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# Critical dynamics of an interacting magnetic nanoparticle system

## 1 Introduction

The dynamics of systems of interacting ferromagnetic nanoparticles has been the focus of extensive research in recent years. A question of considerable controversy has been the existence of a phase transition to a low-temperature spin-glass-like phase . Recent studies on strongly interacting systems have reported a critical slowing down  and a critical divergence of the non-linear susceptibility . In addition, non-equilibrium properties such as ageing, memory and rejuvenation phenomena have been observed in magnetic relaxation and low frequency AC susceptibility measurements at low temperatures . These observations indicate the existence of a low-temperature spin-glass-like state. However, some questions about the collective state of interacting nanoparticles are still not resolved. In a recent experimental study of an interacting maghemite nanoparticle system , it was not possible to find evidence of a finite temperature transition to a spin-glass-like phase. Still, the particle system exhibited non-equilibrium dynamics in magnetic relaxation experiments, typical of spin glasses. The absence of a critical behaviour was in this study linked to mixing of collective and single particle relaxation effects. Mixing of this kind can for instance originate from a broad particle size distribution, or it may be observed in a system with a small volume fraction of particles and therefore comparably weak inter-particle interactions.

In this work, extensive studies of the magnetic dynamics in a close to monodisperse nanoparticle system are presented. Three samples having different volume concentrations of nanoparticles were investigated; one dilute and nominally non-interacting sample and two more concentrated interacting samples. Both interacting samples exhibit collective behaviour due to dipolar interactions at low temperatures, but only the most interacting sample displays critical dynamics in the investigated time window and shows equilibrium dynamics quite similar to that of an atomic spin glass.

## 2 Experimental

The particles were prepared by thermal decomposition of Fe(CO)5 (20.0 ml) in a mixture of carrier liquid (50.0 ml cis-trans decalin) and surfactant (4.0 g oleic acid) by the method described in . This method leads to the formation of surfactant coated particles of the amorphous alloy FexC1-x (x $``$ 0.2-0.3). The decomposition was carried out slowly by using low heating powers. Great care was taken at all times to avoid oxidation of the particles and a flow of Ar/H2 (98/2%) gas through the reaction vessel was maintained throughout the preparation. After preparation, the decalin carrier liquid was evaporated at 140 C under reduced pressure using a gas flow to drive out the vapour and a small amount of de-gassed xylene was added such that the volume fraction of particles in the resulting base ferrofluid was about 5 vol%. More dilute samples were obtained by further dilution of this ferrofluid by addition of xylene and more concentrated samples were obtained by evaporating the xylene at room temperature in vacuum. All sample handling after the preparation of the base ferrofluid was carried out in an argon glove box. The chemical state of the iron in the ferrofluids was checked by Mössbauer spectroscopy, which showed that no significant oxidation of the particles had taken place during the sample preparation and sample handling. The particle volume fractions in the resulting samples were estimated from the iron content determined by atomic absorption spectroscopy. The sizes of the particles were determined from transmission electron microscopy (TEM) studies. A droplet of a dilute ferrofluid was placed onto a grid, that was left in air for about a week to ensure full oxidation of the particles. The size determination from the resulting TEM micrographs was subsequently corrected for the change in density due to the oxidation of the particles. The shape of the particles was spherical to a good approximation. The particle size distribution was obtained using the computer analysis method described in . The analysis of 1579 particles yielded the average particle diameter $`d=5.3`$ nm with the standard deviation 0.3 nm. The volume-weighted volume distribution was well described by the lognormal distribution, $`f(V)dV=(2\pi )^{1/2}(\sigma V)^1\mathrm{exp}[\mathrm{ln}^2(V/V_m)/2\sigma ^2]dV`$, with $`V_m=78.2`$ nm3 and $`\sigma =0.13`$. The saturation magnetisation was estimated to $`1\times 10^6`$ Am-1 from Langevin fits to magnetisation vs. field curves at several temperatures well above the superparamagnetic blocking temperature. The present preparation batch is slightly different from that studied previously in . We have studied three samples with particle concentrations of $`17\pm 4`$, $`5\pm 1`$ and $`0.06\pm 0.02`$ vol%. In the most concentrated sample, most of the carrier liquid was evaporated and the sample had a paste-like consistency. This resulted in poor thermal contact between the sample and the sample container. Thermal stability was not achieved until several minutes after a change in temperature, preventing systematic studies of the non-equilibrium dynamics for this sample.

Two experimental set-ups were used for the magnetic studies. A commercial susceptometer (LakeShore model 7225) was used for DC field scans and AC susceptibility measurements in a frequency range of 15 - 1000 Hz. A non-commercial superconducting quantum interference device (SQUID) magnetometer  was used for AC susceptibility measurements in a frequency range of 10 mHz - 9.1 kHz, zero field cooled (ZFC) relaxation measurements and magnetic noise measurements. The applied AC and DC fields were chosen small enough (0.1 Oe) to ensure linear response from the samples. The background field was less than 1 mOe. The ZFC relaxation measurements were carried out by cooling the sample to the measuring temperature $`T`$ in zero field, equilibrating the system for a wait time $`t_w`$, and then applying a small DC field $`h`$ and measuring the magnetisation $`M(T,t)`$ as a function of time, $`t`$, after that the field was applied. For a slowly relaxing system, it can be shown that $`M(T,t)`$ and the relaxation rate $`S(T,t)h^1M(T,t)/\mathrm{ln}t`$ relate to the real and imaginary components of the AC susceptibility as

$`M(T,t)/h`$ $``$ $`\chi ^{}(T,\omega ),`$ (1)
$`S(T,t)`$ $``$ $`{\displaystyle \frac{2}{\pi }}\chi ^{\prime \prime }(T,\omega ),`$ (2)
with $`t=1/\omega `$. Magnetic noise measurements were performed in zero external field using an HP35670A dynamic signal analyser. The power spectrum of the magnetic fluctuations was measured in three overlapping frequency intervals (i) 0.003-12.5 Hz, (ii) 0.25-400 Hz and (iii) 8-12500 Hz. The background spectra were subtracted from the data. Data of the same order of magnitude as the background signal were not used in the analysis. The fluctuation-dissipation theorem  relates the noise power spectrum to the zero-field limit of the out-of-phase AC susceptibility as

$$P(T,\omega )=4k_BT\frac{\chi ^{\prime \prime }(T,\omega )}{\omega }.$$
(3)
A comparison between the out-of-phase component obtained from AC susceptibility measurements and results obtained from zero field noise measurements verifies that equation (3) is obeyed and hence that the AC data are obtained in the linear response regime.

## 3 Results and discussion

### 3.1 General behaviour

Figure 1 shows the AC susceptibility measured in the commercial set-up for the three samples. The most dilute sample with a 0.06 vol% fraction of particles is intended to serve as an experimental reference for a non-interacting system. However, the peak height of $`\chi ^{\prime \prime }`$ for this sample increases slightly with increasing frequency. This trend is opposite to the expected behaviour for non-interacting nanoparticles  and thus indicates that the dynamics of this sample is influenced by weak inter-particle interactions. Despite this, it is possible to assess the distribution of energy barriers with reasonable accuracy making use of the method described in . This analysis yields $`\tau _0=1\times 10^{12}`$ s and $`K=0.9\times 10^5`$ Jm-3. The extracted values of $`K`$ and $`\tau _0`$ compare reasonably well with previous estimates. For 5.0 nm Fe-C particles, $`K`$ has been estimated to $`1.3\times 10^5`$ Jm-3, and it has been found that $`K`$ increases with decreasing particle size to $`3\times 10^5`$ Jm-3 for 3.2 nm particles . Studies of different preparation batches have reported values of $`\tau _0`$ in the range $`2\times 10^{12}`$ s to $`3\times 10^{11}`$ s .

Figures 2 and 3 show the AC susceptibility data measured in the non-commercial SQUID for the 5 and 17 vol% samples, respectively. For the 5 vol% sample, ZFC relaxation data are also included. A few differences in the behaviour of these samples as compared to the dilute sample can immediately be noticed. The peak height of $`\chi ^{\prime \prime }`$ increases significantly with increasing frequency, and the width of the peak increases with increasing frequency. The onset of a non-zero $`\chi ^{\prime \prime }`$, is shifted towards higher temperatures and it becomes sharper with increasing volume fraction of particles.

Figure 4 shows the relaxation rate for the 5 vol% sample measured for two different wait times at different temperatures. Below 40 K, a clear wait time dependence is observed indicating that non-equilibrium phenomena plays a key role for the dynamics at low temperatures. The same sample has recently been subject to a detailed study of the low temperature non-equilibrium dynamics in which the memory effect in the ac susceptibility was observed and further characterised by temperature cycling ZFC relaxation experiments . It was shown that the non-equilibrium dynamics in this sample is governed by long-range collective behaviour and that well-known concepts for spin glasses such as chaos with temperature and overlap length are necessary to describe the observations. This implies that the magnetic relaxation of the two concentrated samples must be analysed in terms of collective dynamics. A model for weakly interacting particles, such as that proposed in , where the effect of dipolar interaction on the relaxation time is accounted for by introducing the thermodynamic averages of the local dipolar field in a rigorous expression for the single particle relaxation time, is only valid at temperatures much higher than the freezing temperatures of the two concentrated samples. Below, we briefly introduce the concepts of dynamic scaling and discuss the observed dynamics for the two concentrated samples in terms of critical dynamics.

### 3.2 Dynamic scaling

A signature of a continuous magnetic phase transition is the divergence of the correlation length, $`\xi `$, when the phase transition temperature, $`T_g`$, is approached from above as $`\xi /a=ϵ^\nu `$, where $`a`$ is the average distance between interacting moments, $`ϵ=T/T_g1`$ is the reduced temperature and $`\nu `$ is a critical exponent. According to conventional critical slowing down, the longest relaxation time due to correlated dynamics, $`\tau _c`$, is related to the correlation length as $`\tau _c(\xi /a)^z`$, where $`z`$ is the dynamic critical exponent. Hence, for $`TT_g^+`$

$$\tau _c=\tau _{}ϵ^{z\nu },$$
(4)
where $`\tau _{}`$ is a microscopic relaxation time. According to the dynamic scaling hypothesis , for $`TT_g^+`$ and $`t/\tau _{}1`$, the spin auto-correlation function can be written in the scaling form

$$q(t)=t^{\beta /z\nu }Q(t/\tau _c),$$
(5)
where $`\beta `$ is a critical exponent and $`Q(x)`$ is a scaling function. Using linear response theory it is possible from this relation to obtain the complex susceptibility and derive the scaling relation

$$\frac{\chi ^{\prime \prime }(T,\omega )}{\chi _{\mathrm{eq}}(T)}=ϵ^\beta G(\omega \tau _c),$$
(6)
where $`\omega =1/t`$ and $`G(x)`$ is a scaling function. The asymptotic behaviour is $`G(x)x^y`$, with $`y=1`$ and $`y=\beta /z\nu `$ for small and large values of $`x`$, respectively. Using the asymptotic behaviour of $`G(x)`$ in the limit $`\omega \tau _c0`$, the following relation holds

$$\frac{1}{\omega }\frac{\chi ^{\prime \prime }(T,\omega )}{\chi _{\mathrm{eq}}(T)}ϵ^{z\nu +\beta }\tau _c^{1\beta /z\nu },$$
(7)
implying that the left hand side of equation (7) at each temperature reaches a frequency independent plateau.

The meaning of $`\tau _{}`$ is that it is the relaxation time of the individual magnetic entities in the system. For spin glasses, $`\tau _{}10^{13}`$ s and is the fluctuation time of an atomic moment. For nanoparticles, $`\tau _{}`$ can be assigned to the superparamagnetic relaxation time of a single particle of average size. In a dense system, the dipolar interaction may modify this relaxation time compared that of isolated particles. However, as a first approximation, it is reasonable to assume that $`\tau _{}`$ is close to the superparamagnetic relaxation time of an isolated particle, which in the relevant temperature range for our studies can be approximated by the Arrhenius-Neél expression. Below, we compare two approximations: i) $`\tau _{}=`$ constant, and ii) $`\tau _{}=\tau _0\mathrm{exp}(KV_m/k_BT)`$. The first approximation has been used in previous work , but it is only a good approximation if there is little variation of the single particle relaxation time in the temperature interval used for the analysis.

In AC susceptibility experiments, the slowing down of the relaxation time $`\tau _c`$ (equation (4) can be derived from the temperatures where an onset of dissipation occurs (freezing temperatures) as a function of the observation time $`\omega ^1`$. We have considered two criteria for the onset. In the first criterion, the freezing temperature is defined as the temperature at which $`\chi ^{\prime \prime }(T,\omega )`$ attains 15% of its maximum value. In the second criterion, the freezing temperature is defined from the relation $`\chi ^{}(T_f,\omega )=0.98\chi _{eq}(T_f)`$. Figure 5(b) shows the freezing temperatures for the two concentrated samples obtained from $`\chi ^{}`$ data. The superparamagnetic blocking temperatures estimated from the peaks of the $`\chi ^{\prime \prime }`$ data for the dilute sample are included for comparison.

#### 3.2.1 17 vol% sample

First, we consider the approximation $`\tau _{}=`$ constant. Using the out-of-phase susceptibility data, a dynamic scaling analysis according to equation (4) results in $`T_g=49.5\pm 2`$ K, $`z\nu =10.5\pm 2`$ and $`\tau _{}=10^{7.7\pm 1}`$ s . This analysis is performed for reduced temperatures in the range $`0.16<ϵ<\mathrm{\hspace{0.17em}0.37}`$ and corresponds to 4 decades of observation times. A similar analysis using the in-phase susceptibility data results in $`T_g=50.5\pm 2`$ K, $`z\nu =9.5\pm 2`$ and $`\tau _{}=10^{8.3\pm 1}`$ s. The values of $`T_g`$ and $`z\nu `$ from the two analyses are in good agreement, and the value of $`\tau _{}`$ is, considering the temperature interval used in the analysis and the estimates of $`\tau _0`$ and $`K`$ given above, within the limits implied by the Arrhenius-Néel expression. The derived values of $`z\nu `$ also compare well to values found in previous work on nanoparticles: $`z\nu =11\pm 3`$ in  and $`z\nu =10.5\pm 3`$ in , but less well to $`z\nu =7.0\pm 0.3`$ found in reference . A good agreement is also found comparing with canonical 3D Ising and Heisenberg spin glasses, for which $`z\nu =810`$ . An analysis according to the full scaling relation, equation (6), using $`T_g=49.5\pm 1.5`$ and $`z\nu =10.5\pm 2.0`$ yields data collapse for $`\beta =1.1\pm 0.2`$ (see reference , figure 3). This analysis is based on all available $`\chi ^{\prime \prime }`$ data with temperatures corresponding to $`ϵ>0.01`$ ($`T>50`$ K). The value of $`\beta `$ is in good agreement with $`\beta =1.2\pm 0.1`$ obtained from a full scaling analysis of the non-linear magnetic susceptibility on a similar sample , but larger than typical values of $`\beta =0.50.8`$ reported for 3D Ising and Heisenberg spin glasses . The value of $`\beta /z\nu 0.11`$, extracted from the asymptotic behaviour of $`G(x)`$ for large $`x`$, is consistent with the derived values of $`\beta `$ and $`z\nu `$.

Next, we consider the effect of using $`\tau _{}=\tau _0\mathrm{exp}(KV_m/k_BT)`$. It should be noted that this introduces one extra parameters that can be varied in the analysis, and we have therefore explored the critical behaviour for a variety of choices of $`\tau _0`$ and $`KV_m`$ to evaluate the robustness of the estimates of $`z\nu `$ and $`\beta `$. Critical slowing down analyses have been performed for various fixed values of $`\tau _0`$ and $`T_g`$ and the values of $`z\nu `$ and $`KV_m`$ have been estimated and used in the analysis according to the scaling relation, equation (6), to extract the value of $`\beta `$. From these analyses, it is found that both the critical slowing down analysis and the full scaling relation can be fulfilled for $`T_g=50\pm 2`$ K with $`\tau _0=1\times 10^{11}s`$. The estimate of $`KV_m/k_B`$ depends slightly on whether the $`\chi ^{}`$ or the $`\chi ^{\prime \prime }`$ data are used in the critical slowing down analysis, and the corresponding parameter intervals are $`KV_m/k_B=500\pm 100`$ K using $`\chi ^{}`$ (shown in figure 5) and $`KV_m/k_B=650\pm 100`$ K using $`\chi ^{\prime \prime }`$. For both analyses, the extracted critical exponents attain the values $`z\nu =8.5\pm 2`$ and $`\beta =0.9\pm 0.2`$. Other values of $`\tau _0`$ of the order of $`10^{11}`$ s yield slightly different values of $`KV_m/k_B`$ but the same values of the critical exponents. The values of $`KV_m/k_B`$ and $`\tau _0`$ are of the same size as the estimates for the dilute sample, $`KV_m/k_B510`$ K and $`\tau _01\times 10^{12}`$ s, but it is stressed that an exact correspondence is not expected. The values of $`z\nu `$ and $`\beta `$ are slightly smaller than those obtained from the analysis assuming a constant $`\tau _{}`$. The decrease of $`z\nu `$ is due to the fact that the temperature dependence of $`\tau _c/\tau _{}`$ is weaker when $`\tau _{}`$ is allowed to vary with temperature. The reduced value of $`z\nu `$ and the extracted smaller value of $`\beta `$ leads to $`\beta /z\nu 0.11`$, which is the same value as found from the analysis using a constant value of $`\tau _{}`$. The data collapse of $`ϵ^\beta \chi ^{\prime \prime }(T)/\chi _{eq}(T)`$ vs. $`\omega \tau _c`$ to a single function $`G(x)`$ according to equations (4) and (6) using $`\tau _0=10^{11}`$ s and $`KV_m/k_B=570`$ K (the average of the values obtained using $`\chi ^{}`$ and $`\chi ^{\prime \prime }`$ in the critical slowing down analyses) is shown in figure 6. The scaling is of the same quality as that assuming a constant $`\tau _{}`$, and the asymptotic behaviours are the same (in agreement with the estimates of $`\beta `$ and $`z\nu `$).

Figure 7(b) shows $`\chi ^{\prime \prime }(\omega )/\omega \chi _{eq}`$ as a function of $`\omega `$ for different temperatures $`T>T_g`$ in a log-log plot for the 17 vol% sample. The prediction of plateaus at low frequencies from equation (7) holds regardless of a temperature dependence of $`\tau _{}`$ and figure 7(b) shows that the prediction is well confirmed for this sample. In the same figure, the behaviour calculated from equation (6) is also included using the experimentally determined scaling function, $`G(x)`$, and extrapolating using its asymptotic behaviour.

#### 3.2.2 5 vol% sample

For the 5 vol% sample, an apparent scaling according to equation (4) with a constant value of $`\tau _{}`$ can be obtained for temperatures corresponding to $`0.25<ϵ<\mathrm{\hspace{0.17em}0.8}`$ (6 decades of observation times) with $`T_g=35.1\pm 2`$ K, $`z\nu =10.8\pm 1`$ and $`\tau _{}=10^{4.5\pm 0.5}`$ s using $`\chi ^{\prime \prime }`$ data, and with $`T_g=34.6\pm 2`$ K, $`z\nu =10.8\pm 1`$ and $`\tau _{}=10^{4.7\pm 0.5}`$ s using $`\chi ^{}`$ and ZFC relaxation data (shown in figure 5). However, deviations from scaling are found at lower temperatures ($`ϵ<0.25`$). Moreover, it is not possible to obtain data collapse according to the full scaling relation equation (6), with temperatures corresponding to $`0.02<ϵ<\mathrm{\hspace{0.17em}0.8}`$ (or to $`0.25<ϵ<\mathrm{\hspace{0.17em}0.8}`$), for any choice of $`T_g`$, $`z\nu `$ and $`\beta `$. Based on the estimates of $`KV_m`$ and $`\tau _0`$ for the dilute sample and the temperature range used in the analysis above, it is expected that $`\tau _{}10^910^7`$ s. However, the derived value ($`\tau _{}10^{4.6}`$) deviate by orders of magnitude from this range. Furthermore, even introducing an Arrhenius-Néel temperature dependence of $`\tau _{}`$, it is not possible to obtain unambiguous parameters from the critical slowing down analysis and to fulfil scaling according to equation (6). A simple manifestation of critical dynamics, which is independent of a temperature dependence of $`\tau _{}`$, is that $`\chi ^{\prime \prime }(\omega )/\omega \chi _{eq}`$ should settle on plateaus for small values of $`\omega `$. Conferring figure 7(a), it is seen that this prediction is not fulfilled for the 5 vol% sample (except for $`T65`$ K), and this is a further indication of non-critical dynamics in this sample.

Several factors may contribute to deviations from critical behaviour and a possible non-divergence of the correlation length. First, there may be physical clustering of the particles (i.e., regions with a higher density of particles than average). The effect of clustering is two-fold: At comparably high temperatures, where short-range correlations are relevant, the stronger inter-particle interaction in particle clusters will enhance the local correlation length and shift the dynamics to longer time scales than expected from the volume fraction of particles and a homogeneous particle dispersion. In addition, the small scale heterogeneity will create a dispersion of length scales for the collective dynamics that modifies and possibly limits the growth of correlations at lower temperatures. Second, the polydispersivity of the particle system leads to a distribution of single particle relaxation times with a width that increases significantly with decreasing temperature (and is thus more important for the 5 vol% sample than for the 17 vol% sample). At lower temperatures, the largest particles may therefore become thermally blocked on time scales comparable to the longest time scale related to the collective dynamics and act as random magnets instead of taking part in the collective dynamics. This may completely mask or even obstruct long-range collective behaviour, as discussed in . The non-critical behaviour of the present 5 vol% sample is most likely both due to the formation of clusters of particles (see section below) and the dispersion of single particle relaxation times.

### 3.3 Relaxation function

For a spin glass and $`T<T_g`$, $`S(T,t)`$ is history dependent and has a non-trivial variation with $`t`$. However, when quasi-equilibrium is probed, one can write $`S(T,t)t^{y(T)}`$, where $`y(T)`$ attains a positive value close to zero . For $`T>T_g`$, the time dependence of $`S(T,t)`$ is determined by the critical dynamics. As discussed previously, the critical dynamics result in fluctuations spanning all time scales between $`\tau _{}`$ and $`\tau _c`$, and this gives a very broad spectrum of relaxation times. From equation (2) and using the asymptotic behaviours of $`G(x)`$ in equation (6), it is easily seen that $`S(T,t)t^{y(T)}`$ with $`y(T)=\beta /z\nu 0.1`$ for $`\tau _{}t\tau _c`$ and $`y(T)=1`$ for $`t\tau _c`$ . At intermediate observation times, $`y(T)`$ monotonically increases with $`t`$ between the two extremes and a cross-over (or ’knee’) from an essentially flat $`S(T,t)`$ vs. $`t`$ curve to $`S(T,t)t^1`$ is expected at $`t\tau _c`$.

Figure 8 shows the relaxation rate vs time for the three samples at different temperatures in the range $`20`$ K $`T`$ $`70`$ K. For the 0.06 and 17 vol% samples $`\chi ^{\prime \prime }`$ data are shown, and for the 5 vol% sample results from ZFC relaxation, AC susceptibility and magnetic noise measurements are included. For the 17 vol% sample, $`\chi ^{\prime \prime }`$ data for $`T>T_g`$ obtained from equation (6) using the experimentally estimated $`G(x)`$ and the expected asymptotic behaviour for small $`x`$ are also shown. In the low-temperature region, $`T<\mathrm{\hspace{0.17em}30}`$ K, the magnitudes of the relaxation rates for the two interacting samples are much smaller than that for the 0.06 vol% sample. This is a signature of collective dynamics . Moreover, the relaxation rate of the 17 vol% sample is smaller than that of the 5 vol% sample. For temperatures $`T>\mathrm{\hspace{0.17em}40}`$ K and in the investigated time window, the relaxation rate of the 0.06 vol% sample decays with increasing observation time, while the relaxation rate of the the 5 vol% sample at short time scales exhibits a weak frequency dependence followed by a knee and a decrease towards zero at longer time scales. This approach towards zero relaxation rate ($`y(T)0.50.6`$ between 45 and 55 K) is slower than that of an atomic spin glass (for which $`y(T)=1`$) and consistent with the lack of plateaus in the $`\chi ^{\prime \prime }(\omega )/\omega \chi _{eq}`$ curves for the corresponding temperatures in figure 7(a). The time dependence of the relaxation rate at time scales shorter than this knee is also uncharacteristic of a spin glass as it is non-monotonic in time and shows a broad maximum. For the 17 vol% sample and in the temperature range $`35`$ K $`<T<\mathrm{\hspace{0.17em}50}`$ K, the relaxation rate exhibits a slow, monotonous decrease with increasing observation time. The relaxation rate follows a $`S(T,t)t^{y(T)}`$ dependence, with $`y(T)`$ decreasing with decreasing temperature, mimicking the expected behaviour of a spin glass system . It should be noted though, that the particle size distribution will cause a temperature dependent and broad onset of the response on short observation times, as can be envisaged by the relaxation rate curves at the lowest temperatures. At temperatures above $`T_g`$, $`T>50`$ K, a knee appears in the relaxation rate also for this sample and the approach towards zero follows a $`S(T,t)t^1`$. At temperatures $`T65`$ K, the cut-off in the relaxation rate is equally sharp for both interacting samples, and the dynamics of the two samples are rather similar. This indicates, for the 5 vol% sample, that the particle moments participating in the dynamics on long time scales in this temperature range are more strongly interacting than average, i.e. that these particles are part of agglomerates showing properties similar to those of the 17 vol% sample.

## 4 Conclusion

Extensive studies of the magnetic dynamics of a nanoparticle system containing nearly monodisperse ferromagnetic particles have been presented. We have shown that a strongly interacting particle system (the 17 vol% sample) displays critical dynamics reminiscent of that of a spin glass. Furthermore, the effect of an Arrhenius-Néel temperature dependence of $`\tau _{}`$ has been explored and it has been found that dynamic scaling for this sample prevails although with slightly reduced values of the critical exponents $`z\nu `$ and $`\beta `$.

For weakly interacting particle systems, the dipolar interaction will only slightly modify the relaxation compared to a non-interacting system, and the relaxation time can be obtained by introducing thermodynamical averages of the dipolar field in an expression for the single-particle relaxation time, as suggested in . Such a theory will apply for the most dilute sample studied here (0.06 vol% sample) near the blocking temperature.

For a wide range of particle concentrations (interaction strengths), neither a pure model for weakly interacting systems nor a model only assuming critical dynamics will correctly describe the magnetic relaxation of an interacting particle system. In the present work, this has been illustrated by the 5 vol% sample, in which correlations and collective behavior are of importance, as evidenced by non-equilibrium dynamics similar to that exhibited by spin glasses  and an apparent critical slowing down in a limited temperature range. Yet, the deviation from critical slowing down at lower temperatures and the failure to satisfy other signatures of critical dynamics show that the slowing down of the magnetic dynamics in this sample differs profoundly from that in spin glasses. The range of concentrations for which such a complex behaviour occurs becomes wider with increasing width of the particle size distribution, as can be evidenced by comparing to the system studied in . For the sample used in that study, the relative dipole interaction strength ($`=M_s^2\varphi /K`$, where $`\varphi `$ is the volume fraction of particles) is comparable to that of the 17 vol% sample studied here, but that sample has a much wider energy barrier distribution and does not exhibit critical dynamics although it shows collective behaviour.

This work was financially supported by The Swedish Natural Science Research Council (NFR). We would like to thank Christian Bender Koch for the atomic absorption spectroscopy measurements.

## References


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# Dynamic concentration of motors in microtubule arrays

## Abstract

We present experimental and theoretical studies of the dynamics of molecular motors in microtubule arrays and asters. By solving a convection-diffusion equation we find that the density profile of motors in a two-dimensional aster is characterized by continuously varying exponents. Simulations are used to verify the assumptions of the continuum model. We observe the concentration profiles of kinesin moving in quasi two-dimensional artificial asters by fluorescent microscopy and compare with our theoretical results.

The cytoskeleton is a network of polymers essential for the dynamic organization of many eukaryotic cells. Its function depends not only on protein fibers, but also on many accessory components . Among these are motor proteins that reversibly bind to and walk along the surface of cytoskeletal polymers, consuming ATP as a source of energy. A natural consequence of this directed movement in organized fiber arrays is an non-uniform spatial distribution of the motors. In vivo microtubules are often observed in radial arrays, or asters, where all microtubule“minus” ends are at the center, and the “plus” ends are radiating outward. Aster of opposite polarity, in which kinesin moves inward can also be formed in-vitro .

In this letter we present quantitative experiments on a quasi two dimensional aster, fig. (1), formed from long microtubules polymerized between closely separated cover slips. We analyze the results of these experiments using a 2D transport diffusion equation. The theory contains a number of approximations, due to angular averaging and projection from 3 to 2 dimensions. We verify that no major quantitative error is introduced by performing simulations in the full confined geometry. We also consider, theoretically, the case of one and three dimensions: The aster in one dimension corresponds to a tube in which microtubules are all oriented in the same direction. This is the case for example in the axons of nerve cells. As distinct motors move toward the “plus” or the “minus” end, we consider both cases of inward/outward directed motion.

Consider $`N`$ immobile straight microtubules radially arranged in the available volume. Molecular motors are present which can exist in two different states, either attached to a filament, or detached. Unattached motors diffuse freely, with a diffusion constant $`D`$. Attached motors move on their filament (radially in the aster geometry) at a velocity $`v`$. Positive values of $`v`$ corresponds to outward movement. Transitions between the two states are stochastic: The motor spontaneously detaches from the microtubule at an unbinding rate $`p^{\text{off}}`$ ($`s^1`$). Far from saturation, the number of binding events per second is proportional to the local concentration of free motors, and to the number of available binding sites on the microtubules. If the concentration of free motors is expressed in molecules per cubic micrometers, and the available “quantity” of microtubules in micrometers, the constant of proportionality $`p^{\text{on}}`$ has the dimension of a diffusion constant.

Let $`b(r)`$ and $`f(r)`$ be the concentrations of bound and free motors, respectively, at distance $`r`$ from the center, averaged over all angles. Bound motors move radially at speed $`v`$, and create a convective flux $`J_b=vb`$. Unbound motors diffuse freely, creating a radial flux $`J_f=Ddf/dr`$. If $`S`$ is the surface area at distance $`r`$, there are $`p^{\text{off}}Sbdr`$ release events in the volume between the radii $`[r,r+dr]`$, and $`p^{\text{on}}Nfdr`$ attachments per second. We therefore obtain the coupled kinetic equations:

$`{\displaystyle \frac{b}{t}}`$ $`=`$ $`p^{\text{off}}b+{\displaystyle \frac{p^{\text{on}}N}{S}}f{\displaystyle \frac{1}{S}}{\displaystyle \frac{}{r}}(J_bS)`$ (1)
$`{\displaystyle \frac{f}{t}}`$ $`=`$ $`+p^{\text{off}}b{\displaystyle \frac{p^{\text{on}}N}{S}}f{\displaystyle \frac{1}{S}}{\displaystyle \frac{}{r}}(J_fS)`$ (2)
To find the steady state, we use the fact that the net flux $`J_b+J_f`$ is zero, implying $`b=Dv^1(df/dr)`$. Substituting this result into equation (1), and denoting $`f^{}=df/dr`$ and $`f^{\prime \prime }=d^2f/dr^2`$, we find in $`d`$ dimensions

$`0`$ $`=`$ $`f^{\prime \prime }+\left({\displaystyle \frac{1}{\alpha }}+{\displaystyle \frac{d1}{r}}\right)f^{}{\displaystyle \frac{1}{r^{d1}\beta _d}}f`$ (3)
$`b`$ $`=`$ $`\gamma f^{}`$ (4)
The physical parameters in the problem have been reduced to

$`\alpha `$ $`=`$ $`v/p^{\text{off}}`$ (5)
$`\beta _1=S_1D/p^{on}N,\beta _2`$ $`=`$ $`2\pi hD/Np^{\text{on}},\beta _3=4\pi D/p^{on}N`$ (6)
$`\gamma `$ $`=`$ $`D/v.`$ (7)
where $`S_1`$ is the area of the tube in one dimension and $`h`$ is the sample thickness in a quasi two-dimensional geometry. $`\alpha `$ is the average distance that a motor moves on a microtubule, before detaching. $`\beta _d`$ characterizes the geometry of the aster, and $`\gamma `$ determines the relative concentration of bound to free motors. Note that for inward movement, $`\alpha `$ and $`\gamma `$ have negative values, while for outward movement all parameters are positive.

For the motor protein kinesin, experimental data provide values for the parameters in the model. The walking speed of kinesin without load is $`v=0.8`$ $`\mu `$m$`\text{s}^1`$ . The unbinding rate $`p^{\text{off}}`$ is obtained from the average distance that kinesin moves before detaching. Measured average run length, $`\alpha =v/p^{\text{off}}`$, are for kinesin in the range $`0.41.5`$ $`\mu `$ ; we use $`p^{\text{off}}=1`$ $`\text{s}^1`$. Direct chemical measurements of $`p^{\text{off}}`$  agree with this value. The binding rate $`p^{\text{on}}`$ of the kinesin construct used in our experiment has not been directly measured. To estimate it, we assume that interaction between microtubules and motors is diffusion limited : Measurements with kinesin’s soluble dimeric motor domain  provide a value of $`p_{}^{\text{on}}{}_{kin}{}^{}=7.3`$ $`\mu \text{m}^2\text{s}^1`$, and its diffusion constant is $`50`$ $`\mu \text{m}^2\text{s}^1`$ . For single kinesin adsorbed on beads , the equilibrium constant for the binding convection (equal to $`p^{\text{on}}/p^{\text{off}}`$), provides $`p_{}^{\text{on}}{}_{bead}{}^{}=0.25`$ $`\mu \text{m}^2\text{s}^1`$, and a diffusion constant of 2 $`\mu \text{m}^2\text{s}^1`$ . The ratios $`p^{\text{on}}/D`$ are $`0.14`$ and $`0.12`$ respectively, and we use the averaged value $`p^{\text{on}}/D=0.13`$. Finally, based on its molecular weight, we estimated a diffusion constant of $`D=20`$ $`\mu \text{m}^2\text{s}^1`$ , which yields $`p^{\text{on}}=2.6`$ $`\mu \text{m}^2\text{s}^1`$.

In a tubular, quasi one dimensional geometry, all microtubules are oriented in the same direction, (Fig 1), lower left. We find that the steady state profile for the motor concentration is exponential $`f(r)e^{r/a}`$ where the distance $`a`$ is a root of the equation $`a^2+a/\alpha 1/\beta _1=0`$. To relate this result to the situation of motors in a cell, we now consider a tube filled with oriented microtubules connected on one side to a large body. Motors have a concentration which varies exponentially with the distance from the cell body. The concentration at the end of the tube is $`e^{L/a}`$ times smaller (or greater depending on the motor sense) than in the cell body, where $`L`$ is the length of the tube. We estimated $`a`$ for a cellular extension of a diameter of 2 $`\mu `$m, and for parameters of the motor kinesin: If the extension contains 20 microtubules, then $`a=2`$ $`\mu `$m; for the same tube containing a single microtubule, $`a=30`$ $`\mu `$m. Therefore an unregulated kinesin (which can always bind and move) would be concentrated even in short extensions of a cell containing outward polarized microtubules. This is indeed observed in vivo for kinesin heavy chain if it is over-expressed in the absence of the regulatory light chain .

Our experiments were performed in a quasi 2D geometry. We thus give particular weight to the theoretical analysis of this case which also presents some interesting theoretical features: Consider firstly a non-motile binding protein ($`v=0`$). At equilibrium, the unbound molecules are evenly distributed throughout the volume, $`f(r)=\mathrm{const}`$, while the concentration of bound molecules is proportional to the local concentration of microtubule so that $`b(r)1/r`$. Thus binding of motors induces their accumulation in the center, where microtubules are more concentrated.

For general speed $`v`$ the solutions of the equations in 2D can be expressed in terms of Whitaker functions, however, simple analysis (performed by substituting $`f(r)r^x`$ in eq. (2)) shows that the solution in the quasi-two dimensional case is well approximated by power laws beyond the radius $`\alpha ^3/\beta _2^2`$: $`f(r)r^{\alpha /\beta _2}`$, and $`b(r)\gamma f(r)/r.`$ Thus the concentration profile of motors is characterized by an exponent which is a continuous function of the physical parameters. From the above expressions we find $`\alpha =\pm 0.8\mu m`$, $`1\mu m<\beta _2<10\mu m`$, and $`\gamma =\pm 60\mu m`$. The theory shows that in large asters (for kinesin, and a sample thickness of $`9`$ $`\mu `$m, asters with more than $`600`$ microtubules), most of the motors are trapped in the center, and very few motors are left elsewhere in the sample, effectively causing a dynamic “localization”. The depletion from the aster center of a kinesin motor moving outwards is comparatively weaker. For small asters, motors concentration can be higher in the center, merely as a consequence of the binding of motors to microtubules. Total depletion is achieved only for large asters (of 1000 microtubules), for which outward transport overcomes the pure binding effect.

In three dimensions, the perturbation in the concentration due to the presence of the aster is significant only within a distance $`\alpha /\sqrt{\beta _3}`$ from the center. For large radii, $`f(r)(1r_0/r)`$. We did not study this situation further due to the absence of experimental results.

To derive the convection-diffusion equations, we averaged over the directions transverse to the microtubules (both angularly, and over the thickness of the sample). This approximation breaks down experimentally in a thin sample at the center of a aster where the geometry is three dimensional, or at large radial distances where the microtubules are too far apart for angular averaging. We thus performed simulations in a true confined geometry in three dimensions to check that no substantial errors are introduced in the two dimensional theoretical description. In our simulations the aster is formed by microtubules of length $`L=50`$ $`\mu `$m, with their “plus” end in the center of a cylindrical box of radius $`L`$, and of thickness 9 $`\mu `$m. Each motor is characterized by its state (bound or free), and a vector (position). To compute the binding of motors, a rate $`p^+`$ and an interaction range $`ϵ`$ were introduced, so that at each step, a free motor has a probability $`p^+dt`$ to bind to any filament located at a distance (by projection) closer than $`ϵ`$, this effectively corresponds to $`p^{\text{on}}=p^+\pi ϵ^2`$. At each time step $`dt=4.10^5`$s, bound motors may detach with a probability $`p^{\text{off}}dt`$, and otherwise move radially by a distance $`vdt`$; free motors make random steps, with $`<dx^2>=3Ddt`$. The motor parameters were taken to mimic kinesin (see above), with the additional value $`ϵ=50`$ nm , and $`p^+=312`$ $`\text{s}^1`$ (which yield the correct value for $`p^{\text{on}}`$). Other choices of $`ϵ`$ and $`p^+`$ conserving $`p^{\text{on}}`$ gave similar curves. The agreement between simulation and theory, Fig. (2) confirms that our analytical approximations are faithful to the model.

We now turn to our experimental observations on confined quasi two dimensional samples: Using fluorescent microscopy we measured the kinesin distribution in asters with the two possible polarities. These asters have either the plus or the minus ends of the microtubules in the center , and take about 30 minutes to form. All data presented here are extracted from two identically prepared samples, in which many asters of various size formed. We measured 115 regular asters with an automatic epi-fluorescence microscopic setup (Zeiss axioplan 2 with Olympus 100X oil-immersion objective). We detected the motors (labeled with the fluorophore fluorescein) and the microtubules (labeled with rhodamine) independently. Digital pictures were taken with a 12-bit CCD camera (Hamamatsu C4742-95, 1280x1024 pixels). The camera is linear, and unsaturated pixel values reflect the relative quantity of protein in the imaged region. The sample thickness was $`9\mu m`$.

The center of the aster and the profiles of fluorescence intensity are calculated from the image. A common background pixel value was subtracted from the motor profiles, which are then normalized. An exponent is obtained by fitting the profile in the range 1.5-20 $`\mu `$m (the data below 1.5 $`\mu `$m is noisy). To measure the number of microtubules in the aster, we fit the profile of microtubule fluorescence to the function $`(M/r+B)`$, where $`r`$ is the distance from the center. $`B`$ is a background, and $`M`$ is proportional to the number of microtubules. Calibration was done by manually counting the microtubules in five asters. The $`1/r`$ profile corresponds to an homogeneous aster of long microtubules. Experimentally the asters are not perfect (some, like Fig 3, left are not well focused). When the fit of the microtubule-profile to $`1/r`$ is poor, we have no reason to expect the theory to apply. These asters are plotted with a different symbol in Fig. (4).

We measured the distribution of kinesin in asters containing different numbers of microtubules. Three typical examples are given in Fig. ( 3). Motor profiles of individual asters are rather well fitted by a power law. They are almost linear on a log-log plot, and steeper for bigger asters Fig. ( 4), inset. Plotting the exponent of the motor profiles as a function of the number of microtubules extracted from the microtubule profiles allows us to compare directly experiments and theory (see Fig. 4). The data points, each representing one aster, are scattered around the theoretical curve, reflecting the heterogeneity of the asters. However, the major trend in the exponent is correctly predicted by the theory, so that denser asters are characterized by a larger localization exponent for the motors. We also imaged kinesin moving outwards in asters of normal polarity , but the signal was too dim to extract a reliable profile (the predicted kinesin profile in this situation is rather flat).

Accumulation or expulsion of molecular motors in asters may have important functional implications in biology. For instance within a spindle made of two interacting asters of microtubules, minus-ended motors could concentrate at the poles while plus-ended motors would be excluded from the same regions. This could contribute to the mechanism of spindle assembly, and/or to its mechanical stability. Interestingly we find that kinesin accumulates in asters of 300-1000 microtubules, which is comparable to the number of microtubules present in spindle asters of most animal cells. However, the geometry and motors of the spindle are not the one studied here.

We did not consider the regulation of motor activity: In our study motors can always bind and move on filaments. Cells use a variety of processes to counterbalance the impact of motor transport on their localization. For example, the folding of kinesin into a non-motile conformation, in the absence of a cargo  dampens the transport-induced localization. The recombinant kinesin fraction used in our experiment lacks this capacity. Even with this partial inhibition, the movement of loaded kinesin brings them to places from which they have to be recycled. Additional regulation mechanisms include local synthesis and degradation of the motors, involvement of motors of different directionality transporting each other, etc. On the other hand, we can also imagine situations in which the unregulated localization of a motors resulting from their movement can have interesting consequences.

In summary, motor movements on microtubules can effectively cause their “compartmentalization”. The theory provides a full understanding of the influence of all motor kinetic parameters, and of the geometric properties of the microtubule array.

We thank A. Ajdari, S. Blandin, A. Desai, E. Karsenti and S. Leibler.


text:
# The Bennequin number of 𝑛-trivial closed 𝑛-braids is negative

## 1 Introduction

The theory of Vassiliev knot invariants leads to a decreasing filtration on the set of knots. On the other hand, every complexity measurement on knots, like the crossing number or the braid index or the minimal genus, gives rise to an increasing filtration. Although the interplay between these filtrations in opposite directions on the set of knots is still fairly unclear, the results of this paper show that such an interplay shall have a rich content.

In his seminal paper \[Ben83\], Bennequin proved that for any representative of the unknot as a closed $`n`$-braid with exponent sum $`e`$, it always holds that $`en<0`$. Bennequin’s framework for the proof of this inequality was the study of contact structures on the 3-space. A smooth knot, transverse to the standard contact structure on the 3-space, has a well-defined self-linking number. This self-linking number is an invariant of transversal knot types. Bennequin showed that every transversal knot is transversal isotopic to a closed braid. In the case when a closed braid $`\widehat{𝔟}`$ is considered as a transverse knot, this self-linking number is equal to the Bennequin number

$$\beta _t(𝔟):=en.$$

Bennequin’s inequality $`en<0`$ for the unknot also follows from work of Morton \[Mor86\] and independent work of Franks and Williams \[FW87\]. They showed that for a closed braid $`\widehat{𝔟}`$ the Bennequin number is always less than the lowest degree of $`v`$ in the Homfly polynomial. Since the Homfly polynomial of an unknot is identically $`1`$, the Bennequin number is negative in this case.

Our aim is to show that Bennequin’s inequality has a natural finite type generalization. We show that an $`n`$-trivial closed $`n`$-braid has negative Bennequin number (Theorem 3.1). Since taking the mirror image preserves the $`n`$-triviality, we actually have $`|e|<n`$ for an $`n`$-trivial closed $`n`$-braid. From the point of view of the theory of Vassiliev knot invariants, the reason behind this inequality is that algebraically independent Vassiliev invariants become dependent on each other when the braid index is fixed.

One motivation of investigating such an interplay between Vassiliev invariants and the increasing filtration on the set of knots given by the braid index is best described in terms of complexity theory of Vassiliev invariants coming from the Homfly polynomial.

As shown by Bar-Natan \[BN95a\], for a knot with a diagram of $`c`$ crossings the computational complexity for evaluating a given Vassiliev invariant of order $`k`$ at this knot is in $`O(c^k)`$. Moreover, as it was proved in \[JVW90\] the evaluation of the Jones polynomial at all but eight points is $`\mathrm{\#}P`$-hard. Recall that $`\mathrm{\#}P`$ is a class containing $`NP`$. Since the Jones polynomial is a certain evaluation of the Homfly polynomial, this results carries over to the Homfly polynomial. There are points where the evaluation of the Homfly polynomial is $`\mathrm{\#}P`$-hard.

Assuming that $`\mathrm{\#}PNP`$, this implies that for these Vassiliev invariants, which come from the Homfly polynomial, there cannot be an upper bound $`k`$ such that the computation of each of them is possible in $`O(c^k)`$-time.

However, the Homfly polynomial has a definitions in terms of a trace of a certain representation of the braid groups \[Jon87\]. This means that for a fixed braid index, the Homfly polynomial is computable in polynomial time in the word length of the braids.

Therefore, the braid index must lead to some restrictions for Vassiliev invariants involving the word length (exponent sum). Some of them are outlined below. Some others are described in \[DLL00\].

The first author would like to thank Joan Birman for many discussions on the topics of this paper.

## 2 Parametrizing the Homfly polynomial as an honest two variable polynomial

We start with a certain, non-standard definition of the Homfly polynomial, which seems to be more useful from the Vassiliev theory point of view.

###### Proposition 2.1.

Let a polynomial $`\mathrm{\Gamma }=\mathrm{\Gamma }(𝔟)[\mu ,z]`$ for a braid $`𝔟B_n`$ be defined by

$`\mathrm{\Gamma }(𝔟\sigma _i)\mathrm{\Gamma }(𝔟\sigma _i^1)`$ $`=`$ $`z\mathrm{\Gamma }(𝔟)`$ (1)
$`\mathrm{\Gamma }(𝔟\sigma _n^1)`$ $`=`$ $`(1\mu z)\mathrm{\Gamma }(𝔟)`$ (2)
$`\mathrm{\Gamma }(𝔟\sigma _n)`$ $`=`$ $`\mathrm{\Gamma }(𝔟)`$ (3)
$`\mathrm{\Gamma }(id_n)`$ $`=`$ $`\mu ^{n1}`$ (4)
and $`\mathrm{\Gamma }(\mu ,z)`$ is invariant under conjugation and relations in the braid group.

###### Remark 2.2.

For a knot $`\widehat{𝔟}`$ that is the closure of a braid $`𝔟B_n`$ the relation with the Homfly polynomial $`P(v,z)`$ (see e.g. \[Lic88\]) is given by:

$`\left((1\mu z)^{(en+1)/2}\mathrm{\Gamma }(𝔟)(\mu ,z)\right)|_{\mu =\frac{1v^2}{z}}=P(\widehat{𝔟})(v,z).`$ (5)
Here, $`e`$ denotes the exponent sum of $`𝔟`$ with respect to the standard generators of the braid group.

Proofs of properties of the polynomial $`\mathrm{\Gamma }(\mu ,z)`$ rely on the following way to compute it: If we have a braid $`𝔟`$ which closes to a knot then we unknot the knot by crossing changes. The term on the right hand-side of the skein relation (1) corresponds to a link of two components. For a braid $`𝔟`$ which closes to a link with $`c`$ components, we unlink it, i.e. we change crossings in two different components. The term on the right-hand side of Equation (1) is then a link with $`c1`$ components.

###### Proposition 2.3.

The polynomial $`\mathrm{\Gamma }(\mu ,z)=_jp_j(\mu )z^j`$ has the following properties, which are easily checked:

1. For a split link $`L=L_1L_2`$, i.e. $`L_1`$ and $`L_2`$ are unlinked,

$`\mathrm{\Gamma }(L)=\mu \mathrm{\Gamma }(L_1)\mathrm{\Gamma }(L_2).`$ (6)
2. The degree in $`\mu `$ of $`\mathrm{\Gamma }(𝔟)`$ for $`𝔟B_n`$ is less than $`n`$, i.e. each of the $`p_j(\mu )`$’s is a polynomial of degree less than $`n`$.
3. The degree in $`z`$ of $`\mathrm{\Gamma }(𝔟)`$ is less or equal to the word length of $`𝔟`$.
4. The evaluation $`\mathrm{\Gamma }(𝔟)(0,z)`$ is the Alexander polynomial, in its Conway form, of the closed braid $`\widehat{𝔟}`$.
5. The coefficient of $`z^k`$ in $`\mathrm{\Gamma }(𝔟)(\mu ,z)`$, i.e. $`p_k`$ is a Vassiliev knot invariant of order $`k`$ for the (framed) closed braid $`\widehat{𝔟}`$. This follows in the same way as outlined in \[BL93, BN95b\] for related polynomials.

Furthermore we have:

###### Proposition 2.4.

Assume the braid $`𝔟B_n`$ closes to a link of $`c`$ components.

1. The coefficient $`p_j(\mu )`$ is an odd polynomial if $`j+c`$ is even, otherwise $`p_j(\mu )`$ is an even polynomial.
2. $`\mathrm{\Gamma }(\mu ,0)=p_0(\mu )=\mu ^{c1}`$. In particular $`p_0(\mu )=1`$ if the braid closes to a knot.
3. If the braid closes to a knot then

$$p_1(\mu )=\frac{en+1}{2}\mu ,$$

where $`e`$ is the exponent sum of the braid $`𝔟`$ with respect to the standard generators of the braid group.
4. For a braid which closes to a knot, the polynomial $`p_j(\mu )`$ is of degree less than or equal to $`j`$.

###### Proof.

All claims follow by an easy induction. Using the skein relation (1) we express a link as the sum or difference of two links which are either of shorter word length or are “less linked”. ∎

## 3 Closed $`n`$-braids which are $`n`$-trivial

We call a knot $`n`$-trivial if all Vassiliev invariants up to degree $`n`$ vanish on it. The unknot is $`n`$-trivial for each $`n`$. It is not known whether there is another knot with this property. The Volume conjecture (see e.g. \[MM99\]) indeed would imply that there is none. Even for the Jones polynomial there is no example of a non-trivial knot with trivial Jones polynomial known (see e.g. \[DH97\]).

###### Theorem 3.1.

Let $`K`$ be a $`n`$-trivial knot which is given as a closed $`n`$-braid $`\widehat{𝔟}`$. Then the Bennequin number $`\beta _t(𝔟)`$ is negative.

###### Proof.

Let $`𝔟`$, $`𝔟B_n`$ be a braid with exponent sum $`e`$ satisfying our conditions. The polynomial $`\mathrm{\Gamma }(𝔟)(\mu ,z)`$ can be written as

$$\mathrm{\Gamma }(\mu ,z)=p_i(\mu )z^i$$

for some polynomials $`p_i(\mu )`$ of degree less than $`n`$ in $`\mu `$.

Now the coefficients of $`z^k`$ in

$$(1\mu z)^{(en+1)/2}\mathrm{\Gamma }(\mu ,z)$$

is a (framing independent) Vassiliev invariant, which depends on $`\mu `$ and $`e`$.

Since, by our condition, all Vassiliev invariants up to degree $`n`$ vanish, we know that $`p_i(\mu )`$ must be the coefficient $`c_i(\mu ,e)`$ of $`z^i`$ in $`(1\mu z)^{(en+1)/2}`$.

We know that $`p_i(\mu )`$ must have degree less than $`n`$, but $`c_n(\mu ,e)`$ has degree $`n`$. Thus $`c_n(\mu ,e)`$ must be trivial for all choices of $`\mu `$, which means, $`e`$ has to be a root of $`c_n(\mu ,e)`$.

Hence, by applying the Taylor expansion formula to $`(1\mu z)^{(en+1)/2}`$, we conclude that $`e`$ is one of the numbers $`n1,n3,\mathrm{},n2n+1=n+1`$. ∎

###### Remark 3.2.

(Unfortunately) the fact that a closed $`n`$-braid is $`n`$ trivial does not imply that it is trivial or even that its Homfly polynomial is trivial. By the work of Stanford \[Sta96\] if two braids differ by an element in the $`(k+1)`$-th term of the lower central series of the pure braid group $`P_n`$ then all Vassiliev invariants up to degree $`k`$ coincide. Now, take e.g. the braid group $`B_3`$ on $`3`$ strands. The pure braid group $`P_3`$ is the direct product of the center of $`B_3`$ and a free group of rank $`2`$, generated by $`\sigma _1^2`$ and $`\sigma _2^2`$. (This is a special case of Newworld’s Lemma \[DM99\].) By the classification of links given as closed $`3`$-braids \[BM93\] the closure of the concatenation of the braid $`\sigma _1\sigma _2`$ with an element in the $`(k+1)`$-th term of the lower central series is a non-trivial knot. By Stanford’s work, it is $`k`$-trivial, though. Since the Jones polynomial of a closed $`3`$-braids is identically $`1`$, if and only if the knot is trivial \[Bir85\], it follows that the Jones polynomial of this link and thus the Homfly polynomial is non-trivial.

## 4 Dimensions of Homfly subspaces restricted to $`n`$-braids

We would like to point out one fact which becomes more apparent in the framed and reparametrized version $`\mathrm{\Gamma }(\mu ,z)`$ of the Homfly polynomial. Vassiliev invariants are dual to the space of knots. Therefore, one can ask about the dimension of Vassiliev invariants on subsets of knots.

We get

###### Proposition 4.1.

1. The dimension of (framed) Vassiliev knot invariants coming from the coefficient of the (framed) Homfly polynomial $`\mathrm{\Gamma }(\mu ,z)`$ has dimension $`\frac{k}{2}+1`$ in degree $`k`$.
2. Restricted to closed braids in $`B_n`$ one gets for the dimension of Vassiliev invariants in degree $`k`$:

1. If $`k<n`$ then the dimension is $`\frac{k}{2}+1`$.
    2. If $`kn`$ and $`n`$ is odd and $`k`$ is even then the dimension is $`\frac{n}{2}+1`$. In all other cases it is $`\frac{n}{2}`$.

###### Proof.

That the given dimensions form an upper bound, follows from Proposition 2.3 (2) and Proposition 2.4 (1) and (4).

It remains to construct the following: Let $`k`$ be the degree. We will show that there are braids in $`B_{k+1}`$ such that the dimension of the coefficients of $`z^k`$ is $`\frac{k}{2}+1`$.

For a braid $`𝔟B_j`$ the polynomial $`\mathrm{\Gamma }(\mu ,z)`$ satisfies:

$`\mathrm{\Gamma }(𝔟\sigma _j^3)(\mu ,z)`$ $`=`$ $`(1+z\mu +z^2)\mathrm{\Gamma }(𝔟)(\mu ,z).`$ (7)
Furthermore, we have for arbitrary $`k`$:

$`\mathrm{\Gamma }(\sigma _1^1\sigma _2^1\mathrm{}\sigma _k^1)(\mu ,z)`$ $`=`$ $`(1\mu z)^k.`$ (8)
In particular, the coefficient of $`z^k`$ is $`\pm \mu ^k`$.

Combining these two formulas, one sees that the coefficient of $`z^k`$ in

$$\mathrm{\Gamma }(\sigma _1^1\sigma _2^1\mathrm{}\sigma _{k2}^1\sigma _{k1}\sigma _k^3)(\mu ,z)$$

is $`\pm \mu ^{k2}`$. Replacing successively pairs $`\sigma _{j1}^1\sigma _j^1`$ by $`\sigma _{j1}\sigma _j^3`$, where $`j`$ has the same parity as $`k`$, yields polynomials with coefficients of $`z^k`$ equal to $`\pm \mu ^{j2}`$.

Hence the dimension is equal to the number of $`jk`$ with the same parity as $`k`$. ∎

###### Remark 4.2.

Part (1) of the previous proposition should also follow along the lines of \[Men97\].

## 5 Knots whose evaluation of Vassiliev invariants coincide

Our reparametrization allows us to give an improvement of a theorem in \[KSS97\]. The general question is: Given a quantum polynomial and a knot $`K`$ of crossing number $`c`$, up to which degree \- as a function in $`c`$ \- does one has to know the values of Vassiliev invariants at the knot $`K`$, so that the whole polynomial is already determined? Since there are only finitely many knots of crossing number $`c`$, such a function has to exist. It is not clear, however, whether this function has some nice form. In \[KSS97\] it was shown that for the Homfly polynomial such a function is bounded by a quadratic polynomial in $`c`$. We will show, that it is in fact bounded by $`c`$. Why is this important? It is still unknown whether Vassiliev invariants can distinguish knots. The number of knots of crossing number $`c`$ grows exponential \[Wel92\]. On the other hand, the best lower bound known for the dimensions of Vassiliev invariants of degree $`c`$ is exponential in the square root of $`c`$ \[Das00\]. This might indicate that the space of Vassiliev invariants is simply not big enough to distinguish knots.

###### Theorem 5.1.

Let the knots $`\widehat{𝔟}_1`$ and $`\widehat{𝔟}_2`$ be closures of braids of length less or equal than $`c`$, for some number $`c`$.

If the evaluation of all Vassiliev invariants up to order $`c`$ coincide on $`\widehat{𝔟}_1`$ and $`\widehat{𝔟}_2`$ then their Homfly polynomials are equal.

###### Proof.

By Proposition 2.3 (3) we know that the polynomials $`\mathrm{\Gamma }(𝔟_1)`$ and $`\mathrm{\Gamma }(𝔟_2)`$ are polynomials in $`z`$ of degree less than or equal to $`c`$.

Let $`e_1`$ ($`e_2`$, respectively) be the exponent sum of the braid $`𝔟_1`$ ($`𝔟_2`$, respectively) on $`n_1`$ ($`n_2`$, respectively) strands.

We know that the Homfly polynomial $`P(\mu ,z)`$ \- with our reparametrization - is given by a power series in $`z`$

$$P(\widehat{𝔟}_1)(\mu ,z)=(1\mu z)^{(en+1)/2}\mathrm{\Gamma }(𝔟_1)(\mu ,z).$$

The coefficient of $`z^j`$ in $`P(\widehat{𝔟}_1)(\mu ,z)`$ is a Vassiliev invariant of order $`j`$.

Since $`\mathrm{\Gamma }(\widehat{𝔟}_1)(\mu ,z)`$ is of degree in $`z`$ less than or equal to $`c`$, $`\mathrm{\Gamma }(𝔟_1)(\mu ,z)`$ is determined by all Vassiliev invariants up to order $`c`$. In turn, $`P(\widehat{𝔟}_1)(\mu ,z)`$ itself is determined by all terms in $`z^j`$ of degree less than or equal to $`c`$.

The same argument works with $`𝔟_2`$ and we are done. ∎

###### Remark 5.2.

For the definition of $`\mathrm{\Gamma }`$ we do not really need the knot given as a closed braid. We can work with arbitary knot diagrams of framed knots instead. Thus, in the last theorem we can replace the word length by the crossing number. As a corollary we get:

###### Corollary 5.3.

If all Vassiliev invariants up to degree $`c`$ vanish on a knot $`K`$ of crossing number $`c`$ then the knot has trivial Homfly polynomial.