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# Dynamics of Living Polymers

## 1 Introduction

Living polymers are intriguing examples of soft matter and have major roles in technology and biology. The classic system, of major importance for the synthesis of high-grade polymer materials and the subject of a long history of fundamental experimental and theoretical study, is living anionic polymerization szwarcvanbeylen:book ; greer:review ; greer:annual\_review ; greer:living\_review\_jphyschem ; zheng:greer:living\_1 ; zheng:greer:living\_2 ; andrews:greer:living\_3 ; sarkar:greer:living\_4 ; zhuang:greer:living\_5 ; pfeuty:greer:living\_preliminary ; garcia:greer:living\_nonumber ; zhuang:greer\_kinetics ; das:greer:living\_7\_mwd ; kennedywheeler:living\_critical ; wheeler:polymerization\_critical ; wheelerpfeuty:polymerization ; wheelerpfeuty:polymerization\_fluc ; schafer:rg\_mwd ; kaufman:plztn\_equiv\_neighbor\_lattice ; wheelerpetschek:living\_mwd\_bound ; dudowicz:living\_i ; dudowicz:living\_ii ; dudowicz:living\_iii ; schoot:living\_scaling ; frischknechtmilner:living\_aggregation . This class of polymerization is widely employed to manufacture polymers with nearly monodisperse MWDs and controlled architectures such as block and star copolymers webster:living\_review . A recent variant on this theme with immense potential technological impact is living free radical polymerization hawker:review:living\_frp ; georges:living\_frp . Other examples include worm-like surfactant micelles marques:end-evaporation ; milchev:monomer\_mediated\_relaxation ; marquescates:wlike\_dynamics\_exact ; catescandau:living\_review ; wittmer:milchev:cates:equilibrium\_polymers\_montecarlo ; wittmer:wormlike\_mwd\_numerical ; spenley:rheology\_wormlike ; ben:living\_letter  and biological polymers such as actin and tubulin filaments oosawaasakura:book ; hill:aggr\_bio\_book ; korn:actin\_review\_science ; pollardcooper:actin\_review ; desaimitchison:mtub\_review ; flyvbjerg:leibler\_microtubules\_prl  whose special properties are exploited by living cells for motility and structural integrity.

As polymeric or polymer-like materials, the unique feature of these systems is that the chains are dynamic objects, with constantly fluctuating lengths. When subjected to an external perturbation, they are able to respond dynamically via polymerization and depolymerization reactions allowing a new thermodynamic equilibrium to be attained. These systems are “living” in the sense that a change in their environment leads to a new equilibrium molecular weight distribution (MWD). All of this should be compared to conventional inert polymer materials whose MWDs are frozen.

The subject of this paper is the dynamical response of living polymers. We study the class of living polymers which is exemplified by living ionic polymerization, having the following characteristics: (i) monomers add and subtract from chain ends and (ii) the total number of chains is fixed. In the biological world, actin and microtubule filaments satisfy condition (i), and the dynamics of both filaments and filament caps are frequently described by situation (ii) ben:actin\_cap\_letter . Wormlike micelles on the other hand in some cases grow from their ends only marques:end-evaporation ; milchev:monomer\_mediated\_relaxation  (condition (i)) but do not satisfy condition (ii): the number of micelles is not conserved. Interestingly, this makes their dynamical response very different (see discussion section).

Our presentation will focus on living ionic polymerization, though most of our results are completely general. In these systems, polymers grow reversibly from their ionic ends (see fig. 1). Due to their “living” nature, if fresh monomer is added polymers will grow until the extra monomer has been consumed; further addition of a different monomer species, say, will resume polymer growth. The main achievement of this technique is a distribution of chain lengths with very small Poisson fluctuations around the mean. This monodisperse MWD is not however a true equilibrium distribution. For sufficiently long times slow depolymerization reactions become important and lead to a true equilibrium MWD which is in fact extremely broad. For many applications, for example styrene, the timescale to reach equilibrium is extremely large and depolymerization-induced broadening effects are unimportant miyakestockmayer:living . However, in some cases equilibration times are accessible, an example being $`\alpha `$-methylstyrene whose equilibrium properties have been studied in many experiments greer:review ; greer:annual\_review ; greer:living\_review\_jphyschem ; zheng:greer:living\_1 ; zheng:greer:living\_2 ; andrews:greer:living\_3 ; sarkar:greer:living\_4 ; zhuang:greer:living\_5 ; pfeuty:greer:living\_preliminary ; garcia:greer:living\_nonumber ; zhuang:greer\_kinetics ; das:greer:living\_7\_mwd .

The reason that chain length fluctuations in equilibrium are so large is that even when a state is reached where the monomer concentration reaches a steady state value such that polymer growth rates exactly balance depolymerization, through polymerization and depolymerization reactions monomers continue to be reshuffled among living chains. Thus even if one starts with an essentially monodisperse MWD as shown in fig. 2(a), random addition and subtraction of monomers from chain ends will result in a “diffusive” random walk motion of chain ends in $`N`$-space (where $`N`$ is the number of monomer units added to initiator) with a certain characteristic “diffusivity” $`D`$. Since there is no restoring force to this motion, chain ends will eventually diffuse to distances of the same order as the mean chain length, resulting in a broad distribution as shown in fig. 2(b). In a simple mean-field picture where monomer-monomer excluded volume interactions are neglected this leads to the Flory-Schultz equilibrium distribution flory:book ; tobolsky:living\_mwd ; greer:annual\_review

$$\varphi _{\mathrm{}}(N)=\frac{1}{\overline{N}_{\mathrm{}}}e^{N/\overline{N}_{\mathrm{}}},$$
(1)
where $`\overline{N}_{\mathrm{}}`$ is the equilibrium mean length.

The thermodynamic properties of equilibrium living polymers have been studied in a large number of experimental and theoretical works. According to theory, going beyond mean field by accounting for excluded-volume interactions leads to power law modifications schafer:rg\_mwd ; kaufman:plztn\_equiv\_neighbor\_lattice ; wheelerpetschek:living\_mwd\_bound ; wittmer:wormlike\_mwd\_numerical  to eq. (1). Moreover, an analogy kennedywheeler:living\_critical ; wheeler:polymerization\_critical ; wheelerpfeuty:polymerization ; wheelerpfeuty:polymerization\_fluc  between a living polymer system and the much studied Ising spin system in the formal limit of spin dimensionality $`n`$ becoming zero (similar to the well-known analogy in the thermodynamic theory of semidilute polymer solutions gennes:book ; cloizeauxjannink:book  which can in fact be formulated equivalently to a living polymer system cloizeaux:pol\_rg\_many ) showed that the polymerization phase transition near the polymerization temperature is second-order with a number of characteristic power-law exponents. The results of a large number of experiments by the group of Greer, measuring both the MWD itself das:greer:living\_7\_mwd  and other thermodynamic properties greer:review ; greer:living\_review\_jphyschem  are apparently consistent with the above theories, favoring somewhat the non mean-field approach.

The most essential feature of living polymers however, namely their ability to respond dynamically to external perturbations, remains largely unexplored. How does an equilibrium living polymer system respond to a small perturbation? A conceptually simple perturbation is the addition of a small amount of extra monomer (an “$`m`$-jump”). A similar perturbation, easier to perform in practice, is a “$`T`$-jump,” i. e. a small sudden change in temperature. Under such a perturbation, how rapidly and in what manner will the monomer concentration, MWD and mean chain length reach a new equilibrium? In this paper we address these questions theoretically. We will compare our predictions in section 8 with small $`T`$-jump viscosity relaxation experiments by Greer et al. garcia:greer:living\_nonumber . This same group has also monitored monomer and MWD dynamics following much stronger perturbations, finite temperature quencheszhuang:greer\_kinetics ; das:greer:living\_7\_mwd  (see fig. 3).

Our main broad conclusion is that, counter-intuitively, the response to a very small perturbation is extremely strong: even though the initial and final MWDs (the latter attained after relaxation is complete) are very close to one another, the MWD at intermediate times is very strongly perturbed from equilibrium, i. e. its shape is very different from either the initial or final equilibrium shapes. In this sense, there are no small perturbations: a small thermodynamic perturbation well-described by a linear susceptibility (i.e. one inducing a small change in the equilibrium state) has nonetheless a large dynamical effect; intermediate states deviate strongly from equilibrium in the sense that observables are perturbed in a highly non-linear manner. We refer to this as dynamical ultrasensitivity.

A hint of this sensitivity is already apparent in equilibrium, where a very delicate balance is established between growth and shrinkage such that the net polymerization velocity $`v`$ is essentially zero, of order $`1/\overline{N}_{\mathrm{}}`$ (due to the small fraction of special non-depolymerizable chains of length $`N=0`$). Now the effect of a small T-jump (say) is to produce a small but finite velocity which overwhelms this tiny velocity value and destroys the delicate balance sustaining equilibrium. Thus if for example $`v`$ becomes positive, the MWD will uniformly translate toward larger molecular weights, creating a depletion in the MWD at small chain lengths, as shown schematically in fig 4. This translation process stops only after sufficient monomer has been polymerized such that the monomer concentration drops close to its destination equilibrium value, corresponding to a recovery of the zero net growth rate equilibrium condition. We find that only on a much longer timescale does “diffusion” of chain ends fill up the hole and lead the system to the destination equilibrium MWD, as shown in fig. 4.

Why does this hole develop in the MWD? The reason is that chain length scales homogenized by diffusion, $`(Dt)^{1/2}`$, are smaller than scales affected by translational motion, $`vt`$, for times longer than the timescale $`t^{}D/v^2`$. Thus if $`t^{}`$ is shorter than the timescale needed for translation to stop, a depletion hole develops in the MWD. But even when translation is completed earlier than $`t^{}`$, we find that the perturbation is still nonlinear; even though no hole is formed there is still a large amplitude reduction in the MWD, much larger than the relative magnitude of the initial perturbation, $`ϵ`$.

This work is related to earlier theory of Miyake and Stockmayer miyakestockmayer:living  who, following a prior treatment by Brown and Szwarc brownszwarc:living\_ancient , studied analytically and numerically the dynamics in the special case where initially all monomer is unpolymerized (see fig. 5). Their analytical results, applicable in the case of very small depolymerization rates, showed a 2-stage relaxation. During the first, lasting a time $`\overline{N}_{\mathrm{}}`$, living chains grow coherently from zero length up to the equilibrium value. In the second stage the shape of the sharply peaked MWD relaxes slowly toward the equilibrium exponential distribution. Although their perturbation analysis broke down during this stage, Miyake and Stockmayer estimated that its duration scales as $`\overline{N}_{\mathrm{}}^2`$. Later theoretical studies addressed the second stage dynamics nandajain:living\_broadening ; auluck:living\_mwd\_intermediate ; taganov:living\_mwd  of this special case.

A short announcement of the present work has already appeared ben:living\_ionic\_letter . The structure of the paper is as follows. In section 2 we establish the dynamical equations obeyed by living polymers which show the nonlinear coupling between the monomer population and the living chain MWD. For simplicity, we neglect excluded volume interactions and chain length dependent polymerization rates. Starting from the equations of section 2 we then analyze the response to a $`T`$-jump. This response depends on the sign of the velocity induced by the perturbation. The case of positive initial velocity is analyzed in sections 3 and 4, while the negative in section 5. The special case of very small $`T`$-jumps is analyzed in section 6. In section 7 we show that the results of the previous sections directly generalize to small perturbations of arbitrary form. Finally we conclude with a discussion of the results, and the experimental outlook.

## 2 Living Polymer Dynamics: Monomer-Polymer Coupling

An important aspect of living polymers dynamics is the coupling between the two distinct species present in the solution, free monomers and living chain MWD: on the one hand living chain growth rates depend on the concentration of free monomer and on the other hand, due to mass conservation, monomer concentration if a function of the living chain MWD. Stated differently, living chains grow according to a velocity field which is self-consistently updated depending on the response of the MWD. In this section we develop the equations obeyed by monomer and MWD. The dynamical response to perturbations is discussed in the following sections.

A crucial feature of the living polymer systems we study is that the number of living chains remains fixed. This is what arises in the experiments of Greer et al. greer:review ; greer:living\_review\_jphyschem ; greer:annual\_review , where this number is determined by the amount of initiator initially added in the solution. Denoting $`i_0`$ the concentration of living chains (i. e. chains which have been initiated), mass conservation implies that monomer concentration, $`m_t`$, and MWD, $`\varphi _t(N)`$, ($`t`$ denotes time) obey

$$m_t=m_{\mathrm{tot}}i_0\overline{N}_t,\overline{N}_t_0^{\mathrm{}}𝑑NN\varphi _t(N),$$
(2)
where $`m_{\mathrm{tot}}`$ is the total monomer concentration (including polymerized monomers), and $`\overline{N}_t`$ is mean chain length. Here $`\varphi _t`$ is normalized to unity and $`N=0`$ corresponds to free initiator. The coupling between monomer concentration and the MWD is manifest in eq. (2).

Now the dynamical equations equations obeyed by $`\varphi _t`$ are

$`{\displaystyle \frac{\varphi _t(N)}{t}}={\displaystyle \frac{j_t(N)}{N}},`$
$`j_t(N)v_t\varphi _t(N)D_t{\displaystyle \frac{\varphi _t(N)}{N}},j_t(0)=0,`$ (3)
where

$$v_tk^+m_tv^{},D_t(k^+m_t+v^{})/2.$$
(4)
Here $`k^+`$ is the propagation rate constant and $`v^{}`$ is the depolymerization rate. The “diffusion” coefficient $`D_t`$, describes fluctuations in the rate of polymerization/depolymerization. Eq. (2) is identical to the diffusion dynamics of a particle in a linear potential with time-dependent slope $`v_t`$ whose time-dependent diffusion coefficient is $`D_t`$ (see fig. 6). The novelty here is that due to the coupling between the MWD and monomer, both the slope and diffusivity are functionals of $`\varphi `$ itself.

The reflecting boundary condition in eq. (2) at $`N=0`$ represents the fact that when a living chain looses all of its monomers and becomes a free initiator molecule (i. e. reaches length $`N=0`$) it cannot depolymerize further and must grow again. Now we restate eq. (2) as

$$\frac{\varphi _t}{t}=v_t\frac{\varphi _t}{N}+D_t\frac{^2\varphi _t}{N^2},\varphi _t(0)/\varphi _t^{}(0)=D_t/v_t,$$
(5)
where $`\varphi _t^{}\varphi _t/N`$.

Now it might at first seem that despite the coupling of eq. (2), the monomer subsystem would effectively uncouple from the MWD dynamics, since one might naively expect that the monomer dynamics do not depend on the shape of the polymer MWD but only on the number of living chains. This would imply simple first order kinetics for $`m_t`$ resulting in exponential relaxation of the monomer concentration, independent of the MWD dynamics. The coupling however arises from the existence of special chains in the MWD of zero length, i. e. free initiator molecules of which there are $`\varphi _t(0)`$, which unlike all other chains cannot depolymerize. Indeed, the dynamics obeyed by $`m_t`$, or equivalently $`v_t`$, are

$$\frac{dv_t}{dt}=\frac{v_t}{\tau _{\mathrm{fast}}}\frac{D_t\varphi _t(0)}{\tau _{\mathrm{fast}}},\tau _{\mathrm{fast}}\frac{f}{rv^{}}\frac{f\overline{N}_{\mathrm{}}}{(1f)v^{}}.$$
(6)
We see clearly that the only aspect of the living MWD which monomers see is $`\varphi _t(0)`$. Eq. (6) is derived by calculating $`d\overline{N}_t/dt`$ by multiplying eq. (2) by $`N`$, integrating over all $`N`$, using the reflecting boundary condition, and then using eq. (2). The relationship between $`\tau _{\mathrm{fast}}`$ and $`\overline{N}_{\mathrm{}}`$ follows from eq. (8) below. Here we have introduced the two basic independent dimensionless parameters of the system:

$$f\frac{v^{}}{k^+m_{\mathrm{tot}}},r\frac{i_0}{m_{\mathrm{tot}}}.$$
(7)
The physical meaning of $`f`$ is the following: if the system were a pure solution of unpolymerized monomer (plus solvent and initiator) $`f`$ would be the ratio of backward to forward polymerization velocities. The value of $`f`$ is temperature dependent, being unity at the polymerization temperature and smaller or larger than unity in the polymer and non-polymer phase, respectively. The parameter $`r`$, namely the ratio of living chain to total monomer concentration, is independent of temperature and is always much smaller than unity. Its smallness is related to the mean degree of polymerization being much larger than unity in equilibrium (see eq. (8) below).

Now setting the time derivative in eq. (5) to zero and using eq. (2) it is shown in Appendix A that in equilibrium the Flory-Schultz distribution of eq. (1) is recovered and one has to leading order in $`r`$:

$$\overline{N}_{\mathrm{}}\frac{1f}{r},\frac{m_{\mathrm{}}}{m_{\mathrm{tot}}}f,v_{\mathrm{}}\frac{v^{}}{\overline{N}_{\mathrm{}}},D_{\mathrm{}}v^{},$$
(8)
where $`r1`$ and subscript $`\mathrm{}`$ denotes the $`t\mathrm{}`$ equilibrium value for the corresponding variable. We assumed $`(1f)/r^{1/2}1`$, i. e. that the temperature is not extremely close to the polymerization temperature.

An important feature in eq. (8) is that in equilibrium the velocity, i. e. the slope of the “potential” term in eq. (5), settles down to a very small negative value. Were there no diffusion, living chains subject to a negative velocity field would shrink to zero length. However due to the small magnitude of the velocity, diffusion is strong enough to broaden the MWD up to distances of order $`\overline{N}_{\mathrm{}}`$, as illustrated in fig. 2. We show in the following section that any apparently small external perturbation has an enormous effect on the velocity which, depending on the direction of the perturbation, may become either very negative or very positive.

## 3 Response to $`T`$-jump; Positive Velocity Boost

Perhaps the simplest way to perturb an equilibrium living polymer system is by a small temperature change ($`T`$-jump). Taking as an example $`\alpha `$-methylstyrene, the data of fig. 7 show equilibrium fraction of polymerized monomer as a function of temperature; evidently, changes in $`T`$ lead to different values of the equilibrium monomer concentration $`m_{\mathrm{}}`$ and therefore of $`\overline{N}_{\mathrm{}}`$ as well. In this section we consider relaxation dynamics after an equilibrated system is subjected at $`t=0`$ to a small temperature change $`\delta T`$ such that the system will eventually reach new equilibrium values $`m_{\mathrm{}}`$ and $`\overline{N}_{\mathrm{}}`$. That is, we follow the dynamics of the transition from an old equilibrium towards a slightly different new equilibrium state.

The magnitude of the perturbation is measured by the small parameter

$$ϵ\frac{\delta m_0}{m_{\mathrm{}}},$$
(9)
where we define $`\delta m_tm_tm_{\mathrm{}}`$ and similarly for other quantities. All equilibrium values refer to the destination ($`t=\mathrm{}`$) equilibrium values. Thus $`\delta m_0`$ is the initial ($`t=0`$) deviation from the final equilibrium.

The value of $`ϵ`$ is related to the magnitude of the $`T`$-jump. For example in the case of $`\alpha `$-methylstyrene, assuming that the system is initially below the polymerization temperature $`T_p`$ in the region of fig. 7 between 260K and 280K, one has using eq. (9)

$$ϵ\frac{\delta T}{50^{}\mathrm{K}}\text{(}\alpha \text{-methylstyrene)}.$$
(10)
Thus for $`\alpha `$-methylstyrene a temperature increase, $`\delta T>0`$, results in a negative $`\delta m_0`$, i. e. a reduced initial monomer concentration relative to the destination equilibrium value.

Now the $`t=0`$ relative perturbation of the MWD is

$$\frac{\delta \varphi _0(N)}{\varphi _{\mathrm{}}(N)}\frac{\varphi _{\mathrm{}}(N)}{\overline{N}_{\mathrm{}}}\frac{\delta \overline{N}_0}{\varphi _{\mathrm{}}(N)}=\frac{ϵ}{\theta }\left(1\frac{N}{\overline{N}_{\mathrm{}}}\right),\theta \frac{1f}{f}.$$
(11)
This is of order $`ϵ`$ and smaller than unity for all $`N`$ (apart from the unimportant values $`N\overline{N}_{\mathrm{}}`$ where the MWD is exponentially small) as shown in fig. 8(a).

Because velocity, monomer concentration and mean chain length are all linearly related (see eqs. (2),(8) and (4)) changes in these quantities are simply related as

$$\frac{\delta m_t}{m_{\mathrm{}}}\theta \frac{\delta \overline{N}_t}{\overline{N}_{\mathrm{}}}\mathrm{\hspace{0.17em}2}\frac{\delta D_t}{D_{\mathrm{}}}\frac{\delta v_t}{v^{}}.$$
(12)
These relations are true for all times. They allow us to follow the dynamics of velocity alone. Once $`v_t`$ is known, $`\overline{N}_t`$, $`m_t`$, $`D_t`$ are determined.

From eqs. (12) and (9) the initial relative changes in $`v,D`$ are:

$$\frac{\delta v_0}{v_{\mathrm{}}}ϵ\overline{N}_{\mathrm{}},\frac{\delta D_0}{D_{\mathrm{}}}\frac{ϵ}{2}.$$
(13)
The important point is that since $`\overline{N}_{\mathrm{}}1`$, the relative change in $`v`$ is much larger than $`ϵ`$ : the velocity is highly perturbed, as shown in fig. 6. Depending on the sign of $`ϵ`$, the velocity may remain negative as in equilibrium, or it may change sign. Since the relative perturbation in $`D`$ is by contrast small, we see that the delicate velocity-diffusion balance which sustained equilibrium is now destroyed.

We will show below that relaxation to equilibrium now occurs in three stages. During the first, dominated by translational motion, the MWD is boosted far from its equilibrium shape. The next stage involves diffusive restoration of the region of the MWD which suffered maximum distortion during the first stage. The third and final episode entails a very slow diffusion-dominated recovery of the global MWD. For the remainder of this section we treat the case of a positive initial velocity boost, where chains initially grow ($`\delta T<0`$ for $`\alpha `$-methylstyrene). Negative velocity boosts, where chains initially shrink, are considered in section 5.

### 3.1 Coherent Chain Growth: Hole Development

During the first stage of the relaxation process, velocity dominates over diffusion since $`v`$ has been so strongly perturbed. Chains thus grow coherently, consuming the excess monomer in a timescale $`\tau _{\mathrm{fast}}`$ by which time translation will have halted and a highly non-linear hole will have developed in the MWD (see fig. 9). Here $`\tau _{\mathrm{fast}}`$, defined in eq. (6), is the time for the MWD to translate distance $`\delta \overline{N}_0`$ and reach the destination mean, i. e. $`\tau _{\mathrm{fast}}\delta \overline{N}_0/\delta v_0`$ (see eqs. (9), (13) and using eq. (8)).

To see all of this more quantitatively, consider the velocity dynamics eq. (6). Initially, the velocity term on the rhs is much larger in magnitude than the diffusion term. We show in Appendix B that this remains true up until a time $`\tau _{\mathrm{qs}}`$, defined below. It follows that for these times $`v_t`$ relaxes exponentially. The same is true of $`m_t,\overline{N}_t`$ and $`D_t`$ which we recall are linearly coupled to $`v_t`$ (see eq. (12)). Thus

$$\delta v_tϵv^{}e^{t/\tau _{\mathrm{fast}}}v_{\mathrm{}}(t\tau _{\mathrm{qs}}=ϵ\overline{N}_{\mathrm{}}^{3/2}\theta ^{3/2}/v^{}).$$
(14)
Note that for $`t\tau _{\mathrm{fast}}`$ there are no free initiators (at much longer times these are restored, see below). Thus for these intermediate times all chains are identical as far as on and off monomer kinetics are concerned, and the net rate of monomer-polymer mass exchange can only vanish if $`v_t`$ vanishes. For this reason $`v_t`$ decays to zero, though much later it will recover its small negative equilibrium value. The $`\varphi _t`$ dynamics, eq. (5), thus simplify to

$$\frac{\varphi _t}{t}ϵv^{}e^{t/\tau _{\mathrm{fast}}}\frac{\varphi _t}{N}+D_{\mathrm{}}\frac{^2\varphi _t}{N^2}(t\tau _{\mathrm{qs}})$$
(15)
where the diffusion coefficient may be approximated by $`D_{\mathrm{}}`$ since the contribution of $`\delta D_t`$ is negligible (see Appendix B). This linear equation, plus the time-dependent boundary condition of eq. (5), has solution

$$\varphi _t(N)_0^{\mathrm{}}𝑑N^{}G_t^{\mathrm{tran}}(N,N^{})\varphi _0(N^{})(t\tau _{\mathrm{qs}})$$
(16)
which describes a translating and simultaneously broadening MWD, as shown in fig. 9. Here $`G_t^{\mathrm{tran}}(N,N^{})`$ is the propagator of eq. (15) whose properties are calculated in Appendix B.

An important quantity in what follows is $`\varphi _t(0)`$, i. e. the concentration of free initiators. Using eq. (16) we show in Appendix B that

$`\varphi _t(0)/\varphi _{\mathrm{}}(0)`$
$`\{\begin{array}{cc}1C(t/t^{})^{1/2}\hfill & (tt^{})\hfill \\ F(t^{}/t)^{3/2}e^{t/t^{}}\hfill & (t^{}t\tau _{\mathrm{fast}})\hfill \end{array}t^{}{\displaystyle \frac{4D_{\mathrm{}}}{v_0^2}},`$ (19)
where $`C=4/\pi ^{1/2}`$ and $`F=\pi ^{1/2}`$. Eq. (3.1) has a clear physical meaning: as the MWD translates, the position of its peak at $`N=0`$ after time $`t`$ has shifted to chain lengths of order $`v_0t`$. Were diffusion absent, this would have created a depletion region in the MWD at small chain lengths. However diffusion smooths out inhomogeneities on distances of size $`(D_{\mathrm{}}t)^{1/2}`$. Hence for times shorter than the crossover time $`t^{}`$ for which $`v_0t^{}(D_{\mathrm{}}t^{})^{1/2}`$, diffusion has enough time to fill the translationally induced hole and the relative deviation from equilibrium is small. For times longer than $`t^{}`$ however, the MWD translates a distance away from the origin much larger than what diffusion could have homogenized, a hole develops in the MWD, and the concentration of zero length chains becomes exponentially small.

In eq. (3.1) we assumed that the perturbation is large enough such that $`t^{}\tau _{\mathrm{fast}}`$. The special case of extremely small perturbations where this is no longer true is discussed separately in section 5.

### 3.2 Diffusive Length Relaxation: Hole Filling

For times $`t\tau _{\mathrm{fast}}`$ the fast variables monomer and mean chain length have relaxed very close to their equilibrium values. We have seen that velocity becomes exponentially small. Meanwhile (see below) the number of free initiators $`\varphi _t(0)`$ is gradually recovering. At a certain moment, therefore, the 2 terms on rhs of eq. (6) become equal to one another and we show in Appendix B that for all later times the velocity time derivative is much smaller. Hence the velocity dynamics are now fundamentally changed. The new regime is one of quasi-static evolution, enslaved to the dynamics of $`\varphi _t(0)`$:

$$\delta v_tv^{}\delta \varphi _t(0)(t\tau _{\mathrm{qs}}).$$
(20)
Physically, this reflects the fact that the the only aspect of the MWD shape seen by monomers is the amount of special non-depolymerizing zero-length chains. We see that as the MWD slowly rearranges itself, so the fast variables $`v_t,m_t`$ and $`\overline{N}_t`$ variables respond quasi-statically.

Notice that the quasi-static regime does not onset after $`\tau _{\mathrm{fast}}`$ but rather after $`\tau _{\mathrm{qs}}`$. The reason is that during the initial boost the term $`D_t\varphi _t(0)`$ in eq. (6) decays exponentially on a timescale $`t^{}`$; its magnitude therefore at $`\tau _{\mathrm{fast}}`$ is much smaller than $`v_t`$ which decays on a timescale $`\tau _{\mathrm{fast}}`$ (see eqs. (14) and (3.1)). There is thus a cross-over period before the quasi-static balance between the two terms is established.

Now let us examine the MWD dynamics. Since $`v_t`$ becomes exponentially small after the MWD stops translating, we have

$$\frac{\varphi _t}{t}D_{\mathrm{}}\frac{^2\varphi _t}{N^2}(\tau _{\mathrm{fast}}t\tau _{\mathrm{fill}})$$
(21)
with reflecting boundary conditions at the origin. Here once again the contribution of $`\delta D_t`$ is negligible (see eqs. (12), (20), and (23)) and the corresponding term has been neglected in eq. (21). Here

$$\tau _{\mathrm{fill}}ϵ^2\theta ^2\tau _{\mathrm{slow}},\tau _{\mathrm{slow}}\frac{\overline{N}_{\mathrm{}}^2}{4D_{\mathrm{}}}.$$
(22)
The timescale $`\tau _{\mathrm{slow}}`$ is the longest relaxation time of the system, the time for the slow global shape characteristics of the MWD to relax. It equals the diffusion time for the MWD width $`\overline{N}_{\mathrm{}}`$. Meanwhile $`\tau _{\mathrm{fill}}`$ is the diffusion time for the hole width, $`ϵ\overline{N}_{\mathrm{}}/\theta `$. It is shown in Appendix B that eq. (21) has solution

$$\frac{\varphi _t(0)}{\varphi _{\mathrm{}}(0)}H\left(\frac{t}{\tau _{\mathrm{fill}}}\right)^{1/2}e^{\tau _{\mathrm{fill}}/t}(\tau _{\mathrm{fast}}t\tau _{\mathrm{fill}})$$
(23)
where $`H=\pi ^{1/2}`$. Thus for times shorter than $`\tau _{\mathrm{fill}}`$ the concentration of zero length chains remains exponentially small while for longer times the hole fills (see fig. 10) and $`\varphi _t(0)`$ recovers its equilibrium value.

### 3.3 Linearized Dynamics at Long Times

For times beyond $`\tau _{\mathrm{fill}}`$ the hole-filling is complete and the MWD’s non-linear feature has disappeared. Thus, finally, a truly linear regime onsets: relative deviations of all variables from equilibrium are less than unity and perturbation theory can now be applied. This is done in Appendix C where we find

$`{\displaystyle \frac{\delta v_t}{v^{}}}\delta \varphi _t(0)`$
$`\{\begin{array}{cc}J\varphi _{\mathrm{}}(0)(\tau _{\mathrm{fill}}/t)^{1/2}\hfill & (\tau _{\mathrm{fill}}t\tau _{\mathrm{slow}})\hfill \\ Mϵ\varphi _{\mathrm{}}(0)(t/\tau _{\mathrm{slow}})^{3/2}e^{t/(16\tau _{\mathrm{slow}})}\hfill & (t\tau _{\mathrm{slow}})\hfill \end{array}`$ (26)
where $`J,M`$ are positive constants of order unity. Thus $`\delta \varphi _t(0)`$, and all of the fast variables which remain quasi-statically enslaved to $`\varphi _t(0)`$, relax exponentially on a timescale $`\tau _{\mathrm{slow}}`$ with a power law prefactor.

## 4 The Second Moment of the MWD Relaxes More Slowly than the First

A picture has emerged of fast mass-related variables which relax in $`\tau _{\mathrm{fast}}`$ and slow MWD shape properties which relax in the much longer time $`\tau _{\mathrm{slow}}`$. The MWD’s first moment defines the total mass in the polymer system: this is a fast variable and was considered in section 3. The simplest slow shape property is the dispersion $`\mathrm{\Delta }_t`$,

$$\mathrm{\Delta }_t\overline{N_t^2}\overline{N}_t^2,\overline{N_t^2}_0^{\mathrm{}}𝑑NN^2\varphi _t(N),$$
(28)
which is closely related to the second moment. In this section we consider the very different and slow relaxation of this quantity.

Substituting eq. (11) in eq. (28) one finds that following a $`T`$-jump the initial relative perturbation in the dispersion, $`\delta \mathrm{\Delta }_0`$, is

$$\frac{\delta \mathrm{\Delta }_0}{\mathrm{\Delta }_{\mathrm{}}}=2\frac{ϵ}{\theta },\mathrm{\Delta }_{\mathrm{}}=\overline{N}_{\mathrm{}}^2,$$
(29)
where the equilibrium value, $`\mathrm{\Delta }_{\mathrm{}}`$, is found using eq. (1). Now the dynamics of the dispersion can be derived by evaluating the time derivatives of $`\overline{N_t^2},\overline{N}_t`$ in eq. (28). These can in turn be calculated by multiplying eq. (5) by $`N^2`$ and $`N`$, respectively, integrating over all $`N`$ and using the boundary condition of eq. (2). One has

$`{\displaystyle \frac{1}{\mathrm{\Delta }_{\mathrm{}}}}{\displaystyle \frac{d\delta \mathrm{\Delta }_t}{dt}}={\displaystyle \frac{1}{2\tau _{\mathrm{slow}}}}{\displaystyle \frac{D_t}{D_{\mathrm{}}}}\left[1{\displaystyle \frac{\overline{N}_t}{\overline{N}_{\mathrm{}}}}{\displaystyle \frac{\varphi _t(0)}{\varphi _{\mathrm{}}(0)}}\right]`$
$`{\displaystyle \frac{1}{2\tau _{\mathrm{slow}}}}{\displaystyle \frac{\delta \varphi _t(0)}{\varphi _{\mathrm{}}(0)}}.`$ (30)
Here we replaced $`D_t`$ and $`\overline{N}_t`$ with their $`t=\mathrm{}`$ values. This is correct to leading order since the relative perturbations in these quantities are much smaller than that of $`\varphi _t(0)`$ which undergoes much larger changes (see section 3).

Now integrating eq. (4) using eqs. (3.1), (23) and (3.3) one finds that up to the time $`\tau _{\mathrm{fill}}`$ the dispersion has changed very little relative to its value just after the perturbation at $`t=0`$:

$$\frac{\mathrm{\Delta }_t\mathrm{\Delta }_0}{\mathrm{\Delta }_{\mathrm{}}}\{\begin{array}{cccc}(C/3)(t/\tau _{\mathrm{slow}})(t/t^{})^{1/2}\hfill & (tt^{})\hfill & & \\ t/(2\tau _{\mathrm{slow}})\hfill & (t^{}t\tau _{\mathrm{fill}})\hfill & & \end{array}$$
(31)
This is in stark contrast to the first moment which had already relaxed by the much shorter time $`\tau _{\mathrm{fast}}`$. The dispersion’s relaxation process does not properly get going until times of order $`\tau _{\mathrm{slow}}`$:

$$\frac{\delta \mathrm{\Delta }_t}{\mathrm{\Delta }_{\mathrm{}}}\{\begin{array}{cccc}\delta \mathrm{\Delta }_0/\mathrm{\Delta }_{\mathrm{}}+Jϵ\theta ^1(t/\tau _{\mathrm{slow}})^{1/2}\hfill & (\tau _{\mathrm{fill}}t\tau _{\mathrm{slow}})\hfill & & \\ \alpha ϵ(t/\tau _{\mathrm{slow}})^{5/2}e^{t/(16\tau _{\mathrm{slow}})}\hfill & (t\tau _{\mathrm{slow}})\hfill & & \end{array}$$
(32)
where $`\alpha =8M/39`$. The relative perturbation in the dispersion remains of order $`ϵ`$ for $`t\tau _{\mathrm{slow}}`$ and subsequently relaxes exponentially.

## 5 Response to $`T`$-jump; Negative Velocity Boost

In this section we study the case opposite to section 3, when $`ϵ<0`$ and the $`T`$-jump induces a higher equilibrium monomer concentration and a smaller $`\overline{N}_{\mathrm{}}`$ (see eq. (9)). Such a perturbation in the example of $`\alpha `$-methylstyrene would be produced by an increase in temperature as one may see in fig. 7. In this case the sign of the initial perturbed velocity (eq. (13)) is negative (see fig. 6). Thus initially the MWD is not boosted towards larger molecular weights as in section 3, but is instead boosted in the opposite direction, towards smaller $`N`$. Therefore, instead of depletion, an excess of small length chains and free initiators is produced, creating instead of a hole, a sharp peak in the MWD near $`N=0`$ as shown in fig. 11.

Despite the differences between the two cases, many of the results of section 3 remain unchanged. In fact all equations of section 3 up to eq. (16) remain unchanged, the only difference being that $`ϵ`$ is negative. Thus eq. (16) now describes a MWD coherently shrinking and simultaneously broadening with diffusion coefficient $`D_{\mathrm{}}`$. But since free initiators cannot depolymerize, excess polymer must build up near $`N=0`$. Indeed, starting from eq. (16) it is shown in Appendix D that

$`{\displaystyle \frac{\varphi _t(0)}{\varphi _{\mathrm{}}(0)}}\{\begin{array}{cc}1+C^{}(t/t^{})^{1/2}\hfill & (tt^{})\hfill \\ F^{}(t/t^{})\hfill & (t^{}t\tau _{\mathrm{fast}})\hfill \end{array}`$ (35)
where $`C^{}=4/\pi ^{1/2}`$ and $`F^{}=4`$. Eq. (35) has a similar interpretation to eq. (3.1). For $`tt^{}`$ diffusion is fast enough to smooth out the excess polymer accumulated by the negative velocity at the origin and thus $`\varphi _t(0)`$ remains close to its initial value (see fig. 11 (a)). For $`tt^{}`$ however the flow towards the origin is faster than what diffusion can smear out and a peak forms whose height increases with time, as shown in fig. 11(b). (Once again it is assumed that the perturbation is not so small that $`t^{}\tau _{\mathrm{fast}}`$; the opposite case is examined in section 5).

After the completion of the first stage at times of order $`\tau _{\mathrm{fast}}`$, similarly to section 3, the fast $`m_t,\overline{N}_t`$ variables have essentially relaxed and start to respond quasi-statically to the slow diffusion-driven shape changes of the MWD. In fact we show in Appendix D that eqs. (14) and (20) still apply, but now with a different crossover timescale, $`\tau _{\mathrm{qs}}=\tau _{\mathrm{fast}}\mathrm{ln}\overline{N}_{\mathrm{}}`$. This difference arises because unlike the positive boost case $`\varphi _t(0)`$ does not become exponentially small and so needs less time to catch up with the $`v_t`$ term in the velocity dynamics, eq. (6).

Similarly to the positive boost, eq. (21) still applies for $`t<\tau _{\mathrm{fill}}`$. By this time the accumulation at the origin is able to diffuse to distances of the same size as the region from which it was transferred from during the first stage. Hence $`\varphi _t(0)`$ becomes of order its initial value, and thereafter perturbation theory is valid. In Appendix D we show that

$`\varphi _t(0)/\varphi _{\mathrm{}}(0)`$
$`\{\begin{array}{ccc}K^{}(\tau _{\mathrm{fill}}/t)^{1/2}\hfill & (\tau _{\mathrm{fast}}t\tau _{\mathrm{fill}})\hfill & \\ 1+J^{}(\tau _{\mathrm{fill}}/t)^{1/2}\hfill & (\tau _{\mathrm{fill}}t\tau _{\mathrm{slow}})\hfill & \\ 1+M^{}ϵ(t/\tau _{\mathrm{slow}})^{3/2}e^{t/(16\tau _{\mathrm{slow}})}\hfill & (t\tau _{\mathrm{slow}})\hfill & \end{array}`$ (39)
where $`K^{},J^{},`$ and $`M^{}`$ are positive constants of order unity. Note there is apparently no smooth cross-over at $`t=\tau _{\mathrm{fast}}`$ between the forms of eqs. (35) and (5). This is because there is in fact an extra episode at times of order $`\tau _{\mathrm{fast}}`$ during which the very thin peak spreads from width $`(D_{\mathrm{}}t^{})^{1/2}`$ to a width $`(D_{\mathrm{}}\tau _{\mathrm{fast}})^{1/2}`$. Note also that the time behavior for $`t\tau _{\mathrm{fill}}`$ has been derived using the linearized dynamics of Appendix C.

Finally, to obtain the dispersion dynamics we use eqs. (35) and (5) in eq. (4) to obtain

$`\delta \mathrm{\Delta }_t/\mathrm{\Delta }_{\mathrm{}}\delta \mathrm{\Delta }_0/\mathrm{\Delta }_{\mathrm{}}`$
$`\{\begin{array}{cc}(C^{}/3)(t/\tau _{\mathrm{slow}})(t/t^{})^{1/2}(tt^{})\hfill & \\ F^{}/4(t/\tau _{\mathrm{slow}})(t/t^{})(t^{}t\tau _{\mathrm{fast}})\hfill & \\ K^{}ϵ\theta ^1(t/\tau _{\mathrm{slow}})^{1/2}(\tau _{\mathrm{fast}}t\tau _{\mathrm{fill}})\hfill & \\ J^{}ϵ\theta ^1(t/\tau _{\mathrm{slow}})^{1/2}(\tau _{\mathrm{fill}}t\tau _{\mathrm{slow}})\hfill & \\ \delta \mathrm{\Delta }_0/\mathrm{\Delta }_{\mathrm{}}(8M^{}/39)ϵ(\tau _{\mathrm{slow}}/t)^{5/2}e^{t/(16\tau _{\mathrm{slow}})}\hfill & \\ (t\tau _{\mathrm{slow}})\hfill & \end{array}`$ (47)
which is very similar to eqs. (31) and (32) for the positive boost case. Again the dispersion relaxes on a timescale $`\tau _{\mathrm{slow}}`$, much longer then the relaxation time of $`\overline{N}_t`$.

## 6 Very Small $`T`$-jumps: $`ϵ`$ less than its critical value $`ϵ_\mathrm{c}`$

Hitherto we implicitly assumed sufficiently strong velocity boosts that the timescale $`t^{}`$ after which translational motion dominates diffusion and a hole or peak begins to form is shorter than the time for full development of the hole or peak, namely $`\tau _{\mathrm{fast}}`$. Now the ratio of these timescales is

$$\frac{t^{}}{\tau _{\mathrm{fast}}}\left(\frac{ϵ_\mathrm{c}}{ϵ}\right)^2,ϵ_\mathrm{c}\frac{\theta ^{1/2}}{\overline{N}_{\mathrm{}}^{1/2}},$$
(48)
which defines a critical value of the perturbation parameter, $`ϵ_\mathrm{c}`$. Clearly, the system’s response must be different for $`ϵ`$ values below this rather small threshold. We consider such very small perturbations in this section. Although a full hole or peak does not have time to develop, we will find that the response is still strong and non-linear.

Since such weak perturbations do not involve the creation of a complete hole or a peak in the MWD, one expects that the timescales $`t^{}`$ and $`\tau _{\mathrm{fill}}`$ associated with the their creation and destruction lose their physical meaning as cross-over timescales. This is shown in Appendix E where, using similar arguments to the ones of sections 3 and 5, it is proved that weak perturbations are identical to stronger perturbations except that the regime up to $`t^{}`$ is truncated at $`\tau _{\mathrm{fast}}`$ and the following regime (which for stronger perturbations lasted till $`\tau _{\mathrm{fill}}`$) deleted. In Appendix E it is shown that for both positive and negative boosts, one has for the fast variables

$$\frac{\delta v_t}{v^{}}\{\begin{array}{cc}ϵe^{t/\tau _{\mathrm{fast}}}\hfill & (t\tau _{\mathrm{fast}})\hfill \\ \delta \varphi _t(0)\hfill & (\tau _{\mathrm{fast}}t\tau _{\mathrm{slow}})\hfill \end{array}$$
(49)
Note that that the timescale $`\tau _{\mathrm{qs}}`$ does not appear since its magnitude lies between those of $`t^{}`$ and $`\tau _{\mathrm{fill}}`$.

The evolution of the MWD (see figs. 13, 14) is similarly shown in Appendix E to lead to the following solution for $`\varphi _t(0)`$ in the case of a positive initial velocity:

$$\frac{\varphi _t(0)}{\varphi _{\mathrm{}}(0)}\{\begin{array}{cc}1C(t/t^{})^{1/2}\hfill & (t\tau _{\mathrm{fast}})\hfill \\ 1Q\left(\tau _{\mathrm{fill}}/t\right)^{1/2}\hfill & (\tau _{\mathrm{fast}}t\tau _{\mathrm{slow}})\hfill \end{array}(v_0>0)$$
(50)
while for a negative initial velocity one has instead

$$\frac{\varphi _t(0)}{\varphi _{\mathrm{}}(0)}\{\begin{array}{cc}1+C^{}(t/t^{})^{1/2}\hfill & (t\tau _{\mathrm{fast}})\hfill \\ 1+Q^{}(\tau _{\mathrm{fill}}/t)^{1/2}\hfill & (\tau _{\mathrm{fast}}t\tau _{\mathrm{slow}})\hfill \end{array}(v_0<0)$$
(51)
where $`Q,Q^{}`$ are positive constants. Finally, it is straightforward to show that the relaxation for for $`t\tau _{\mathrm{slow}}`$ is exponential as for the stronger perturbations, eq. (3.3).

The most important result of this section is that even though the $`ϵ<ϵ_\mathrm{c}`$ case is “weak” as compared to sections 3 and 4, the system’s response remains large and nonlinear. One sees from eqs. (50) and (51) that at $`\tau _{\mathrm{fast}}`$ when the deviation of $`\varphi _t(0)`$ from equilibrium is largest, the relative deviation of $`\varphi _t(0)`$ from equilibrium is much larger than $`ϵ`$. Therefore even in the weak case a hole or peak does form in the MWD but of a smaller amplitude as compared to the stronger perturbation case (see figs. 13, 14).

Now the dispersion dynamics may be similarly evaluated using eqs. (50) and (51) in eq. (4). One finds that $`\mathrm{\Delta }_t`$ relaxes once again on a timescale $`\tau _{\mathrm{slow}}`$. For the positive initial velocity case one finds

$`\delta \mathrm{\Delta }_t/\mathrm{\Delta }_{\mathrm{}}\delta \mathrm{\Delta }_0/\mathrm{\Delta }_{\mathrm{}}`$
$`\{\begin{array}{cc}(C/3)(t/\tau _{\mathrm{slow}})(t/t^{})^{1/2}(t\tau _{\mathrm{fast}})\hfill & \\ Qϵ\theta ^1(t/\tau _{\mathrm{slow}})^{1/2}(\tau _{\mathrm{fast}}t\tau _{\mathrm{slow}})\hfill & \\ \delta \mathrm{\Delta }_0/\mathrm{\Delta }_{\mathrm{}}+(8M/39)ϵ(\tau _{\mathrm{slow}}/t)^{5/2}e^{t/(16\tau _{\mathrm{slow}})}\hfill & \\ (t\tau _{\mathrm{slow}})\hfill & \end{array}`$ (56)
while for a negative initial boost

$`\delta \mathrm{\Delta }_t/\mathrm{\Delta }_{\mathrm{}}\delta \mathrm{\Delta }_0/\mathrm{\Delta }_{\mathrm{}}`$
$`\{\begin{array}{cc}(C^{}/3)(t/\tau _{\mathrm{slow}})(t/t^{})^{1/2}(t\tau _{\mathrm{fast}})\hfill & \\ Q^{}ϵ\theta ^1(t/\tau _{\mathrm{slow}})^{1/2}(\tau _{\mathrm{fill}}t\tau _{\mathrm{slow}})\hfill & \\ \delta \mathrm{\Delta }_0/\mathrm{\Delta }_{\mathrm{}}(8M^{}/39)ϵ(\tau _{\mathrm{slow}}/t)^{5/2}e^{t/(16\tau _{\mathrm{slow}})}\hfill & \\ (t\tau _{\mathrm{slow}})\hfill & \end{array}`$ (61)
## 7 General Perturbations

We have so far considered a specific type of perturbation, namely $`T`$-jumps. In this section we consider general perturbations. We will see that almost all of the phenomenology remains unchanged.

Let us start with another simple type of perturbation: addition of a very small amount of monomer to an equilibrated system. (This would require special care to avoid introducing impurities which in current experimental methods are destroyed by the initiators before polymerization greer:review .) Changing the total amount of monomer perturbs both independent system parameters, $`r`$ and $`f`$ (see eq. (7)), while a $`T`$-jump perturbed only $`f`$. Despite this, the results of the previous sections remain identical. The reason is that since in both cases the initial MWD is an exponential distribution whose mean is different from the new target equilibrium MWD, the only variable parameterizing the perturbation is $`\delta \overline{N}_0`$, or equivalently $`\delta m_0`$. Thus one sees from eq. (9) that monomer addition is simply equivalent to a positive velocity boost induced by a $`T`$-jump.

Consider now the most general perturbation, i. e. one generating an initial MWD of arbitrary shape as shown in fig. 8(b). (This should be compared to the $`T`$-jump and $`m`$-jump which produce initial MWDs of exponential shape with a mean slightly displaced from equilibrium.) Such a general perturbation is small provided

$$\frac{|\delta \varphi _0(N)|}{\varphi _{\mathrm{}}(N)}\stackrel{<}{}ϵ$$
(62)
for all $`N`$. As for the $`T`$-jump case, we have now

$$ϵ\frac{\delta m_0}{m_{\mathrm{}}}\frac{\delta \overline{N}_0}{\overline{N}_{\mathrm{}}}\theta =\frac{\theta }{\overline{N}_{\mathrm{}}}_0^{\mathrm{}}𝑑NN\delta \varphi _0(N)$$
(63)
Since eq. (63) is of the same form as eq. (9), all the arguments of section 3 leading to the large relative perturbation in $`v`$ (eq. (13)) remain unchanged. Moreover, in our analysis of sections 3, 4, and 5, the exact shape of the perturbed MWD did not matter in any of the leading order results we obtained. The reason is that the effect of the velocity field on the MWD is so drastic that to first order the response of any MWD close enough to equilibrium is the same, in the sense that the MWD simply translates, creating a hole (or peak). Thus the analysis of sections 3, 4 and 5 directly apply to the general case.

A special exception is when the first moment of the perturbation $`\delta \varphi _t(0)`$ is arranged to have a value much smaller than $`ϵ\overline{N}_{\mathrm{}}`$. In this case the relative amount of monomer-polymer mass transfer is much less than $`ϵ`$ and this in turn reduces the velocity perturbation. For example, if the first moment were chosen to be so small that $`\delta m_0/m_{\mathrm{}}\stackrel{<}{}\mathrm{\hspace{0.17em}1}/\overline{N}_{\mathrm{}}`$, then from eq. (13) one sees that the relative perturbation in $`v_t`$ is of order $`ϵ`$, much less than the order $`ϵ\overline{N}_{\mathrm{}}`$ produced by a $`T`$-jump. In such cases, linear response applies for all times. However, if the first moment of $`\delta \varphi _0`$ is much greater than unity the response remains nonlinear.

## 8 Discussion

The peculiarity of living polymers is that different moments of the MWD relax to equilibrium on different timescales. In the present work we have shown that the first moment, i. e. the mean length, $`\overline{N}_t`$, relaxes on a timescale $`\tau _{\mathrm{fast}}`$. However the shape of the MWD measured by the second moment, or equivalently the dispersion, $`\mathrm{\Delta }_t`$, relaxes after $`\tau _{\mathrm{slow}}`$. Because the two timescales depend on different powers of $`\overline{N}_{\mathrm{}}`$ their ratio may be extremely large:

$$\tau _{\mathrm{fast}}\frac{\overline{N}_{\mathrm{}}}{v^{}}\frac{f}{(1f)},\tau _{\mathrm{slow}}\frac{\overline{N}_{\mathrm{}}^2}{4v^{}},$$
(64)
where $`1/v^{}`$ is the natural time scale and $`fm_{\mathrm{}}/m_{\mathrm{tot}}`$ is approximately the fraction of non-polymerized monomer. Our only assumption has been that $`f`$ is not extremely close to unity, i. e. the system is not very close to the polymerization temperature.

In addition to the MWD, the other important observable is the free monomer concentration, $`m_t`$. We emphasize that since the number of chains is fixed by the number of initiators, thus $`m_t`$ is linearly coupled to $`\overline{N}_t`$ by mass conservation for all times. Hence the relaxation of these two quantities is identical and $`m_t`$ relaxes after $`\tau _{\mathrm{fast}}`$. Note that for certain other living polymers such as end-polymerizing wormlike surfactant micelles, this is not true marques:end-evaporation ; milchev:monomer\_mediated\_relaxation ; wattisking:beckerdoring . In these systems there is no separate initiator species and a pair of monomers may spontaneously unite to form a living chain. The dynamics are thus very different and $`m_t`$ and $`\overline{N}_t`$ may relax on different timescales. Marques et al. marques:end-evaporation  studied this class of living polymer; after linearizing dynamical equations they found that after a small $`T`$-jump $`m_t`$ relaxes much more rapidly than $`\overline{N}_t`$ which subsequently relaxes in time $`\overline{N}_{\mathrm{}}^2`$. In numerical simulations of this same class of system, Milchev et al. milchev:monomer\_mediated\_relaxation  report a $`1/t`$ decay of mean chain length after a time $`\overline{N}_{\mathrm{}}^5`$. In the related system of spherical micelle aggregation anianssonwall:living\_micelle\_kinetics ; anianssonwall:living\_micelle\_kinetics\_correction ; aniansson:micelle\_kinetics\_theory\_expt\_etal ; wennerstrom:micelle\_review , the number of micelles can change and again the kinetics are very different ben:living\_ionic\_letter  to the present case.

A summary of our findings is shown in fig. 15, for the case emphasized here where a small $`T`$-jump induces a positive velocity boost to chain growth. The figure shows the very different relaxation times of first and second MWD moments. It also shows the interesting behavior of the number of free initiators, $`\varphi _t(0)`$, which suffers enormous depletion at intermediate times despite ultimately recovering to a level very close to its initial value. We showed that whilst virtually all of the relaxation of the fast variables $`\overline{N}_t,m_t`$ occurs on a timescale $`\tau _{\mathrm{fast}}`$, they are actually not completely relaxed by this time. The final very late stages of their relaxation during which their values are fine-tuned (to relative order $`1/\overline{N}_{\mathrm{}}`$) to the final equilibrium values, occurs on a timescale $`\tau _{\mathrm{slow}}`$. During this episode their values evolve quasi-statically, enslaved to $`\varphi _t(0)`$ according to $`\delta \overline{N}_t\theta /\overline{N}_{\mathrm{}}\delta m_t/m_{\mathrm{}}\delta \varphi _t(0)`$. The novel behavior of $`\varphi _t(0)`$, as well as its central role in late relaxation of the fast variables suggests this as an interesting quantity to measure experimentally. This might be achieved spectroscopically and would have the advantage of being a relatively uninvasive probe. We remark that for bifunctional initiators, e.g. those used in studies by the Greer group, the meaning of $`\varphi _t(0)`$ is the concentration of “half-chains,” i. e. those having at least one chain end which is a bare initiator molecule.

We have demonstrated that the type of dynamical response depends on the magnitude and sign of the perturbation. For example, if the temperature change is reversed in sign, then the velocity boost also changes sign. Thus for $`\alpha `$-methylstyrene a negative $`T`$-jump produces the positive velocity boost phenomenology of fig. 15 whereas a small temperature increase causes a negative boost. In this case, instead of short chains being annihilated, their number increases dramatically during the relaxation process. As far as perturbation magnitude is concerned, if the relative value $`ϵ`$ is less than a critical value $`1/\overline{N}_{\mathrm{}}^{1/2}`$ then the response is milder but remains non-linear. For a positive boost, the hole in the MWD is no longer complete, but instead has a relative depth less than unity but still much bigger than $`ϵ`$.

How do our predictions compare with experiment? In ref. garcia:greer:living\_nonumber  small $`T`$-jumps were imposed on $`\alpha `$-methylstyrene systems in the semi-dilute regime at concentrations high enough to be nearly entangled. Relaxation was monitored by measuring viscosity $`\eta `$ as a function of time. Now generally we expect viscosity to scale as a polymer-concentration-dependent power of mean chain length, $`\eta c_\varphi \overline{N}^\gamma `$, where the value of $`\gamma `$ is predicted by standard theories of polymer physics doiedwards:book ; gennes:book . For a general MWD, note the coefficient $`c_\varphi `$ which depends on the shape of the MWD, i. e. it depends on the full function $`[\varphi (N)]`$. (This is because $`\eta `$ depends not only on the first moment, but in general has a complex dependence on chain length distribution). Thus we predict an initial fast relaxation of $`\eta `$ lasting time $`\tau _{\mathrm{fast}}=\overline{N}/(\theta v^{})`$ (corresponding to the relaxation of $`\overline{N}`$) followed by a much slower relaxation in $`\tau _{\mathrm{slow}}`$ (this is the relaxation of the prefactor $`c_\varphi `$). The fast relaxation time is independent of $`T`$-jump magnitude (i. e. independent of $`ϵ`$). Now from eqs. (6) and (7) we can rewrite $`\tau _{\mathrm{fast}}=1/(rk^+m_{\mathrm{tot}})`$. Using garcia:greer:living\_nonumber  $`r=4.7\times 10^4`$, $`m_{\mathrm{tot}}=0.29gm/cm^3`$ and a measured value zhuang:greer\_kinetics  $`k^+0.2M^1sec^1`$ one estimates $`\tau _{\mathrm{fast}}1000`$ secs. (Note that this work involved bifunctional initiators. In ref. ben:living\_ionic\_letter  we incorrectly estimated $`\tau _{\mathrm{fast}}`$ to be twice the value calculated here based on a wrong estimate of the number of living chains which was taken to be equal to the number of bifunctional initiators instead of twice this value.) Similarly, with greer:review  $`f0.5`$, $`v^{}=0.1sec^1`$ one finds $`\tau _{\mathrm{slow}}`$ 1 month. Hence for these experiments (timescales much less than months) $`\eta `$ should relax in approximately $`1000`$ secs. In the experiments, jumps $`\delta T1`$ <sup>0</sup>C were imposed at various temperatures in the range $`283^o`$K $`\stackrel{<}{}T\stackrel{<}{}\mathrm{\hspace{0.17em}290}^o`$K. Now the temperature dependence of $`\tau _{\mathrm{fast}}1/k^+`$ is determined by $`k^+`$ which is reported zhuang:greer\_kinetics  to vary by $`10\%`$ over this temperature range. Thus we expect only a slight variation in the viscosity relaxation time at the different temperatures studied (despite the fact that $`\overline{N}_{\mathrm{}}`$ changes significantly). These predictions are very close to the experimental findings, where relaxation times at all temperatures were found to be about 2000 seconds, with very little variation from one temperature to another. This is in sharp contrast to the relative changes in $`\eta `$ itself, which varied by almost an order of magnitude.

We have emphasized small perturbations in this work. In fact, the response to a large perturbation is obtained, qualitatively speaking, by setting $`ϵ=1`$ in our results. This case was addressed by Miyake and Stockmayer miyakestockmayer:living  who considered an initial condition in which all initiators are free (i. e. $`\overline{N}_0=0`$). They were the first to identify the two timescales of the system, $`\tau _{\mathrm{fast}}`$ and $`\tau _{\mathrm{slow}}`$, in the limit of very small depolymerization rates ($`f1`$). Their analytical results applied to the $`t<\tau _{\mathrm{fast}}`$ stage where they found an initially uniformly translating and broadening MWD peak, reaching $`\overline{N}_{\mathrm{}}`$ after $`\tau _{\mathrm{fast}}`$ as shown in fig. 5. Seen from the viewpoint of a general perturbation of magnitude $`ϵ`$, in this case $`\tau _{\mathrm{fill}}`$ and $`\tau _{\mathrm{slow}}`$ coincide because $`ϵ=1`$. That is, the “hole” (in this case the entire region between $`0`$ and $`\overline{N}_{\mathrm{}}`$) fills up on the same timescale in which the whole MWD relaxes. The linearized dynamics, which for a small perturbation applied for $`t>\tau _{\mathrm{fill}}`$ due to $`\delta \varphi _t(0)/\varphi _{\mathrm{}}(0)`$ becoming small (see section 3.3) cannot be employed. Describing dynamics at times of order $`\tau _{\mathrm{slow}}`$ in this case is thus a difficult nonlinear problem nandajain:living\_broadening ; auluck:living\_mwd\_intermediate ; taganov:living\_mwd .

In recent experiments, Greer’s group zhuang:greer\_kinetics ; das:greer:living\_7\_mwd  studied such large perturbations using $`\alpha `$-methylstyrene. After a rapid quench below the polymerization temperature, monomer concentration and MWD were analyzed after a time delay. The time dependent relaxation was probed by repeating the procedure for different time delays and samples. They found different relaxation times for the monomer concentration and the MWD width, as predicted by theory miyakestockmayer:living . However, $`\overline{N}_t`$ and $`m_t`$ did not have the same relaxation, as mass conservation would seem to dictate. This may be due either to side-reactions during polymerization or living chain ionic association effects fetters:living\_aggregation ; stellbrink:living\_aggregation ; balsarafetters:living\_aggregation\_reeval  which have been studied theoretically frischknechtmilner:living\_aggregation . Dynamic light scattering measurements ruizgarciacastillo:living\_aggregation\_greer  suggest that prior to polymerization the initiators self-assemble into long polymeric structures and it has been suggested das:greer:living\_7\_mwd  that initiators may not all be equally available for polymerization following the $`T`$-quench. However, lifetimes of aggregate structures would need to be extremely long for these effects to interfere with polymerization dynamics since as we have seen the MWD relaxation times are very large.

In conclusion, our hope is that this work will motivate further experimental study of the dynamical sensitivity of living polymers to small perturbations. The drastic effect on the MWD in the small chain region, in particular the depletion or excess of free initiators, is a natural focus for experimental measurement. One can think of other time-dependent perturbations such as small amplitude thermal cycling which would probe interesting aspects of their ultrasensitive dynamics. Finally, the systems we have analyzed here are model starting points for the considerably more complex biological living polymers, actin filaments and microtubules, which are intimately involved in the locomotion and structural integrity of living cells korn:actin\_review\_science ; pollardcooper:actin\_review ; desaimitchison:mtub\_review .

###### Acknowledgements.

This work was supported by the Petroleum Research Fund, grant no. PRF-33944-AC7.

## Appendix A Derivation of Equilibrium Values $`m_{\mathrm{}}`$, $`\overline{N}_{\mathrm{}}`$, $`v_{\mathrm{}}`$, $`D_{\mathrm{}}`$.

The equilibrium MWD can be calculated by setting the time derivative in eq. (5) to zero. Its solution is the Flory distribution, eq. (1), where

$$\overline{N}_{\mathrm{}}=D_{\mathrm{}}/v_{\mathrm{}}.$$
(65)
Solving the system of eqs. (65) and (2) for $`m_{\mathrm{}},\overline{N}_{\mathrm{}}`$ one has

$`{\displaystyle \frac{m_{\mathrm{}}}{m_{\mathrm{tot}}}}={\displaystyle \frac{1}{2}}\left\{1+f+{\displaystyle \frac{r}{2}}\left[(1f)^2+r(1+3f)+{\displaystyle \frac{r^2}{4}}\right]^{1/2}\right\}`$
$`\overline{N}_{\mathrm{}}={\displaystyle \frac{1}{r}}\left(1{\displaystyle \frac{m_{\mathrm{}}}{m_{\mathrm{tot}}}}\right).`$ (66)
For $`r1`$ and assuming $`(1f)/r^{1/2}1`$, by expanding eq. (A) in powers of $`r`$ and keeping only the first term of the expansion one recovers eq. (8). The values of $`v_{\mathrm{}},D_{\mathrm{}}`$ in eq. (8) are obtained by substitution of $`m_{\mathrm{}},\overline{N}_{\mathrm{}}`$ in eq. (4).

## Appendix B Self-Consistency of Results of Subsections 3.1 and 3.2

### B.1 Coherent Chain Growth

The solution for the $`v_t`$ dynamics, eq. (14), follows by solving eq. (6) after neglecting the $`\varphi _t(0)`$ term on the rhs. For $`t\tau _{\mathrm{qs}}`$, this is a self-consistent solution since then the $`\varphi _t(0)`$ term is negligible with respect to the remaining terms as can be seen using the solutions for $`v_t,\varphi _t(0)`$ of eqs. (14), (3.1), and eq. (23).

Eq. (15) is derived by substituting $`v_t`$ from eq. (14) in eq. (5), replacing $`D_t=D_{\mathrm{}}+\delta D_t`$, and dropping the $`\delta D_t`$ term. The fact that this term can be neglected may be seen as follows. Even if $`\delta D_t`$ did not decrease but remained of order $`\delta D_0`$ throughout this regime this would lead to replacing $`D_{\mathrm{}}`$ by $`D_{\mathrm{}}(1+ϵ)`$ in all results obtained in section 3 (see eq. (13)). This upper bound on the effect of $`\delta D_t`$ can easily be seen to lead to higher order in $`ϵ`$ terms (see eg. eq. (3.1)) and the $`\delta D_t`$ term can therefore be neglected.

Now let us consider the propagator of the dynamics of eq. (15), which appears in eq. (16). For short times, $`t\tau _{\mathrm{fast}}`$, one may replace $`v_t`$ in eq. (15) by $`v_0`$. Eq. (15) then has constant coefficients and its propagator including the boundary condition may be calculated exactly hill:aggr\_bio\_book :

$`G_t^{\mathrm{tran}}(N,N^{})={\displaystyle \frac{1}{(4\pi D_{\mathrm{}}t)^{1/2}}}\times `$
$`\left\{e^{(NN^{}v_0t)^2/(4D_{\mathrm{}}t)}+e^{N^{}v_0/D_{\mathrm{}}}e^{(N+N^{}v_0t)^2/(4D_{\mathrm{}}t)}\right\}`$
$`{\displaystyle \frac{v_0}{2D_{\mathrm{}}}}e^{Nv_0/D_{\mathrm{}}}\mathrm{erfc}\left({\displaystyle \frac{N+N^{}+v_0t}{(4D_{\mathrm{}}t)^{1/2}}}\right)(t\tau _{\mathrm{fast}})`$ (67)
Here $`\mathrm{erfc}(x)1\mathrm{erf}(x)`$, where $`\mathrm{erf}`$ is the error function.

The solution for $`\varphi _t(0)`$ is derived by substituting eq. (B.1) in eq. (16) and setting $`N=0`$. One has

$`{\displaystyle \frac{\varphi _t(0)}{\varphi _{\mathrm{}}(0)}}\mathrm{erfc}(x)+2x^2\mathrm{erfc}(x)2\pi ^{1/2}xe^{x^2},`$
$`x(t/t^{})^{1/2}(t\tau _{\mathrm{fast}})`$ (68)
Here we used the fact that since the values of $`N^{}`$ contributing to the integration are much smaller than $`\overline{N}_{\mathrm{}}`$, one may approximate $`\varphi _0(N^{})`$ by $`\varphi _{\mathrm{}}(0)`$ in the integrand of eq. (16) (with relative errors of order $`1/\overline{N}_{\mathrm{}}`$). Eq. (3.1) of the main text follows from eq. (B.1) by taking the two corresponding limits. Note that eq. (B.1) approximates $`\varphi _t(0)`$ for all $`t\tau _{\mathrm{fast}}`$, including times of order $`t^{}`$.

### B.2 Hole Filling

Eq. (20) is a self-consistent solution of eq. (6) since for $`t\tau _{\mathrm{qs}}`$, assuming the validity of eqs. (20) and (3.1) one may verify that eq. (6) is satisfied with the term on the lhs being much smaller in magnitude than both terms on the rhs which balance one another.

Consider now the validity of eq. (21) for $`\tau _{\mathrm{fast}}t\tau _{\mathrm{fill}}`$. Substituting eq. (23) into eq. (20) one has explicit solutions for $`m_t,\overline{N}_t,v_t,D_t`$. One thus sees that in the time regime of consideration the velocity term in eq. (5) is exponentially small and therefore can be deleted in eq. (21) with very small error.

The MWD dynamics are therefore described by eq. (21) whose propagator satisfying reflecting boundary conditions is

$`G_t^{\mathrm{diff}}(N,N^{})={\displaystyle \frac{1}{(4\pi D_{\mathrm{}}t)^{1/2}}}\times `$
$`\left\{e^{(NN^{})^2/(4D_{\mathrm{}}t)}+e^{(N+N^{})^2/(4D_{\mathrm{}}t)}\right\}.`$ (69)
The solution of eq. (21) is thus

$`\varphi _t(N)`$ $``$ $`{\displaystyle _0^{\mathrm{}}}𝑑N^{}\varphi _{t_{\mathrm{cross}}}(N^{})G_{tt_{\mathrm{cross}}}^{\mathrm{diff}}(N,N^{})`$ (70)
$``$ $`{\displaystyle _{ϵ\overline{N}_{\mathrm{}}/\theta }^{\mathrm{}}}𝑑N^{}\varphi _0(N^{}ϵ\overline{N}_{\mathrm{}}/\theta )G_t^{\mathrm{diff}}(N,N^{})`$
$`(\tau _{\mathrm{fast}}t\tau _{\mathrm{fill}}).`$
where $`t_{\mathrm{cross}}`$ satisfies $`\tau _{\mathrm{fast}}t_{\mathrm{cross}}\tau _{\mathrm{qs}}`$, i. e. it belongs to the time regime described simultaneously by eqs. (15) and (21). In going from the first integral in eq. (70) to the second we used the fact that at $`t_{\mathrm{cross}}`$ the MWD has approximately the shape of the initial MWD, boosted in the positive direction by $`ϵ\overline{N}_{\mathrm{}}/\theta `$. The effect of diffusion during the initial boost of the MWD may be shown to be small. Notice also that evolution in the last expression in eq. (70) starts at $`t=0`$; for $`tt_{\mathrm{cross}}`$ we may to leading order replace $`tt_{\mathrm{cross}}`$ in $`G^{\mathrm{diff}}`$ in eq. (70) by $`t`$.

Substituting eq. (B.2) in eq. (70) and setting $`N=0`$ one obtains

$$\frac{\varphi _t(0)}{\varphi _{\mathrm{}}(0)}\mathrm{erfc}\left[\left(\frac{\tau _{\mathrm{fill}}}{t}\right)^{1/2}\right],(\tau _{\mathrm{fast}}t\tau _{\mathrm{fill}})$$
(71)
Considering times much shorter than the crossover time $`\tau _{\mathrm{fill}}`$, eq. (23) is recovered.

## Appendix C Linearized Dynamics, $`t\tau _{\mathrm{fill}}`$

Ultrasensitivity is such that the dynamics cannot be linearized until the later stages, $`t\tau _{\mathrm{fill}}`$. For these times we may linearize eq. (5) by dropping terms proportional to products of $`\delta \varphi _t,\delta v_t,\delta D_t`$. One has

$`{\displaystyle \frac{\delta \varphi _t}{t}}v_{\mathrm{}}{\displaystyle \frac{\delta \varphi _t}{N}}+D_{\mathrm{}}{\displaystyle \frac{^2\delta \varphi _t}{N^2}}+\mu _t,`$
$`\mu _t{\displaystyle \frac{\delta v_t}{\overline{N}_{\mathrm{}}}}\left[\varphi _{\mathrm{}}(N)\delta (N)\right],`$ (72)
with reflecting boundary conditions at the origin. In eq. (C) the $`\delta D_t`$ term was neglected since its magnitude is smaller by $`1/\overline{N}_{\mathrm{}}`$ than the corresponding $`\delta v_t`$ term. The $`\delta `$-function in the source term in eq. (C) arises from linearizing the boundary condition in eq. (5). Notice that by definition, $`\delta \varphi _t(0)`$ is normalized to zero and that the source term in eq. (C) preserves this normalization since its integral over all $`N`$ is zero.

Performing the corresponding linearization in eq. (6) one has

$$\frac{d}{dt}\delta v_t\frac{1}{\tau _{\mathrm{fast}}}\delta v_t\frac{1}{\tau _{\mathrm{fast}}}D_{\mathrm{}}\delta \varphi _t(0).$$
(73)
Now since eq. (C) is of the same form as eq. (15), its propagator, $`G_t^{\mathrm{linear}}(N,N^{})`$, is given by eq. (B.1) with $`v_0`$ replaced by $`v_{\mathrm{}}`$. Thus if $`\delta \varphi _{t_L}(N)`$ is known at time $`t_L`$, then the solution of eq. (C) for subsequent times is

$$\delta \varphi _t(N)_0^{\mathrm{}}𝑑N^{}G_{tt_L}^{\mathrm{linear}}(N,N^{})\delta \varphi _{t_L}(N^{})+R_t(N),$$
(74)
where

$`R_t(N){\displaystyle _0^{\mathrm{}}}𝑑N^{}{\displaystyle _{t_L}^t}𝑑t^{}G_{tt^{}}^{\mathrm{linear}}(N,N^{})\mu _t^{}(N^{})`$
$`{\displaystyle _{t_L}^t}𝑑t^{}{\displaystyle \frac{D_{\mathrm{}}\delta \varphi _t(0)}{\overline{N}_{\mathrm{}}}}\left[\varphi _{\mathrm{}}(N)G_{tt^{}}^{\mathrm{linear}}(N,0)\right].`$ (75)
Here the last expression for $`R_t(N)`$ is obtained by performing the $`N^{}`$ integration using the expression for $`\mu _t`$ from eq. (C) and the fact that $`\varphi _{\mathrm{}}(N)`$ remains unchanged when evolved with $`G^{\mathrm{linear}}`$. In eq. (C) we also used

$$\delta v_tD_{\mathrm{}}\delta \varphi _t(0)$$
(76)
which is valid throughout the linearized time regime as one may derive using eq. (73). The solution of eqs. (C) and (73) is thus found by setting $`N=0`$ in eq. (74), solving for $`\delta \varphi _t(0)`$, and then using the calculated expression in eqs. (74) and (76) to find $`\delta \varphi _t(N)`$ and $`\delta v_t`$. Let us now perform this analysis for two time regimes.

(i) $`\tau _{\mathrm{fill}}t\tau _{\mathrm{slow}}`$. In this regime, we will see the source term can in effect be ignored. The top expression on the rhs of eq. (3.3) is a self-consistent solution of eq. (74) which is proved as follows. As one may see from eqs. (23) and (3.3) there exists a constant $`\beta `$ of order unity such that for $`t>\beta \tau _{\mathrm{fill}}`$ the relative perturbation in $`\varphi _t(N)`$ is much smaller than unity and eq. (C) applies. (More precisely, for any desired relative smallness there exists a different constant $`\beta `$.) Thus setting $`t_L=\beta \tau _{\mathrm{fill}}`$ and $`N=0`$ in eq. (74) and using the expression for $`\delta \varphi _t(0)`$ from eq. (3.3) one finds that with appropriate choice of $`J`$, eq. (74) is satisfied with $`R_t(0)`$ being much smaller than the remaining two terms in eq. (74). The integral term in eq. (74) is calculated using the fact that as seen from eqs. (23), (3.3), and fig. 10, $`\delta \varphi _{t_L}(N)`$ is of order $`\delta \varphi _{t_L}(0)ϵ\varphi _{\mathrm{}}(N)`$ for $`Nϵ\overline{N}_{\mathrm{}}/\theta `$ and of order $`ϵ\varphi _{\mathrm{}}(N)`$ for larger $`N`$. We also used

$`G_{tt^{}}^{\mathrm{linear}}(0,N^{})`$ $`\{\begin{array}{cc}1/\left[D_{\mathrm{}}(tt^{})\right]^{1/2}\hfill & (N^{}D_{\mathrm{}}(tt^{}))\hfill \\ 0\hfill & (N^{}D_{\mathrm{}}(tt^{}))\hfill \end{array}`$ (80)
$`(t,t^{}\tau _{\mathrm{slow}})`$
which may be derived from eq. (B.1).

(ii) $`t\tau _{\mathrm{slow}}`$. Using eq. (B.1) one finds

$$G_t^{\mathrm{linear}}(0,N^{})S_{\mathrm{}}+(S_tS_{\mathrm{}})\lambda (N^{})(t\tau _{\mathrm{slow}}),$$
(81)
where

$`S_tG_t^{\mathrm{linear}}(0,0),S_{\mathrm{}}=\varphi _{\mathrm{}}(0)=1/\overline{N}_{\mathrm{}},`$
$`\lambda (N^{})\left(1{\displaystyle \frac{N^{}}{2\overline{N}_{\mathrm{}}}}\right)e^{N^{}/(2\overline{N}_{\mathrm{}})}.`$ (82)
Now setting $`t_L=\tau _{\mathrm{slow}}`$ in eq. (74) and using eqs. (C) and (81) one has

$`\delta \varphi _t(0)`$ $`(S_tS_{\mathrm{}}){\displaystyle _0^{\mathrm{}}}𝑑N^{}\lambda (N^{})\delta \varphi _{\tau _{\mathrm{slow}}}(N^{})+`$ (83)
$`{\displaystyle \frac{1}{4S_{\mathrm{}}\tau _{\mathrm{slow}}}}{\displaystyle _{\tau _{\mathrm{slow}}}^t}𝑑t^{}\left(S_{tt^{}}S_{\mathrm{}}\right)\delta \varphi _t^{}(0)`$
where we used the fact that $`\delta \varphi _{\tau _{\mathrm{slow}}}(N^{})`$ is normalized to zero.

Now the self-consistency of the $`t>\tau _{\mathrm{slow}}`$ expression on the rhs of eq. (3.3) is proved by substituting eq. (3.3) in eq. (83). Since $`\delta \varphi _{\tau _{\mathrm{slow}}}(N^{})`$ is of order $`ϵ/\overline{N}_{\mathrm{}}`$, the magnitude of the integral of $`\delta \varphi _{\tau _{\mathrm{slow}}}(N^{})`$ in eq. (83) is of order $`ϵ`$. The last integral term in eq. (83) is evaluated using eq. (3.3) and

$`S_tS_{\mathrm{}}`$
$`\{\begin{array}{cc}1/(D_{\mathrm{}}t)^{1/2}\hfill & (t\tau _{\mathrm{slow}})\hfill \\ 16S_{\mathrm{}}\pi ^{1/2}\left(\tau _{\mathrm{slow}}/t\right)^{3/2}e^{t/(16\tau _{\mathrm{slow}})}\hfill & (t\tau _{\mathrm{slow}})\hfill \end{array}`$ (86)
which may be proved using eqs. (C) and (B.1). One finds that for $`t\tau _{\mathrm{slow}}`$ all terms in eq. (83) have the same time dependence and are of the same order of magnitude. Thus eq. (83) may be satisfied by appropriate choice of the numerical coefficient $`M`$ in eq. (3.3).

## Appendix D Self-Consistency of the Results of Section 5

### D.1 Coherent Chain Shrinking

The validity of eq. (14) is verified using the same arguments as in the first paragraph of Appendix B but now using the expression for $`\varphi _t(0)`$ from eq. (35).

Setting $`N=0`$ in eq. (70) one obtains eq. (B.1) with $`x`$ now replaced by $`x`$. Considering times much greater and much less than $`t^{}`$ leads to eq. (35).

### D.2 Peak Decay

The validity of eq. (20) is proved using exactly the same arguments as the ones in the first paragraph of the corresponding section of Appendix B, but now using the expression for $`\varphi _t(0)`$ from eq. (5). One finds that the crossover time $`\tau _{\mathrm{qs}}\tau _{\mathrm{fast}}\mathrm{ln}(\overline{N}_{\mathrm{}})`$ is different from the respective crossover time found in Appendix B.

The solution of eq. (21) is now

$`\varphi _t(N){\displaystyle _0^{\mathrm{}}}𝑑N^{}\varphi _0(N^{}ϵ\overline{N}_{\mathrm{}}/\theta )G_t^{\mathrm{diff}}(N,N^{})+`$
$`G_t^{\mathrm{diff}}(N,0){\displaystyle _0^{ϵ\overline{N}_{\mathrm{}}/\theta }}𝑑N^{}\varphi _0(N^{})(\tau _{\mathrm{fast}}t\tau _{\mathrm{slow}}).`$ (88)
Here the evolved MWD consists of two parts, corresponding to the two terms on the rhs (see fig. 11(c)). The first is the initial MWD, $`\varphi _0`$, shifted by $`ϵ\overline{N}_{\mathrm{}}/\theta `$ towards smaller $`N`$. The second part is the excess peak accumulated by the negative boost at the origin and whose amount was the polymer initially lying between zero and $`ϵ\overline{N}_{\mathrm{}}/\theta `$. Here, as in section 3, the effects of diffusive broadening during $`t<\tau _{\mathrm{fast}}`$ have been neglected, and $`\tau _{\mathrm{fast}}`$ in eq. (D.2) has been replaced by zero.

Now substituting eq. (B.2) in eq. (D.2) and setting $`N=0`$ one obtains eq. (5) similarly to the derivation of eq. (23) in Appendix B.

## Appendix E Self-Consistency of the Results of Section 6

For times $`t\tau _{\mathrm{fast}}`$, all results and analysis are identical to those for the strong perturbation ($`ϵ>ϵ_\mathrm{c}`$) case in the regime $`tt^{}`$. Eq. (49) can be shown to be a self-consistent solution using the same arguments as those of Appendices B and D to prove eqs. (14) and (20), respectively. For times longer than $`\tau _{\mathrm{fast}}`$ linearization of the dynamics can be performed and the results of Appendix C directly apply.


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# Untitled Document

The Proof that the Standard Transformations of $`𝐄`$ and $`𝐁`$ and the Maxwell

Equations with $`𝐄`$ and $`𝐁`$ are not Relativistically Correct

Tomislav Ivezić

Rud er Bošković Institute, P.O.B. 180, 10002 Zagreb, Croatia

ivezic@irb.hr

In this paper it is exactly proved that the standard transformations of the three-dimensional (3D) vectors of the electric and magnetic fields $`𝐄`$ and $`𝐁`$ *are not* relativistically correct transformations. Thence the 3D vectors $`𝐄`$ and $`𝐁`$ *are not* well-defined quantities in the 4D spacetime and, contrary to the general belief, the usual Maxwell equations with the 3D $`𝐄`$ and $`𝐁`$ *are not* in agreement with the special relativity. The 4-vectors $`E^a`$ and $`B^a,`$ as well-defined 4D quantities, are introduced instead of ill-defined 3D $`𝐄`$ and $`𝐁.`$ The proof is given in the tensor and the Clifford algebra formalisms.

PACS numbers: 03.30.+p

It is generally accepted by physics community that there is an agreement between the classical electromagnetism and the special relativity (SR). The standard transformations of the three-dimensional (3D) vectors of the electric and magnetic fields, $`𝐄`$ and $`𝐁`$ respectively, are considered to be the Lorentz transformations (LT) of these vectors, see, e.g., ,  Sec. 11.10, or  par.24. The usual Maxwell equations (ME) with the three-vectors (3-vectors) $`𝐄`$ and $`𝐁`$ are assumed to be physically equivalent to the field equations (FE) expressed in terms of the electromagnetic field tensor $`F^{ab}.`$ In this paper it will be exactly proved that the above mentioned standard transformations of $`𝐄`$ and $`𝐁`$ *are not* relativistically correct transformations in the 4D spacetime and consequently that the usual ME with $`𝐄`$ and $`𝐁`$ and the FE with $`F^{ab}`$ *are not* physically equivalent. The whole consideration will be mainly presented in the tensor formalism (TF), since it is better known, and only briefly in the Clifford algebra formalism (CAF). It will be shown that in the 4D spacetime the well-defined 4D quantities, the 4-vectors of the electric and magnetic fields $`E^a`$ and $`B^a`$ in the TF (as in ), or, e.g., the 1-vectors $`E`$ and $`B`$ in the CAF (as in ), have to be introduced instead of ill-defined 3-vectors $`𝐄`$ and $`𝐁.`$

Let us start with some general definitions. The electromagnetic field tensor $`F^{ab}`$ is defined without reference frames, i.e., it is an abstract tensor, a geometric quantity; Latin indices a,b,c, are to be read according to the abstract index notation, as in  and . When some reference frame (a physical object) is introduced and the system of coordinates (a mathematical object) is adopted in it, then $`F^{ab}`$ can be written as a coordinate-based-geometric quantity (CBGQ) containing components and a basis. The system of coordinates with the Einstein synchronization of clocks and Cartesian spatial coordinates (it will be called the Einstein system of coordinates (ESC)) is almost always chosen in the usual treatments. (In my approach to SR that uses 4D quantities defined without reference frames,  and  in the TF, and  in the CAF, any permissible system of coordinates, not necessary the ESC, can be used on an equal footing.) When $`F^{ab}`$ is written as a CBGQ (with the ESC) it becomes $`F^{ab}=F^{\mu \nu }\gamma _\mu \gamma _\nu ,`$ where Greek indices $`\mu ,\nu `$ in $`F^{\mu \nu }`$ run from 0 to 3 and they denote the components of the geometric object $`F^{ab}`$ in some system of coordinates, here the ESC, $`\gamma _\mu `$ are the basis 4-vectors (not the components) forming the standard basis $`\left\{\gamma _\mu \right\}`$ and $`{}_{}{}^{}_{}^{}`$ denotes the tensor product of the basis 4-vectors. In the TF I shall often denote the unit 4-vector in the time direction $`\gamma _0`$ as $`t^b`$ as well. Then in some reference frame (with the ESC, i.e., with the standard basis $`\left\{\gamma _\mu \right\}`$) $`t^b`$ can be also written as a CBGQ, $`t^b=t^\mu \gamma _\mu `$, where $`t^\mu `$ is a set of components of the unit 4-vector in the time direction ($`t^\mu =(1,0,0,0)`$). Almost always in the standard covariant approaches to SR one considers only the components of the geometric quantities taken in the ESC, and thus not the whole tensor. However the components are coordinate quantities and they do not contain the whole information about the physical quantity.

In the standard treatments one defines the sets of components of the electric and magnetic fields as

$`E^\mu `$ $`=`$ $`F^{\mu \nu }t_\nu ,B^\mu =(1/2)\epsilon ^{\mu \nu \lambda \sigma }F_{\lambda \sigma }t_\nu =(F^{})^{\mu \nu }t_\nu ,`$
$`E^0`$ $`=`$ $`0,E^i=F^{i0};B^0=0,B^i=(1/2)\epsilon ^{0ikl}F_{lk},`$ (1)
where $`(F^{})^{\alpha \beta }=(1/2)\epsilon ^{\alpha \beta \gamma \delta }F_{\gamma \delta }`$ is the dual tensor (the components). (The signature of the Minkowski tensor is $`2`$, $`\epsilon ^{0123}=1,`$ and $`c=1`$). *The temporal components of* $`E^\mu `$ *and* $`B^\mu `$ *are zero.* Note that we can select a particular - but otherwise arbitrary \- inertial frame of reference (IFR) $`S`$ as the frame in which the relations (1) hold. $`t^\mu `$ can be interpreted as the 4-velocity (the components in the ESC) of the observers that are at rest in $`S`$. In the standard treatments the 3-vectors $`𝐄`$ and $`𝐁`$, as *geometric quantities in the 3D space*, are constructed from the spatial components $`E^i`$ and $`B^i`$ from (1) and *the unit 3-vectors* $`𝐢,`$ $`𝐣,`$ $`𝐤,`$ e.g., $`𝐄=F^{10}𝐢+F^{20}𝐣+F^{30}𝐤.`$ These results are quoted in numerous textbooks and papers treating relativistic electrodynamics in the TF, see, e.g., . Actually in the usual covariant approaches, e.g., , one forgets about $`E^0`$ and $`B^0`$ components and simply makes the identification of six independent components of $`F^{\mu \nu }`$ with three components $`E^i`$, $`E^i=F^{i0}`$, and three components $`B^i`$, $`B^i=(1/2)\epsilon ^{ikl}F_{lk}.`$ Since in SR we work with the 4D spacetime the mapping between the components of $`F^{\mu \nu }`$ and the components of the 3D vectors $`𝐄`$ and $`𝐁`$ is mathematically better founded by the relations (1) than by their simple identification. Therefore we proceed the consideration using (1). Note that the whole procedure is made in an IFR with the ESC. In another system of coordinates that is different than the ESC, e.g., differing in the chosen synchronization (as it is the ’r’ synchronization considered in ), the identification of $`E^i`$ with $`F^{i0},`$ as in (1) (and also for $`B^i`$), is impossible and meaningless. Further the components $`E^i`$ and $`B^i`$ are determined in the 4D spacetime in the standard basis $`\left\{\gamma _\mu \right\}.`$ Thence when forming the geometric quantities the components would need to be multiplied with the unit 4-vectors $`\gamma _i`$ and not with the unit 3-vectors.

Let us now apply the LT to the components given in (1). Under the passive LT the sets of components $`E^\mu `$ and $`B^\mu `$ from (1) transform to $`E^\mu `$ and $`B^\mu `$ in the relatively moving IFR $`S^{}`$

$`E^\mu `$ $`=`$ $`F^{\mu \nu }v_\nu ^{},B^\mu =(1/2)\epsilon ^{\mu \nu \lambda \sigma }F_{\lambda \sigma }^{}v_\nu ^{}=(F^{})^{\mu \nu }v_\nu ^{},`$
$`E^\mu `$ $`=`$ $`(\beta \gamma E^1,\gamma E^1,E^2,E^3),B^\mu =(\beta \gamma B^1,\gamma B^1,B^2,B^3),`$ (2)
where $`v_\nu ^{}=(\gamma ,\beta \gamma ,0,0).`$ The unit 4-vector (the components) $`t^\mu `$ in the time direction in $`S`$ transforms upon the LT into the unit 4-vector $`v^\nu `$, the 4-velocity of the moving observers, that contains not only the temporal component but also $`0`$ spatial component. Thence, the LT transform the set of components (1) into (2). Note that $`E^\mu `$ *and* $`B^\mu `$ *do have the temporal components as well.* Further the components $`E^\mu `$ ($`B^\mu `$) in $`S`$ transform upon the LT again to the components $`E^\mu `$ ($`B^\mu `$) in $`S^{}`$; there is no mixing of components. Actually this is the way in which every well-defined 4-vector (the components) transforms upon the LT. A geometric quantity, an abstract tensor $`E^a,`$ can be represented by CBGQs in $`S`$ and $`S^{}`$ (both with the ESC) as $`E^\mu \gamma _\mu `$ and $`E^\mu \gamma _\mu ^{},`$ where $`E^\mu `$ and $`E^\mu `$ are given by the relations (1) and (2) respectively. *All the primed quantities (components and the basis) are obtained from the corresponding unprimed quantities through the LT.* Of course it must hold that

$$E^a=E^\mu \gamma _\mu =E^\mu \gamma _\mu ^{},$$
(3)
since the components $`E^\mu `$ transform by the LT and the basis $`\gamma _\mu `$ transforms by the inverse LT thus leaving the whole CBGQ invariant upon the passive LT. The invariance of some 4D CBGQ upon the passive LT is the crucial requirement that must be satisfied by any well-defined 4D quantity. It reflects the fact that such mathematical, invariant, geometric 4D quantity represents *the same physical object* for relatively moving observers. The use of CBGQs enables us to have clearly and correctly defined the concept of sameness of a physical system for different observers. The importance of this concept in SR was first pointed out in . However they also worked with components in the ESC (the covariant quantities) and not with geometric quantities (the invariant quantities). It should be noted that in all other standard treatments, e.g., \[1-3\], the importance of such concept is completely overlooked what caused many difficulties in understanding SR. It can be easily checked by the direct inspection that (3) holds when $`E^\mu `$ and $`E^\mu `$ are given by (1) and (2). (The same holds for $`B^a.`$)

In contrast to the above consideration in all usual treatments, e.g.,  and  eqs. (3.5) and (3.24), in $`S^{}`$ one again simply makes the identification of six independent components of $`F^{\mu \nu }`$ with three components $`E^i`$, $`E^i=F^{i0}`$, and three components $`B^i`$, $`B^i=(1/2)\epsilon ^{ikl}F_{lk}^{}.`$ This means that standard treatments assume that under the passive LT the set of components $`t^\mu =(1,0,0,0)`$ from $`S`$ transform to $`t^\nu =(1,0,0,0)`$ ($`t^\nu `$ are the components of the unit 4-vector in the time direction in $`S^{}`$ and in the ESC), and consequently that $`E^\mu `$ and $`B^\mu `$ from (1) transform to $`E_{st.}^\mu `$ and $`B_{st.}^\mu `$ in $`S^{},`$

$`E_{st.}^\mu `$ $`=`$ $`F^{\mu \nu }t_\nu ^{},B_{st.}^\mu =(F^{})^{\mu \nu }t_\nu ^{};E_{st.}^\mu =(0,E^1,\gamma E^2\gamma \beta B^3,\gamma E^3+\gamma \beta B^2),`$
$`B_{st.}^\mu `$ $`=`$ $`(0,B^1,\gamma B^2+\gamma \beta E^3,\gamma B^3\gamma \beta E^2),`$ (4)
where the subscript - st. is for - standard. *The temporal components of* $`E_{st.}^\mu `$ *and* $`B_{st.}^\mu `$ *in* $`S^{}`$ *are again zero as are the temporal components of* $`E^\mu `$ *and* $`B^\mu `$ *in* $`S.`$This fact clearly shows that *the transformations given by the relation* *(4) are not the LT of some well-defined 4D quantities; the LT cannot transform a 4-vector for which the temporal component is zero in one frame* $`S`$ *to the 4-vector with the same property in relatively moving frame* $`S^{}`$. Also *the LT cannot transform the unit 4-vector in the time direction in one frame* $`S`$ *to the unit 4-vector in the time direction in another relatively moving frame* $`S^{}.`$ Obviously $`E_{st.}^\mu `$ and $`B_{st.}^\mu `$ are completely different quantities than $`E^\mu `$ and $`B^\mu `$ (2) that are obtained by the LT. We can easily check that

$$E_{st.}^\mu \gamma _\mu ^{}E^\mu \gamma _\mu ,B_{st.}^\mu \gamma _\mu ^{}B^\mu \gamma _\mu .$$
(5)
This means that, e.g., $`E^\mu \gamma _\mu `$ and $`E_{st.}^\mu \gamma _\mu ^{}`$ *are not the same quantity for observers in* $`S`$ *and* $`S^{}.`$ As far as relativity is concerned the quantities, e.g., $`E^\mu \gamma _\mu `$ and $`E_{st.}^\mu \gamma _\mu ^{},`$ are not related to one another. Their identification is the typical case of mistaken identity. The fact that they are measured by two observers does not mean that relativity has something to do with the problem. The reason is that observers $`S`$ and $`S^{}`$ are not looking at the same physical object but at two different objects. *Every observer makes measurement on its own object and such measurements are not related by the LT.* Thus the transformations (4) are not the LT and $`E_{st.}^\mu `$ and $`B_{st.}^\mu `$, in contrast to $`E^\mu `$ and $`B^\mu ,`$ are not well-defined 4D quantities.

From *the relativistically incorrect transformations* (4) one simply derives the transformations of the spatial components $`E_{st.}^i`$ and $`B_{st.}^i`$. As can be seen from (4) *the transformations of* $`E_{st.}^i`$ *and* $`B_{st.}^i`$ *are exactly the standard transformations of components of the 3-vectors* $`𝐄`$ *and* $`𝐁`$ that are obtained by Einstein in  and subsequently quoted in almost every textbook and paper on relativistic electrodynamics. Then in the same way as in $`S`$ the 3-vectors $`𝐄^{}`$ and $`𝐁^{}`$ as *geometric quantities in the 3D space* are constructed in $`S^{}`$ from the spatial components $`E_{st.}^i`$ and $`B_{st.}^i`$ and *the unit 3-vectors* $`𝐢^{},`$ $`𝐣^{},`$ $`𝐤^{},`$ e.g., $`𝐄^{}=F^{10}𝐢^{}+F^{20}𝐣^{}+F^{30}𝐤^{}.`$ Both the transformations (4) and the transformations for $`E_{st.}^i`$ and $`B_{st.}^i`$ (i.e., for $`𝐄^{}`$ and $`𝐁^{}`$) are typical examples of the ”apparent” transformations (AT) that are first discussed in  and . The AT of the spatial distances (the Lorentz contraction) and the temporal distances (the dilatation of time) are elaborated in detail in  and  (see also ), and in  I have discussed the AT of $`𝐄`$ and $`𝐁`$. It is explicitly shown in  that the true agreement with experiments that test SR exists only when the theory deals with well-defined 4D quantities, i.e., the quantities that are invariant upon the passive LT.

In all previous treatments of SR, e.g., \[1-3\] , the transformations for $`E_{st.}^i`$ and $`B_{st.}^i`$ are considered to be the LT of the 3D electric and magnetic fields. However our analysis shows that the transformations for $`E_{st.}^i`$ and $`B_{st.}^i`$ are derived from *the relativistically incorrect transformations* (4) and that the 3-vectors $`𝐄^{}`$ and $`𝐁^{}`$ are formed by an incorrect procedure in 4D spacetime, i.e., by multiplying these *relativistically incorrect components* with *the unit 3-vectors.* All this together exactly proves that the standard transformations for $`𝐄^{}`$ and $`𝐁^{}`$ have absolutely nothing to do with the LT, and that the quantities $`E_{st.}^i`$ and $`B_{st.}^i,`$ i.e., the 3-vectors $`𝐄`$ and $`𝐁`$ are not well-defined 4D quantities. Consequently *the usual ME with 3D* $`𝐄`$ *and* $`𝐁`$ *are not in agreement with SR and they are not physically equivalent with relativistically correct FE with* $`F^{ab}`$ (see also ).

The relation (1) reveals that we can always select a particular - but otherwise arbitrary - IFR $`S`$ in which the temporal components of $`E^\mu `$ and $`B^\mu `$ are zero. Then in that frame the usual ME for the spatial components $`E^i`$ and $`B^i`$ (of $`E^\mu `$ and $`B^\mu `$) will be fulfilled. As a consequence the usual ME can explain all experiments that are performed in one reference frame. However as shown above the temporal components of $`E^\mu `$ and $`B^\mu `$ are not zero; (2) is relativistically correct, but it is not the case with (4). This means that the usual ME cannot be used for the explanation of any experiment that test SR, i.e., in which relatively moving observers have to compare their data *obtained by measurements on the same physical object.*

The relations (2) imply that in the ESC the well-defined 4D electric and magnetic fields will be CBGQs, the 4-vectors, $`E^\mu \gamma _\mu =F^{\mu \nu }v_\nu \gamma _\mu `$ and $`B^\mu \gamma _\mu =(F^{})^{\mu \nu }v_\nu \gamma _\mu `$ respectively. In an arbitrary chosen IFR $`S`$ $`v_\nu `$ can be taken to be in the time direction, i.e., $`v_\nu =t_\nu `$, whence one finds (1) in $`S`$ and (2) in any relatively moving IFR $`S^{}.`$ (The components in the ESC, e.g., $`E^\mu =F^{\mu \nu }v_\nu `$, and the covariant formulation of electrodynamics with them, are considered in ,  and ). In order to have the electric and magnetic 4-vectors defined without reference frames, i.e., *independent of the chosen reference frame and of the chosen system of coordinates in it*, we employ the abstract tensors and write $`E^a=F^{ab}v_b`$ and $`B^a=(1/2)\epsilon ^{abcd}v_bF_{cd},`$ see  and . The velocity $`v_b`$ and all other quantities entering into these relations are defined without reference frames. $`v_b`$ characterizes some general observer. Thus *the relations for* $`E^a`$ *and* $`B^a`$ *hold for any observer.* When some reference frame is chosen with the ESC in it and when $`v_b`$ is specified to be in the time direction in that frame, i.e., $`v_b=t_b`$, then all results of the classical electromagnetism are recovered in that frame. However, in contrast to the description of the electromagnetism with the 3D $`𝐄`$ and $`𝐁,`$ the description with $`E^a`$ and $`B^a`$ is correct not only in that frame but in all other relatively moving frames and it holds for any permissible choice of coordinates. In  I have also presented the form of the LT that is independent of the chosen coordinates. Furthermore I have developed three equivalent but independent, consistent and complete formulations of electrodynamics with abstract tensors, with $`F^{ab}`$, $`E^a`$ and $`B^a,`$ and with their complex combination. (Note that the above relations for $`E^a`$ and $`B^a`$ are not the physical definitions of $`E^a`$ and $`B^a`$ but they simply connect the independent and complete formulations with $`F^{ab}`$ and $`E^a,`$ $`B^a`$. The physical definitions of $`E^a`$ and $`B^a`$ are given in terms of the Lorentz force expressed with $`E^a`$ and $`B^a`$ and Newton’s second law, as in  in the TF and in the first paper in  in the CAF.)

The same situation as in TF happens in the standard CAF, e.g., . The ESC, i.e., the standard basis $`\left\{\gamma _\mu \right\},`$ is chosen from the outset and the relations for $`E`$ and $`B`$ are written explicitly using the basis 1-vector in the time direction, $`\gamma _0`$. In some IFR$`S,`$ $`E=F\gamma _0=F^{k0}\gamma _k`$, and $`B=\gamma _5(F\gamma _0)=(1/2)\epsilon ^{0ikl}F_{lk}\gamma _i`$, where $`\gamma _5`$ is the pseudoscalar for the frame $`\left\{\gamma _\mu \right\}`$, ’$``$’ and ’$``$’ denote the inner and outer products of the basis 1-vectors. (This form for $`E`$ and $`B`$ is equivalent to the forms given in the standard CAF, e.g., .) Then it is wrongly assumed that under the active LT (expressed in CAF by rotors; see , ) the new, i.e., the Lorentz transformed, $`E^{}`$ and $`B^{}`$ are $`E_{st.}^{}=F^{}\gamma _0`$ and $`B_{st.}^{}=\gamma _5(F^{}\gamma _0).`$ However when $`E`$ is transformed by the active LT then $`R(F\gamma _0)\stackrel{~}{R}`$ *is not* equal to ($`RF\stackrel{~}{R})\gamma _0=E_{st.}^{}`$ (for the explicit form of the rotor $`R`$ see, e.g.,  ch.6 and ). Really the components of $`E_{st.}^{}`$($`B_{st.}^{}`$) are the same as in the AT (4), while the components of $`RE\stackrel{~}{R}`$ ($`RB\stackrel{~}{R}`$) are the same as in the correct LT (2). Finally the standard transformations for the 3D $`𝐄`$ and $`𝐁`$ are derived from the AT for $`E_{st.}^{}`$ and $`B_{st.}^{}`$, see  Sec. 18 and  Ch. 7. In  I have presented the relativistically correct form for $`E`$ and $`B`$ by replacing $`\gamma _0`$ with $`v`$, the velocity of some general observer, which is also defined, as in TF, without reference frames. The CAF from  enabled me to develop *four* equivalent but independent, consistent and complete formulations of electrodynamics with field bivector $`F`$, with 1-vectors $`E`$ and $`B`$ , with complex 1-vector $`\mathrm{\Psi }`$ and, what is specific for the CAF, with a *real* Clifford multivector $`\mathrm{\Psi }`$. Furthermore all relevant quantities for the electromagnetism, the stress-energy 1-vector $`T(v)`$, the energy density $`U`$ (scalar), the Poynting 1-vector $`S`$, the angular momentum density $`M`$ (bivector) and the Lorentz force $`K`$ (1-vector) are directly derived from the FE and all of them are defined without reference frames.

The whole consideration explicitly shows that the 3D quantities $`𝐄`$ and $`𝐁`$, their transformations and the equations with them are ill-defined in the 4D spacetime. More generally, the 3D quantities do not have an independent physical reality in the 4D spacetime. Thence the relativistically correct physics must be formulated with 4D quantities that are defined without reference frames, or by the 4D CBGQs (e.g., as in ,  in the TF and  in the CAF). The principle of relativity is automatically included in such theory with well-defined 4D quantities, while in the standard approach to SR  it is postulated outside the mathematical formulation of the theory. The comparison with experiments from  and  reveals that the true agreement with experiments that test SR can be achieved only when such well-defined 4D quantities are considered.

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