(MC)}`$. To observe the small initial effects we for each value of chain length $`N`$ and wave vector $`|𝐪|`$ averaged over $`10^4`$ short runs with $`t_{\mathrm{max}}^{(MC)}=10^5`$, taking data up to $`t^{(MC)}=1.410^4`$. These data are denoted by small dots in the later figures. In the intermediate time range, $`t_{\mathrm{max}}^{(MC)}=10^8`$, we measured the structure function for $`10^4t^{(MC)}10^7`$ and always performed 50 runs (big dots in the figures). In the long time range, $`t_{\mathrm{max}}^{(MC)}=510^{10}`$, we took data for $`10^5t^{(MC)}4.510^9`$, averaging over 30 to 100 runs (circles in the figures). For each set of runs with given maximal time, we also measured the average of $`S_c(q,0;N)`$.

For additional information on the statistical accuracy of our data, we measured the imaginary part of $`S_c(q,t^{(MC)};N)`$, which rigorously vanishes for $`t^{(MC)}=0`$, but fluctuates about zero for $`t^{(MC)}>0`$ in a finite sample. For longer times we typically found average values of order $`\pm 0.01S_0(q,N)`$, again smaller than the uncertainty of $`S_c(q,0;N)`$ in long-time runs.

### C Momentum range

First considerations suggest to restrict the analysis to the momentum range $`R_g^2q^2\mathrm{}_0^2`$. Momenta of order $`q^2R_g^21`$ do not resolve the tube but rather see a cloud of beads. For momenta $`q^2\mathrm{}_0^21`$ the micro-structure of the chain might play a role. In our simulations the above condition can only poorly be satisfied. For our longest chain $`(N=320)`$ it reads $`0.02q^2\mathrm{}_0^21`$, leaving at best a small window close to $`q\mathrm{}_00.4`$.

However, a closer inspection reveals that these considerations do not seriously restrict dynamic measurements. To check the relevance of the condition $`q^2\mathrm{}_0^21`$ we analyzed the dynamics of a free chain. As is well known, asymptotically the standard Rouse dynamics is found if for a lattice chain ‘kink jumps’: $`\{𝐫_j𝐫_{j1}=𝐬_1,𝐫_{j+1}𝐫_j=𝐬_2\}\{𝐫_j𝐫_{j1}=𝐬_2,𝐫_{j+1}𝐫_j=𝐬_1\},𝐬_1𝐬_2=0`$ are allowed besides hairpin-moves. We found that with this modified dynamics, the normalized coherent structure function is in excellent agreement with the relaxation function calculated from the continuous chain Rouse model, even for $`q\mathrm{}_0=1`$. Micro-structure effects arising from the finite segment size die out very rapidly on the scale of about 10 $`MC`$-steps and therefore should be negligible also for reptation dynamics. Of course this does not exclude the possibility of dynamical micro-structure effects which might influence the short time regime and are not accounted for by the reptation model. In particular, reptation does not properly treat the dynamics of fluctuations perpendicular to the tube axis.

Concerning the condition $`q^2R_g^21`$, we note that smaller wave vectors, of course, provide little information on the details of the internal motion of the chain, but at least they measure the global motion of the coil. However, the slowness of this motion asks for extremely large time ranges $`t_{\mathrm{max}}^{(MC)}T_3`$. We therefore performed only one series of simulations for $`|𝐪|\mathrm{}_0=0.1,N=160`$, corresponding to $`q^2R_g^2=0.267`$. Most of our simulations use values $`3q^2R_g^250`$, with a maximal value of $`q^2R_g^253`$ reached for $`|𝐪|\mathrm{}_0=1,N=320`$.

### D Normalization

In our simulations we choose $`𝐪`$ to point into one of the three lattice directions. For that choice, the static correlations between segments $`j`$ and $`k`$ take the form

$`e^{i𝐪(𝐫_j(0)𝐫_k(0))}`$ $`=`$ $`\left({\displaystyle \frac{2}{3}}+{\displaystyle \frac{1}{3}}\mathrm{cos}|𝐪|\right)^{|kj|}`$ (9)
$`=`$ $`\mathrm{exp}(\overline{q}^2|kj|),`$ (10)
where

$$\overline{q}^2=\mathrm{ln}\left(\frac{2}{3}+\frac{1}{3}\mathrm{cos}|𝐪|\right).$$
(11)
Recall that the lattice constant $`\mathrm{}_0`$ defines the unit of length. Summing the segment indices over the chain, we find the static structure function which is used in normalizing our results:

$`S_0(q,N)`$ $`=`$ $`{\displaystyle \underset{j,k=1}{\overset{N}{}}}\mathrm{exp}(\overline{q}^2|kj|)`$ (12)
$`=`$ $`N+{\displaystyle \frac{2}{(e^{\overline{q}^2}1)^2}}\left[e^{\overline{q}^2(N1)}N+(N1)e^{\overline{q}^2}\right].`$ (13)
In our simulations, we for each run averaged over all three lattice directions.

## III Comparison of data and simplified reptation type theories

### A Asymptotic form of $`S_c(q,t;N)`$ derived by Doi and Edwards

A simplified version of the reptation model concentrates on the dynamics of the ‘primitive chain’ , which is a reduced form of the chain, lying stretched in the tube. In the Evans-Edwards model the primitive chain can be viewed as the non-reversal random walk derived from the random walk configuration of the physical chain by cutting off all hairpins. All internal degrees of freedom are neglected so that within time interval $`\mathrm{\Delta }t`$, all parts of the primitive chain move the same distance $`\mathrm{\Delta }s`$ along the tube. The length of the primitive chain is taken to be fixed. (This model often is addressed as ‘the reptation model’. We will use the term ‘primitive chain model’ to distinguish it from the full reptation model which deals with the dynamics of spared length as the elementary process.)

With its simplifications, the primitive chain model treats only the destruction of the initial tube, as resulting from the global motion of the chain. It neglects tube length fluctuations which are due to the uncorrelated motion of the chain ends as well as relaxation in the interior of the tube. Since both these additional effects are governed by the equilibration time $`T_2`$ of the chain, the primitive chain model is restricted to times $`tT_2`$. Furthermore, the segment indices are taken as continuous variables, and this ‘continuous chain limit’ restricts the theory to long chains: $`N1`$.

Within this model the time dependent correlation function of two beads:

$$S(q,t;j,k,N)=\overline{\mathrm{exp}\left[i𝐪(𝐫_j(t)𝐫_k(0))\right]},$$
(14)
obeys a diffusion equation. Solving this equation and integrating $`j,k`$ over the chain, Doi and Edwards arrive at the following result for the normalized coherent structure function (see Ref. , chapter 6.3.):

$$\overline{S}_c(q,t;N)=\frac{S_c(q,t;N)}{S_c(q,0;N)}=\overline{S}_{DE}(q^2R_g^2,t/T_3)$$
(15)
$$\overline{S}_{DE}(Q,\tau )=\frac{1}{D(Q)}\underset{p=1}{\overset{\mathrm{}}{}}\frac{Q\mathrm{sin}^2\alpha _p}{\alpha _p^2(Q^2/4+Q/2+\alpha _p^2)}\mathrm{exp}\left(\alpha _p^2\tau \right).$$
(16)
Here the $`\alpha _p`$ are the positive solutions of

$$\alpha _p\mathrm{tan}\alpha _p=\frac{1}{2}Q=\frac{1}{2}q^2R_g^2,$$
(17)
and

$$D(Q)=\frac{2}{Q^2}(e^Q1+Q)$$
(18)
is the Debye function. With the assumptions of the theory, the reptation time attains its asymptotic behavior $`T_3N^3`$. Note that $`T_3`$ is related to the time scale $`\tau _d`$ introduced in Ref.  by $`T_3=\frac{\pi ^2}{4}\tau _d`$.

The result (3.2),(3.3) for $`\overline{S}_c(q,t;N)`$ depends only on $`Q=q^2R_g^2\overline{q}^2N`$ and $`\tau =t/T_3t/N^3`$, but not on $`N`$ separately. To test this feature, we carried through simulations for $`N=320,q=0.25`$ and $`N=80,q=0.5024`$, both parameter sets resulting in $`q^2R_g^23.3`$. Fig. 3 compares our simulation results to $`\overline{S}_{DE}`$, plotted as function of $`\mathrm{log}_{10}(t/T_3)`$. The Monte Carlo time has been scaled so that in the region $`t/T_31`$, the data for $`N=320`$ fit to the theoretical curve. In view of $`T_3N^3`$, for $`N=80`$ an additional factor $`4^3`$ has been included in the time scale. With this scaling, the deviation between the two sets of data shown in Fig. 3 proves that we have not yet reached chain lengths large enough for the primitive chain model to hold.

Still, for larger times, $`\overline{S}_{DE}`$ and the data for $`N=320`$ agree quite well. This suggests to treat $`T_3=T_3(N)`$ as a fit parameter in adjusting the data to $`\overline{S}_{DE}(q^2R_g^2,t/T_3)`$, giving up the strict proportionality $`T_3N^3`$. However, a closer inspection of Fig. 3 reveals that the data initially decrease faster than $`\overline{S}_{DE}`$. This is a systematic effect, observed for all chain lengths and wave vectors. It points to the influence of relaxation modes neglected in the primitive chain model. According to a suggestion of de Gennes , internal relaxation, in particular, yields an initial decrease of $`\overline{S}_c(q,t;N)`$ which saturates at some $`q`$-dependent plateau value. We thus should fit the data to $`B_{DE}\overline{S}_{DE}(q^2R_g^2,t/T_3)`$, with $`B_{DE}`$ as another free parameter.

A detailed analysis of the reptation model points to tube length fluctuations as the origin of the initial decrease, rather than internal relaxation. (See Sect. 4.C and Ref. .) Still we may fit our data to $`B_{DE}\overline{S}_{DE}`$, where $`B_{DE}=B_{DE}(q,N)`$, $`T_3=T_3(N)`$. Fig. 4 shows the results for $`N=320`$. We clearly find very good agreement among theory and data in the time region $`t20T_2`$. (The estimate for $`T_2`$ has been taken from our theory, see Sect. 4.B.) Deviations occur for smaller times, which is consistent with the approximations inherent in the primitive chain model. Within the realm of that model the central segment moves according to $`\overline{(r_{N/2}(t)r_{N/2}(0))^2}(t/N)^{1/2},T_2tT_3`$ (cf. Eq. (1.1)), and from our previous work  we know that this law certainly is not attained before $`t20T_2`$. The results shown in Fig. 4 are typical also for other chain lengths.

Since $`T_3`$ now plays the role of an effective fit parameter, it a priori could depend both on $`N`$ and $`q`$. Parameters $`T_3=T_3(q,N)`$, $`B_{DE}=B_{DE}(q,N)`$ extracted by fitting our data are collected in Table 1. Any $`q`$-dependence of $`T_3`$ is found to be weak, if significant at all. $`B_{DE}`$ depends on $`q`$, but is essentially independent of $`N`$.

Ignoring any $`q`$-dependence, we in Fig. 5 have plotted the values of $`T_3(N)`$ normalized to the asymptotic behavior $`T_3^{\mathrm{}}`$ resulting from Eqs. (4.5), (4.7), (4.12) below. It must be stressed that we here define a reptation time in terms of the large time behavior of the scattering function (and the Doi-Edwards form $`\overline{S}_{DE}`$). Other definitions based on other observables (or other theoretical expressions) may yield somewhat different results. In previous work , we defined a reptation time $`\stackrel{~}{T}_3`$ by the criterion that the mean squared distance moved by a chain end equals the equilibrium mean squared end-to-end distance: $`\overline{(𝐫_0(\stackrel{~}{T}_3)𝐫_0(0))^2}=R_e^2`$. The previous data are included in Fig. 5 (open circles). The two definitions yield somewhat different results for the corrections to the asymptotic behavior. In the range of $`N`$ measured here, $`\stackrel{~}{T}_3`$ is about 30 % below $`T_3`$ as taken from the scattering function. It, however, must be noted that the values extracted from the scattering functions depend somewhat on the time range included in the fit. We estimate this uncertainty to be of the order of 5 %. In Fig. 5 we included lines corresponding to effective power laws $`T_3N^z`$. The effective powers are consistent with expectations based on previous work .

To summarize, our results show that the coherent structure function of the primitive chain model may well be used to fit data for large times, $`t20T_2`$, provided we allow for some phenomenological prefactor $`B_{DE}`$ and take the reptation time $`T_3`$ as an effective parameter defined by the fit. For smaller times, deviations are seen, that increase with increasing $`q`$.

### B Comparison to Gennes’ theory

In his work , de Gennes considers only intermediate values of $`q`$: $`\mathrm{}_0^2q^2R_g^2`$ and constructs the scattering function as a sum of two terms. For $`tT_2`$ the ‘creep’ term dominates. This term is just the limiting form of $`\overline{S}_{DE}`$ (Eq. (3.3)) for $`Q\mathrm{}`$:

$$\overline{S}^{(c)}(t,N)=\frac{8}{\pi ^2}\underset{p=0}{\overset{\mathrm{}}{}}(2p+1)^2\mathrm{exp}\left[(2p+1)^2\frac{\pi ^2}{4}\frac{t}{T_3}\right].$$
(19)
It tends to $`1`$ for $`t/T_30`$. It is combined with some contribution of local relaxation, which is calculated in two steps. First the interior relaxation of a Rouse chain in one dimensional space is calculated, where the chain is stretched so that the end-to-end distance equals the tube length. In the second step this one dimensional motion is embedded into the three dimensional random walk configuration of the tube. Tube length fluctuations are neglected. With some additional approximation, this model of a Rouse chain in a coiled tube yields a ‘local’ contribution

$$\overline{S}^{(\mathrm{})}(q,t)=e^{t_1}\text{erfc}\sqrt{t_1},$$
(20)
where

$$t_1=\frac{3}{4}\frac{N}{N_e}(q^2R_g^2)^2\frac{t}{T_3}.$$
(21)
Since again the validity of the asymptotic law $`T_3N^3/N_e`$ is assumed, the chain length $`N`$ and the entanglement length $`N_e`$ drop out in Eq. (3.8), as expected for a contribution resulting from strict one dimensional internal relaxation. $`\overline{S}^{(\mathrm{})}(q,t)`$ describes internal relaxation on length and time scales exclusively determined by $`q`$. The total result for the normalized coherent scattering function reads

$`\overline{S}_c(q,t;N)=\overline{S}_{dG}(q,t;N)=`$ (23)
$`(1B_{dG})\overline{S}^{(\mathrm{})}(q,t)+B_{dG}\overline{S}^{(c)}(t,N),`$
where according to de Gennes

$$B_{dG}=B_{dG}(q)=1\frac{N_e}{36}q^2\mathrm{}_0^2$$
(24)
is independent of $`N`$.

In an attempt to extend the range of wave vectors to $`q\mathrm{}_01`$, Schleger et al  used $`B_{dG}(q)=\mathrm{exp}(q^2\mathrm{}_0^2N_e/36)`$. With this choice it was found  that $`\overline{S}_{dG}(q,t;N)`$ over a large range of wave vectors and for several chain lengths yields a good fit to neutron scattering data from melts of Polyethylene. However, Pütz et al , using the same form of $`\overline{S}_{dG}(q,t;N)`$ to analyze simulation data for melts of very long chains, found only poor agreement. In later work  they argued that this was due to some ambiguity in the relation between entanglement length $`N_e`$ and tube diameter.

In our recent work  we reconsidered the model of a Rouse chain in a tube. Our analysis reveals some serious deficiency of this model: it does not start from equilibrium initial conditions. An ensemble of stretched one dimensional random walk chains folded into the three dimensional random walk configuration of the tube is not identical to the equilibrium ensemble of three dimensional random walk chains. The local structure of the chains differs on the scale of the tube diameter. For the static structure function, this yields a correction of relative order $`N_e/N`$ that vanishes in the limit $`q^2R_g^2=\text{const},N\mathrm{}`$. For the time dependence, however, the effect is serious since the non-equilibrium initial conditions relax only on scale $`T_2`$. Our analysis shows that this unphysical relaxation indeed dominates the time dependence of the ‘local’ contribution $`\overline{S}^{(\mathrm{})}(q,t)`$, as calculated from this model (see Fig. 3 of Ref. ). Data analysis based on Eq. (3.9) with $`\overline{S}^{(\mathrm{})}(q,t)`$ taken from the model of a Rouse chain in a tube therefore is not particularly meaningful.

Still, in view of the experimental findings cited above, we may ask whether Eqs. (3.6) - (3.9) can be used as heuristic modeling of the coherent structure function resulting from reptation. Fig. 6 shows the result for the longest chain $`(N=320)`$ and largest wave-vector $`(q=1.0)`$ measured. The resulting value $`q^2R_g^253.3`$ is large enough for a reasonable test of the form (3.9), which assumes $`q^2R_g^21`$. Replacing in Eq. (3.9) $`\overline{S}_c`$ by the full result $`\overline{S}_{DE}`$ of the primitive chain model does not seriously change the picture. The reptation time is fixed by the long-time tail and is taken from Table 1. For $`B_{dG}`$, we used the form suggested by Schleger et al: $`B_{dG}=\mathrm{exp}(q^2\mathrm{}_0^2N_e/36)`$. $`N_e`$ in principle is known from our previous analysis of segment motion: $`N_e=3.69`$ (see Sect. 4.B). Thus all parameters are fixed, and the result for $`\overline{S}_{dG}`$ (full curve in Fig. 6) strongly deviates from the data, except for the extreme long-time tail. This is no surprise since the value $`B_{dG}0.9`$, resulting for $`N_e=3.69`$, considerably exceeds the value $`B_{DE}0.78`$ extracted from fitting with the Doi-Edwards form. (See Table 1.) If we treat $`B_{dG}`$ as a free parameter, we clearly in the range $`t20T_2`$ can enforce agreement among theory and data, (see Fig. 4), at the expense of considerably underestimating $`\overline{S}_c`$ for $`tT_2`$. The situation can be improved only, if we also change the scale of $`t_1`$, dividing $`t_1`$, (Eq. 3.8), by a factor of order 200. Quite similar results are found for $`N=160`$, where $`t_1`$ has to be divided by a factor of order 50 to reproduce the average trend of the data for $`tT_2`$.

We conclude that also from a purely phenomenological point of view, the form (3.9) of $`\overline{S}_c`$ is not justified. The large and chain length dependent rescaling required for $`t_1`$ suggests that tube length fluctuations governed by time scale $`T_2`$ might be much more important than internal relaxation processes governed by an $`N`$-independent scale.

We finally note that in Ref.  a modified form of Eq. (3.9) has been proposed, in which the creep term $`\overline{S}^{(c)}`$ is calculated from tube length fluctuations, but the form (3.7) of the local contribution is retained. The analysis is restricted to the time range $`tT_2`$, which is the relevant range for neutron scattering experiments. From Fig. 6 it is clear that with the proper parameter values $`N_e=3.69,t_1`$ as given in Eq. (3.8), this modification cannot improve the fit for $`tT_2`$, since tube length fluctuations only decrease the contribution $`\overline{S}^{(c)}`$. Again a reasonable fit can be reached only if we take both $`B_{dG}`$ and the scale of $`t_1`$ as free parameters.

## IV Results of the full reptation model

### A Basic ideas of our approach

The primitive chain model neglects all internal degrees of freedom, and an attempt to model internal relaxation as one dimensional Rouse motion leads to unphysical initial conditions, which seriously affect the results up to times of the order of the internal relaxation time $`T_2`$. However, the simplifying assumptions underlying these approaches are no essential part of the original reptation model. As recalled in the introduction, reptation as single elementary process involves the diffusion of spared length along the chain, together with its decay and creation at the chain ends. The separation of the dynamics into internal relaxation, tube length fluctuations and motion of the primitive chain therefore is somewhat artificial. In particular, tube length fluctuations cannot properly be separated from the motion of the primitive chain, as will be discussed in Sect. 4.C. Furthermore, from our analysis of segment motion we know that for typical experimental chain lengths we are in a crossover region where all dynamic effects must be treated on the same level by evaluating the consequences of full reptational dynamics.

In our analytical work  we use a very simple implementation of the reptation idea, in which the wiggles of spared length are represented by particles which hop along the chain, with hopping probability $`p`$ per time step. The particles do not interact, and a given particle sees the others just as part of the chain. If a particle passes a bead, it shifts the position of this bead in the tube by the spared length $`\mathrm{}_S`$. The chain ends are coupled to large particle reservoirs, which absorb and emit particles at such a rate that the equilibrium density $`\rho _0`$ of spared length on the chain is maintained on the average. Absorption or emission of a particle prolongs or shortens the tube at the corresponding chain end by the spared length $`\mathrm{}_S`$. Keeping track of the change in the occupation number of the reservoirs, we therefore control the tube length fluctuations as well as the destruction of the original tube. In particular, within time interval $`[0,t]`$ an end piece of length $`\mathrm{}_Sn_{\mathrm{max}}(t)`$ of the original tube has been destroyed, where $`n_{\mathrm{max}}(t)`$ is the largest negative fluctuation of the occupation number of the corresponding reservoir during this time interval.

All moments of the stochastic processes which determine the motion of internal segments or the occupation of the reservoirs, can be evaluated rigorously, but the determination of the maximal fluctuation $`n_{\mathrm{max}}(t)`$ poses a serious problem. The occupation number of a reservoir carries out a correlated random process, since a particle emitted can be reabsorbed by the same reservoir later. This correlation dies out only on scale of the internal equilibrium time $`T_2`$ of the chain. It does not prevent the evaluation of arbitrary moments, but the maximal fluctuation cannot be calculated rigorously. Such a calculation is possible  only for an uncorrelated random process. To determine the degree of tube destruction, we therefore have to resort to some approximation. In our method, we basically for each final time $`t`$ replace the correlated random process by that uncorrelated random walk which for this time yields the correct moments. The effective hopping rate of this random walk depends on the final time $`t`$. It changes from the microscopic rate $`\rho _0p`$ for $`tT_2`$ to the mobility $`\rho _0p/N`$ of the primitive chain for $`tT_2`$, which is a physically most reasonable behavior.

In essence, this ‘mean hopping rate’ approximation for the coherent structure function smoothly interpolates between two rigorously accessible limits. For $`tT_2`$, tube renewal does not influence the motion of an interior piece of the chain, and the coherent structure function of such pieces can be calculated rigorously. For $`tT_2`$ the correlations of the stochastic processes are negligible and the mean hopping rate approximation should become exact. Indeed, we find that in this limit the motion of all chain segments is tightly bound to the motion of the chain ends. As a result, the problem reduces to the uncorrelated motion of a single stochastic variable, as in the primitive chain model. The details of our approximation are discussed extensively in Refs. , and will not be repeated here.

The coherent scattering function can be determined by summing the contribution of two beads

$$S(q,t;j,k,N)=\overline{e^{i𝐪(𝐫_j(t)𝐫_k(0))}}$$
(25)
over the bead indices $`j,k`$. For this function we in Ref. , Sect. 6.A, have derived an integral equation of the form

$`S(q,t;j,k,N)`$ $`=`$ $`S^{(T)}(q,t;j,k,N)`$ (26)
$`+`$ $`{\displaystyle _0^t}dt_0{\displaystyle \underset{j_0=0}{\overset{N}{}}}\{𝒫^{}(j_0,t_0|0)\mathrm{exp}(\overline{q}^2|j_0k|)S(q,tt_0;j,0,N)`$ (27)
$`+`$ $`𝒫^{}(j_0,t_0|N)\mathrm{exp}(\overline{q}^2|j_0k|)S(q,tt_0;j,N,N)\}.`$ (28)
Here $`dt_0𝒫^{}(j_0,t_0|m),m=0,N`$, is the probability that the initial tube is finally destroyed within time interval $`[t_0,t_0+dt_0]`$, its last piece being the initial position of segment $`j_0`$, which at time $`t_0`$ is occupied by chain end $`0`$ or $`N`$, respectively. The exponential factors result from the random walk configuration of the tube, cf. Eqs. (2.4), (2.5). The inhomogeneity $`S^{(T)}(q,t;j,k,N)`$ is the contribution to $`S(q,t;j,k,N)`$ of all those stochastic processes, which do not completely destroy the original tube.

Summing Eq. (4.2) over the segments $`j,k`$ we find a system of two equations which have to be solved numerically. The kernel $`𝒫^{}`$ and the inhomogeneity $`S^{(T)}`$ are determined within the mean hopping rate approximation. The results are lengthy and will not be reproduced here. We rather in Subsect. D give an analytical expression, which in the range of wave vectors and chain lengths considered in the present work, reasonably well reproduces the numerical results of our theory.

We finally note that we analytically can prove (Ref. , Sect. 7) that our theory in the limit of infinite chain length $`N\mathrm{}`$, with $`t/T_3`$ and $`q^2R_g^2`$ kept fixed, reproduces the result of the primitive chain model. Also the relation to the model of a Rouse chain in a tube can be analyzed in precise terms, if we consider an interior piece of length $`M`$ in an infinitely long chain. We find (Ref. , Sect. 5) that this model reproduces the results of reptation only for $`t/T_2(M)\mathrm{}`$, $`q^2R_g^2(M)`$ fixed, where $`T_2(M)`$ or $`R_g(M)`$ are the equilibration time and the radius of gyration of the subchain considered. For $`t/T_2(M)1`$ the non-equilibrium initial condition seriously affect the scattering function, as has been discussed in Sect. 3.B.

### B Microscopic parameters of the reptation model

The microscopic parameters of the model are the segment size $`\mathrm{}_0=|𝐫_j𝐫_{j1}|`$, the average density $`\rho _0`$ of mobile particles on the chain, the spared length per particle $`\mathrm{}_S`$, and the hopping rate $`p`$. Measuring all lengths in units of $`\mathrm{}_0`$, we introduce the dimensionless spared length

$$\overline{\mathrm{}}_S=\frac{\mathrm{}_S}{\mathrm{}_0}.$$
(29)
It turns out that for all times beyond truly microscopic times $`t2/p`$, the hopping rate $`p`$ combines with $`t`$ to yield the time variable

$$\widehat{t}=pt,$$
(30)
which we will use in the sequel. The relation of $`\widehat{t}`$ to the Monte Carlo time $`t^{(MC)}`$ introduces the fit parameter $`\tau _0`$:

$$\widehat{t}=\tau _0t^{(MC)}.$$
(31)
Also $`\rho _0`$ and $`\overline{\mathrm{}}_S`$ combine into a single important parameter. The number of particles that passed over a bead on average increases with time, and if it is sufficiently large, the discreteness of the individual hopping processes becomes irrelevant. The results then depend only on the combination $`\overline{\mathrm{}}_S^2\rho _0`$. In our previous work on the motion of individual segments , we found that $`\overline{\mathrm{}}_S`$ and $`\rho _0`$ separately enter the results only for $`\widehat{t}10^3`$. In this time region, a segment on average has moved less than 10 steps in the tube and still feels the discreteness of the process. For the structure function we find that not even this small time region is seriously affected. If we ignore the discreteness of the hopping process, the results for all $`\widehat{t}>1`$ change by less than 0.5 %, which coincides with the accuracy of our numerical evaluation. Thus the only microscopic parameters relevant for the coherent structure function are the combination $`\overline{\mathrm{}}_S^2\rho _0`$ and the time scale $`\tau _0`$. The reason behind this empirically observed suppression of initial discreteness effects will be discussed in Subsect. 4.C.

We furthermore note that also the discreteness of the underlying chain turns out to be unimportant. Provided we normalize the coherent structure function by the static structure function calculated for the same micro-structure, we for $`N50`$ and wave vectors $`q\mathrm{}_02`$ within the above quoted accuracy find the same results for a continuous chain as for the model where we sum over discrete bead indices $`j,k`$. This observation is consistent with the independence of statics and dynamics discussed in Sect. 2.B and illustrates that our calculation indeed yields universal results.

Since in our simulations we use the same model as in our previous work on segment motion , we can take the numerical values of the microscopic parameters from there. In analyzing the Monte Carlo data, we thus use the value

$$\overline{\mathrm{}}_S^2\rho _0=1.23.$$
(32)
Having a much larger set of data available than previously, we somewhat readjust the time scale. We use

$$\tau _0=6.810^2,$$
(33)
rather than the previous value $`\tau _0=6.09210^2`$. For the logarithmic scale $`\mathrm{log}_{10}\widehat{t}`$ of the figures in Ref. , this amounts to a shift by $`0.048`$, which does not change the good agreement among theory an experiment which in Ref.  is shown to hold over about 6 decades of time.

In our formulation of the reptation model, the entanglement length $`N_e`$, or the tube diameter $`\mathrm{}_0N_e^{1/2}`$, equivalently, do not show up explicitly. They are hidden in the spared length and the density of the particles, i.e., in the overall mobility of the chain. In contrast, the previous approaches explicitly involve these parameters. As discussed at the end of the last subsection, our theory in appropriate limits reproduces the previous results, which allows us  to relate our parameters $`\overline{\mathrm{}}_S,\rho _0,p`$ to those of these other models. Specifically, we find a relation for the entanglement length:

$$N_e=3\overline{\mathrm{}}_S^2\rho _0.$$
(34)
With the numerical value (4.6) this yields $`N_e=3.69`$ and implies that for the Evans-Edwards model with the smallest possible obstacle spacing it needs about 4 steps before the obstacles come into play seriously.

We note that $`\overline{\mathrm{}}_S\rho _0`$ and thus $`N_e`$ have been determined  by fitting data for the motion of individual segments in the time range $`\widehat{t}>10^3`$. $`N_e`$ is thus not influenced by the deviations from the full reptation model occuring in the initial range $`\widehat{t}10^3`$, as discussed below, (Sect. 5). Thus consistency of the analysis clearly enforces use of the same value $`N_e`$ for all observables. We estimate the uncertainty of this value to be in the range of 5 %.

We now also can give a quantitative definition of the time scales. Identifying the equilibration time $`T_2`$ with the Rouse time of a free chain of $`N`$ segments we from the asymptotic relations among the models find

$$\widehat{T}_2=pT_2=\frac{(N+1)^2}{\pi ^2}.$$
(35)
The reptation time can be defined as the average life time of the original tube

$$\widehat{T}_3=p_0^{\mathrm{}}𝑑t_0t_0𝒫^{}(t_0).$$
(36)
Here $`dt_0𝒫^{}(t_0)`$ is the probability that the tube is finally destroyed within time interval $`[t_0,t_0+dt_0]`$. It is related to the distribution $`𝒫^{}(j_0,t_0|m)`$ introduced in Eq. (4.2) via

$$𝒫^{}(t_0)=\underset{j_0=0}{\overset{N}{}}\left[𝒫^{}(j_0,t_0|0)+𝒫^{}(j_0,t_0|N)\right].$$
(37)
Evaluation in the asymptotic limit $`N\mathrm{}`$ yields

$$\widehat{T}_3^{(\mathrm{})}=\frac{N^3}{4\overline{\mathrm{}}_S^2\rho _0}=\frac{3}{4}\frac{N^3}{N_e}.$$
(38)
In this limit, $`\widehat{T}_3`$ is related to the reptation time $`\tau _d`$ introduced for the primitive chain model  as

$$\widehat{T}_3^{(\mathrm{})}=\frac{\pi ^2}{4}p\tau _d,$$
(39)
which is the relation used in Sect. 3 in our analysis of the primitive chain model.

### C Qualitative discussion of the coherent structure function

Tube destruction, tube length fluctuations, and internal relaxation are different facets of the same microscopic dynamics. Therefore any separation of these processes is to some extent artificial. Yet some rough discussion based on these concepts is useful with regard to the interpretation of the data presented in Sect. 5.

We first consider tube length fluctuations $`\mathrm{\Delta }L`$. Here a precise definition is possible by identifying $`\mathrm{\Delta }L`$ with the fluctuations of the total spared length. On average the spared length equals $`\mathrm{}_S\rho _0N`$, where $`\rho _0N`$ is the average number of particles on the chain. Since the fluctuations of the particle number essentially are Gaussian distributed we find

$$\frac{\mathrm{\Delta }L}{\mathrm{}_0}\overline{\mathrm{}}_S\sqrt{\rho _0N}=\sqrt{\frac{1}{3}N_eN},$$
(40)
where $`N_e`$ is introduced via Eq. (4.8). Within the equilibration time $`T_2`$ tube length fluctuations on average on both chain ends replace a piece of length $`\mathrm{\Delta }L/2`$ of the original tube by a new piece. In real three dimensional space, this new piece has an average extension of $`\sqrt{\mathrm{}_0\mathrm{\Delta }L/2}`$, and to observe the effect, the scattering vector must obey $`q^2\mathrm{}_0\mathrm{\Delta }L/21`$, or

$$q^2\mathrm{}_0^2\sqrt{\frac{12}{N_eN}},$$
(41)
equivalently. For large wave vectors, the coherent structure function $`S_c(q,t;N)`$ is determined by the part of the original tube that still exists at time $`t`$. Taking only tube length fluctuations into account, we therefore find for $`tT_2`$:

$`\overline{S}_c(q,T_2;N)`$ $`=`$ $`{\displaystyle \frac{S_c(q,t;N)}{S_c(q,0;N)}}{\displaystyle \frac{N\mathrm{\Delta }L/\mathrm{}_0}{N}}`$ (42)
$``$ $`1\sqrt{{\displaystyle \frac{N_e}{3N}}},`$ (43)
provided $`q`$ is large compared to the bound (4.15). This estimate yields the effect of fully developed tube length fluctuations. With increasing chain lengths it clearly is suppressed, but it should be well visible up to fairly long chains $`N/N_e10^2`$.

Tube destruction in the sense of the primitive chain model is responsible for the main part of the decay of the coherent structure function. According to Eq. (4.16), it is the dominant effect as soon as $`1\overline{S}_c(q,t,N)\sqrt{N_e/3N}`$. For $`tT_2`$, it is strongly correlated with tube length fluctuations which, seen from a microscopic point of view, drive the tube destruction. It therefore is no surprise that evaluating the coherent structure function of the primitive chain model, $`\overline{S}_{DE}(q^2R_g^2,t/T_3)`$, for $`q^2R_g^21`$ and time $`t=T_2`$, we find a decrease of the same order of magnitude as that due to tube length fluctuations.

$`1\overline{S}_{DE}(q^2R_g^2,{\displaystyle \frac{T_2}{T_3}})\stackrel{q^2R_g^21}{=}1\overline{S}^{(c)}(T_2,N)`$ (45)
$`=\sqrt{{\displaystyle \frac{2}{\pi }}{\displaystyle \frac{T_2}{T_3}}}+O(e^{\text{const}T_3/T_2})\sqrt{{\displaystyle \frac{8}{3\pi ^3}}{\displaystyle \frac{N_e}{N}}}+O(e^{\text{const}N}).`$
Recall that $`\overline{S}^{(c)}(t,N)`$ (Eq. (3.6)) is the limit of $`\overline{S}_{DE}`$ for $`q^2R_g^21`$. Comparison of Eqs. (4.16), (4.17) illustrates that tube length fluctuations cannot properly be separated from tube destruction. Being of the same order of magnitude for $`tT_2`$, they strongly interfere in the full theory.

We finally note that the use of $`T_3`$ as fit parameter, necessary to fit the results of the primitive chain model to our data, illustrates that tube length fluctuations influence the efficiency of tube destruction for all times , even for chains of lengths $`N/N_e100`$.

Internal relaxation can be analyzed by considering a subchain of length $`M`$ in the center of an infinitely long chain. We thus consider the coherent structure function

$$S_c(q,t;M,\mathrm{})=\underset{j,k=1}{\overset{M}{}}\overline{e^{i𝐪(𝐫_j(t)𝐫_k(0))}}^{\mathrm{}}.$$
(47)
Within time $`t`$, segment $`j`$ is displaced along the tube by $`\overline{\mathrm{}}_sn`$ steps, and since the tube has a random walk conformation, the average over the paths of segment $`j`$ yields

$`e^{i𝐪(𝐫_j(t)𝐫_k(0))}^{\mathrm{}}=e^{\overline{q}^2|j+\overline{\mathrm{}}_snk|}.`$
This expression is to be averaged over the distribution $`𝒫_1(n,t)`$ of the number $`n`$ of particles that diffused over bead $`j`$. We note that in the situation considered here $`𝒫_1(n,t)`$ is independent of $`j`$, since the process is translationally invariant along an infinitely long chain. We thus find

$$S_c(q,t;M,\mathrm{})=\underset{n=\mathrm{}}{\overset{+\mathrm{}}{}}𝒫_1(n,t)\underset{j,k=1}{\overset{M}{}}e^{\overline{q}^2|j+\overline{\mathrm{}}_snk|}.$$
(48)
Now shifting $`j+\overline{\mathrm{}}_Snj`$, we can rewrite this expression as

$`S_c(q,t;M,\mathrm{})`$ $`=`$ $`{\displaystyle \underset{n=\mathrm{}}{\overset{+\mathrm{}}{}}}𝒫_1(n,t)\{{\displaystyle \underset{j,k=1}{\overset{M}{}}}e^{\overline{q}^2|jk|}`$ (49)
$`+`$ $`{\displaystyle \underset{k=1}{\overset{M}{}}}[{\displaystyle \underset{j=M+1}{\overset{M+\overline{\mathrm{}}_sn}{}}}e^{\overline{q}^2|jk|}{\displaystyle \underset{j=1}{\overset{\overline{\mathrm{}}_sn}{}}}e^{\overline{q}^2|jk|}]\}`$ (50)
Since $`𝒫_1(n,t)`$ is normalized to $`1`$, the first term in Eq. (4.20) yields the static structure function of the subchain. All time dependence results from the motion of the end pieces of the subchain and thus is due to the length fluctuations and the shift of the subchain in the tube. Proper interior relaxation within the subchain has no effects on the coherent structure function.

We want to stress that this does not imply that our theory neglects interior relaxation. The basic relation (4.19) only exploits the fact that the segment $`j`$ has carried out a random walk of $`\overline{\mathrm{}}_Sn`$ steps. It does not imply that this walk is along the precise original configuration of the chain. Rather the path will have changed by the motion of other segments, i.e., internal relaxation. What our result shows is that the effects of interior relaxation average out in the structure function as calculated within the reptation model. This also explains the observation in Subsect. 4.B that the discreteness of the individual steps is unimportant numerically. It yields only a correction to the second term in Eq. (4.20), which by itself is very small in the time range $`\widehat{t}10^3`$ where discreteness corrections might show up. Deviations among theory and data which we will find for short times and wave vectors of the order of the inverse segment size therefore must originate from effects not taken into account in the reptation model.

In this context some further remark on the model of Rouse motion in a coiled tube seems appropriate. Concerning the dynamics along the tube, our hopping model is essentially equivalent to Rouse motion. Specifically, beyond microscopic times the motion of individual segments approaches Rouse type motion, as has been shown in Ref. , Sect. 3. The difference found for the structure function results from the imposed initial conditions, only. It reflects the fact that the structure function measures correlations between two segments $`j,k`$ and thus is influenced by the initial configuration of the subchain connecting $`j`$ with $`k`$.

To summarize, we have seen that in the limit $`N\mathrm{}`$ with $`q^2R_g^2q^2N`$ kept fixed, the coherent structure function of the total chain varies only on scale $`T_3`$. In this limit, $`\overline{S}_c(q,t;N)`$ is given by the primitive chain model. For shorter chains, tube length fluctuations come into play. They change the effective reptation time and lead to an initial decrease of $`\overline{S}_c`$ on time scale $`T_2`$. Both effects are important for chains up to lengths $`N/N_e10^2`$, at least. Proper internal relaxation, however, averages out.

With regard to the data presented in Sect. 5, we want to close this subsection with a brief discussion of the scattering $`S_c(q,t;M,N)`$ from the central subchain of length $`MN`$ in a chain of finite length $`N`$. For small times (and sufficiently large wave vectors), we expect to see small fluctuations of the length of the part of the tube occupied by the subchain. Since, however, these fluctuations do not lead out of the original tube, they are much less efficient in reducing the scattering function than the tube length fluctuations relevant for the total chain: on average, up to times of the order of the relaxation time $`T_2(M)`$ of the subchain, its position in the tube has not changed seriously. A definite decrease of $`S_c(q,t;M,N)`$ sets in for times large enough for the subchain to leave its original part of the tube. For very large chain lengths $`N`$, this may occur for times $`tT_2(N)`$. $`S_c`$ then decreases like $`t^{1/4}`$, this law reflecting the $`t^{1/4}`$-law (Eq. (1.1)) for the motion of an internal segment. For $`T_2(N)tT_3(N)`$, the motion of the subchain is driven by particles created by the chain ends which leads to a decrease like $`t^{1/2}`$ (cf. Eq. (1.1)). Finally, of course, this behavior is cut off by tube destruction reaching the position of the subchain. On the quantitative level this behavior can be extracted from our theory. In the discussion of our data we in some figures will include curves which show the effect of relaxation of the (sub-) chain moving in an infinitely long tube, i.e., neglecting all tube renewal effects.

### D Approximate analytical parameterization of our results for the total chain

The integral equations which yield the normalized coherent structure function $`\overline{S}_c(q,t;N)`$ of the full reptation model, can be solved only numerically. Furthermore, also the kernel and the inhomogeneity in these equations do not take a simple form . In particular, the inhomogeneity is given by some integral with a lengthy integrand. Thus, to present the results in a more easily tractable form some more or less heuristic analytical parameterization might be useful.

It should be clear that such a parameterization cannot be very simple. The coherent scattering function involves two time scales: $`T_2`$ and $`T_3`$. Furthermore also wave vector and chain length combine into two relevant variables: $`q^2R_g^2`$ and $`q^2\mathrm{}_0^2\sqrt{N_eN}q^2R_g^2\sqrt{N_e/N}`$. The latter variable should govern the contribution of tube length fluctuations (cf. Eq. (4.15)). In searching for a reasonable parameterization we exploit the fact that for very long chains our results reduce to those of the primitive chain model. Furthermore, as shown in Sect. 3.A, the functional form of $`\overline{S}_c`$, given by this model, can be used to fit the long-time tail also for non-asymptotic chain lengths. This suggests to use an ansatz similar to de Gennes’ form (3.9):

$$\overline{S}_{\text{Fit}}(q,t;N)=(1B)H(q,t;N)+B\overline{S}_{DE}(q^2R_g^2,\frac{\widehat{t}}{\widehat{T}_{3,\text{Fit}}})$$
(52)
The function $`\overline{S}_{DE}(Q,\tau )`$ is given by Eqs. (3.2)-(3.5). Analyzing the numerical results of our theory in a large range of wave vectors and chain lengths which exceeds that used in the simulations, we find that the effective reptation time weakly depends on $`q`$. We use the expression

$`\widehat{T}_{3,\text{Fit}}={\displaystyle \frac{3}{4}}N_e^2\left({\displaystyle \frac{N}{N_e}}\right)^3`$ (54)
$`\{1[{\displaystyle \frac{2.1}{(9+N/N_e)^{0.5}}}{\displaystyle \frac{2.5}{9+N/N_e}}](1+{\displaystyle \frac{0.25}{(1+0.3q^2R_g^2)^2}})\}.`$
The leading term gives the asymptotic law (4.12), the first correction is of order $`\sqrt{N_e/N}`$, in agreement with a result by Doi . The prefactor of this correction differs somewhat from Doi’s result. However it must be noted that eqs. (4.21) - (4.25) are meant to reproduce the scattering function in a wide parameter range. Thus eq. (4.22) should not literally be compared to Doi’s result.

We now turn to the coefficient $`B`$, which is taken as

$$B=\mathrm{exp}\left\{\left(\frac{q^2R_g^2\sqrt{\frac{N_e}{N}}}{1+q^2R_g^2\sqrt{\frac{N_e}{N}}}\right)^{0.6}\frac{2.8}{2.4+\sqrt{N/N_e}}\right\}.$$
(55)
This form is consistent with the discussion of the influence of tube length fluctuations given in the previous subsection. $`B`$ tends to 1 for $`q^2R_g^2\sqrt{N_e/N}1`$ and yields $`B1O(\sqrt{N_e/N})`$ in the limit $`N\mathrm{}`$, $`q`$ fixed.

The initial decrease of the scattering function over a sizeable range of time is approximated by a stretched exponential with an effective exponent which strongly decreases with increasing $`q^2R_g^2`$. We take

$$H(q,t,N)=\mathrm{exp}\left\{\left(\frac{\widehat{T}_2}{\widehat{T}_{3,\text{Fit}}}\right)^{x_1}\left[3.2\left(\frac{q^2R_G^2}{0.7+q^2R_g^2}\right)^2\frac{\widehat{t}}{\widehat{T}_2}\right]^{x_2}\right\}$$
(56)
$`x_1`$ $`=`$ $`0.1+{\displaystyle \frac{0.9}{1+0.2q^2R_g^2}}`$ (57)
$`x_2`$ $`=`$ $`0.25+{\displaystyle \frac{0.75}{1+0.1q^2R_g^2}}.`$ (58)
We recall Eq. (4.9): $`\widehat{T}_2=(N+1)^2/\pi ^2`$.

The parameterization (4.21)-(4.25) is fitted to the numerical evaluation of our theory in the range $`0.1q^2R_g^250`$; $`10N/N_e340`$; $`0\widehat{t}<\mathrm{}`$. In most of that range it reproduces our full results within deviations less than $`0.015`$ in absolute value. It becomes worse for shorter chains $`(N/N_e30)`$ and larger wave vectors $`(q\mathrm{}_02)`$ in the large time regime $`(\widehat{t}0.1\widehat{T}_3)`$. In this region the large-time tail predicted by the full theory deviates somewhat from the functional form given by the primitive chain model, and also small differences between the continuous and the discrete version of the model start to show up. For $`N/N_e10`$ our theory breaks down, mainly due to the fact that tube length fluctuations become important even for $`\widehat{t}\widehat{T}_3`$. They thus affect the kernel $`𝒫^{}(j_0t_0|m)`$ of the integral equation (4.2), and this effect has not been considered in our theory.

In the sequel we compare our Monte Carlo data to the results of the numerical evaluation of our full theory. It should be noted, however, that on the scale of the plots shown the difference between the results of the full theory and the effective parameterization (4.21)-(4.25) would be almost invisible.

## V Comparison of Monte Carlo data to full reptation theory

The reptation model in full detail treats the motion along the tube axis, but it does not account for all relaxation processes in a realistic chain. In particular, motions ‘perpendicular to the tube’, like the creation and decay of larger side branches, will be present for the Monte Carlo chain but are not treated properly in the reptation model. Since larger side branches emerge by fusion of hairpins, they in the framework of our model would introduce some kind of interaction of the particles. Scattering vectors of magnitude $`q1`$ certainly resolve such effects which result in some additional relaxation on a microscopic time scale. In fitting the data to the theory we therefore allow for a phenomenological amplitude $`A1`$, multiplying the normalized structure function $`\overline{S}_c(q,t;N)`$ calculated for pure reptation. We typically find values $`A0.9`$ for $`q=1`$, $`A0.98`$ for $`q=0.5`$, and $`A1`$ for all smaller $`q`$ measured. Thus the deviations among theory and data which are found for small times, rapidly decrease with decreasing $`q`$.

For a first illustration, we in Fig. 7 show our results for $`N=80,q=0.5024(q^2R_g^2=3.32)`$. Data points result from runs extending to $`10^5`$ or $`10^8`$ Monte Carlo steps. The full curve gives the result of our theory, with the amplitude adjusted to $`A=0.985`$. Long dashes represent a fit to the primitive chain model, with $`B_{DE}`$ and $`\widehat{T}_3=\tau _0T_3^{(MC)}`$ taken from Table 1. The short dashed curve results by neglecting tube destruction and is calculated as the structure function of a chain of length $`N`$ in an infinitely long tube. Since the primitive chain model takes care only of tube destruction, the difference among the two dashed curves is due to tube length fluctuations. Thus Fig. 7 demonstrates that the tube length fluctuations strongly influence the structure function up to times $`tT_2`$. For much larger times tube destruction is the dominant process.

These results are typical for all chain lengths and wave vectors. Figs. 8 and 9 show our results for $`N=160`$ and $`320`$, respectively. Beyond some short time regime, we find excellent agreement between theory and data, with only the amplitude $`A=A(q,N)`$ taken as adjustable parameter. Comparing Fig. 9 to Fig. 4, (note the difference of times scales: $`\mathrm{log}_{10}\widehat{t}=\mathrm{log}_{10}t^{(MC)}1.167)`$, we again see the effect of tube length fluctuations: for $`N=320`$, the primitive chain model can fit the data only for $`t20T_2`$. For smaller times, tube length fluctuations become relevant, their effect increasing with increasing $`q`$, as expected. For $`N=160,q=0.1(q^2R_g^20.267)`$, scattering cannot resolve the structure of the tube and the effect of tube length fluctuations is suppressed. The corresponding curve shown in Fig. 8 essentially coincides with the result of the primitive chain model, provided we adjust the effective time scale $`T_3`$.

To gain additional information on the chain dynamics, we also measured and calculated the structure function of the central piece of length $`M`$ in a chain of length $`N`$. Fig. 10 shows our results for $`M=80,N=320,q=0.5`$. With these parameter values it is directly comparable to Fig. 7, where $`M=N=80,q=0.5024`$. The central piece evidently is not influenced by tube length fluctuations. In contrast to Fig. 7, the decrease of $`\overline{S}_c(q,t;M,N)`$, in Fig. 10 must be due to relaxation within the initial tube, up to times where tube destruction reaches the subchain measured. Indeed, in Fig. 10 the structure function calculated neglecting tube destruction (broken line) over a large time range coincides with the results of our full theory and simulations. The time $`T_R(M,N)`$ it needs for tube destruction to reach the subchain, can be estimated from the relation

$$\overline{\mathrm{}}_Sn_{\mathrm{max}}(T_R(M,N))=\frac{1}{2}(NM).$$
(59)
This time is indicated in Fig. 10 and is close to the time where the dashed line starts to deviate from our full result. Recall from Sect. 4.A that $`\mathrm{}_S\overline{n_{\mathrm{max}}(t)}`$ gives the average length of the end-piece of the tube that has been destroyed up to time $`t`$.

As pointed out in Sect. 4.C, the decrease of $`\overline{S}_c(q,t;M,N)`$ seen in Fig. 10 in the range $`t<T_R(M,N)`$ is not due to relaxation within the subchain $`M`$ considered, but results from the internal dynamics of the total chain which leads to fluctuations of the position of the subchain in the original tube. This is illustrated in Fig. 11, which for given $`N=320`$ and $`q=1.0`$ compares the scattering from central subchains of lengths $`M=40,\mathrm{\hspace{0.33em}80},\mathrm{\hspace{0.33em}160},\mathrm{\hspace{0.33em}320}`$. We note some peculiar behavior: as function of time, the normalized scattering function of the total chain $`M=N=320`$ initially decreases faster and eventually crosses results for internal pieces. This shows the efficiency of tube length fluctuations in comparison to the internal dynamics of the chain. According to the discussion of Sect. 4.C, subchains $`MN\sqrt{\frac{1}{3}N_eN}300`$ (for $`N=320)`$ are not influenced by tube length fluctuations, and for a large time range scattering from such subchains is determined by the diffusive motion of the total subchain in the initial tube. Since the diffusion coefficient of this motion scales as $`1/M`$, the diffusion of the longer subchains is very slow. Taking place in the initial tube, it is also less efficient in reducing $`\overline{S}_c`$ than tube length fluctuations or the tube destructing shift of the total chain. For these reasons, the normalized coherent scattering for $`M=160`$ stays above the result for the total chain up to times $`tT_3\left(N\right)`$. For larger times the theory predicts that as for the shorter subchains the normalized scattering from subchain $`M=160`$ falls below the scattering from the total chain, but the effect is too small to be visible in Fig. 11, and it clearly is not resolved by the accuracy of the data. We also note that tube destruction reaches the initial position of the subchain $`M=160`$ only for $`pT_R(160,320)10^{5.8}`$. With decreasing $`M`$, diffusion in the tube becomes faster, and for the shortest subchain, $`M=40`$, we see indications of a new regime: the slope of the curve seems to change near $`\widehat{t}=10^{5.4}`$. A doubly logarithmic plot reveals that in the range $`10^{5.4}\widehat{t}10^{6.1}`$ the data approach a $`\widehat{t}^{1/2}`$-law, and the upper bound of this interval is close to the time $`pT_R(40,320)10^{6.4}`$. These observations are consistent with the discussion of Sect. 4.C.

Finally we consider the deviations between theory and data present for $`\widehat{t}10^3`$ and large wave vectors. A first important observation is that these deviations roughly are of the same size for interior pieces of the chain as for the total chain, see Fig. 11. Therefore their dominant source cannot be searched in our treatment of tube length fluctuations in the mean hopping rate approximation. To show this in more detail, we in Fig. 12 have plotted the deviation between data and theory for wave vector $`q=1.0`$ and all chains and subchains measured. We note some end-effect: for the total chain $`N=160=M`$ the deviation is about 20 % larger than for the central piece $`M=160`$ in the chain $`N=320`$. However, the bulk of the effect is independent of $`N>M`$, as illustrated by the curves for $`M=40`$ and $`M=80`$, which each in fact combine data for $`N=160`$ and $`N=320`$. For these internal pieces, tube length fluctuations are irrelevant, and in the time range shown, our evaluation of the reptation model is exact within the accuracy (0.5 %) of our numerics. Consequently the initial deviations must be dominated by some relaxation in the interior of the subchain $`M`$ which is not taken into account by the reptation model. We note that the amplitude $`A`$ of the effect depends on $`M`$ only weakly, but strongly increases with $`q`$, as is illustrated by Figs. 8 and 9. It roughly is proportional to $`q^2`$. These observations are consistent with an interpretation as micro-structure effects, which clearly increase strongly with the resolving power of the experiment and are expected to show a weak dependence $`1/M`$ on (sub-)chain length.

In our previous work on the motion of individual segments, we found initial transients which also decayed on a time scale $`\widehat{t}10^3`$. These could be traced back to the discreteness of both the hopping process and the underlying chain and could be largely explained by a fully discrete analysis of our model. As mentioned in Sect. 4.A, it turns out that for $`\overline{S}_c(q,t,M,N)`$ this discreteness numerically is irrelevant. In the light of the discussion of Sect. 4.C, this is quite understandable: the internal dynamics of the subchain averages out. We thus have to search for effects going beyond our implementation of the reptation model. One source of discrepancy immediately comes into mind. A particle sitting on a bead is no exact representation of a hairpin. It, for instance, is not clear whether the bead sits in the tip or in the base of the hairpin. Simple estimates of such effects easily yield a correction amplitude $`1A`$ of the desired order of magnitude. However, the dynamics of single hairpins cannot explain a time scale of order $`10^3`$ since it essentially relaxes within one Monte Carlo step. Slower relaxation occurs for larger side branches. Already a structure created by fusion of two hairpins shows a relaxation time of the order of $`10MC`$ steps. Indeed, the fusion of hairpins destroys mobile units of the Monte Carlo chain. In the language of our model this induces some dynamical interaction of the particles. We therefore believe that the observed initial transients are due to the interference of reptation with the dynamics of larger side branches.

## VI Conclusions

In this paper, we presented results of simulations of the Evans-Edwards model, measuring the coherent structure function of a reptating chain in a large range of time and wave vector. This model contains the full reptational dynamics of a single chain, including internal relaxation, tube length fluctuations, and tube renewal, but omits all the dynamics of the environment. In particular, it ignores constraint release. We compared the data to two simplified versions of the reptation model as well as to our recent evaluation of the full theory. We found that the primitive chain model proposed by Doi and Edwards  yields a good fit to the data for times large compared to the Rouse time $`T_2`$, provided we allow for a phenomenological amplitude factor and treat the reptation time $`T_3`$ as a second adjustable parameter. De Gennes’ approach  which adds a contribution meant to take one dimensional internal relaxation along the tube into account, cannot explain the data consistently. So the success of this approach in fitting neutron scattering data on polymer melts  indicates that the local contribution $`S^{(\mathrm{})}(q,t)`$ to De Gennes’ structure function phenomenologically accounts for some dynamics not contained in the reptation model. In view of our findings for the Evans-Edwards model we would search the origin of the observed initial decay in a coupling of reptation to motion perpendicular to the tube. Since in the experimental time range the initial decay accounts for most of the variation of the experimental curves , we have not tried to fit these curves with our theory.

Provided we allow for a single adjustable amplitude factor we, beyond the short time range influenced by microstructure relaxation, find quantitative agreement between our simulation data and our analytical evaluation  of full reptation theory. The theory in all details explains not only the scattering function of the total chain but also the scattering from interior subchains. Except for the phenomenological amplitude, which notably differs from $`1`$ only for wave vectors of the order of the inverse segment size, all parameters of the theory essentially are fixed by our previous analysis  of the motion of internal segments. Thus our version of the reptation model consistently explains both details of the internal motion and global features like the scattering function.

Our analysis shows that the effects of internal relaxation contained in the reptation model and seen, for instance, in the motion of internal segments, for the scattering functions average out. In the reptation model, the time dependence of the scattering functions is determined solely by the interplay of tube destruction and tube length fluctuations. The latter not only determine the scattering function up to times of order $`T_2`$, but also for intermediate chain lengths lead to the decrease  of the reptation time $`T_3`$ in comparison to the asymptotic law, clearly seen also in the scattering function. Numerically evaluating our theory, we found these effects to be well visible up to chain lengths of the order of 300 entanglement lengths. This is obvious from the numerical parameterization of our results, given in Section 4 D.

Our theory deviates from the results of the simulation in the initial time region $`\widehat{t}10^3`$. We stress that this is not due to the approximations inherent in our treatment of tube destruction. Deviations of the same order of magnitude occur for the total chain and for internal subchains, and the coherent structure function of internal subchains in the initial time region is not affected by our approximations. Thus the need to introduce some phenomenological parameter to take short time relaxation into account illustrates that even for the Evans-Edwards model, which is the most accurate computer-experimental implementation of the reptation model we can think of, some relaxation ’perpendicular’ to the tube shows up. Clearly, for a melt, such effects must be much larger. However, our analysis suggests some way to suppress these contributions. The scattering from a chain of length $`N=M`$ should be compared to the scattering from the central piece of length $`M`$ in a chain of length $`N2M`$. Up to small end effects, the difference of the two coherent scattering functions should be due to reptation alone, and can be calculated from our theory. To observe an effect, the experiments must cover a time range extending at least up to the Rouse time, with chain length being of the order $`N/N_e20`$. Unfortunately, for physical experiments, this seems to be out of reach. As shown by the work of Ref.  it might be feasible in simulations.
Acknowledgment: This work was supported by the Deutsche Forschungsgemeinschaft, SFB 237.