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# Violation of the Fluctuation-Dissipation Theorem for fast superdiffusion

## 1 Introduction

Since its formulation, the Fluctuation-Dissipation Theorem (FDT) has played a central role in non-equilibrium statistical mechanics in the linear response regime (LNESM). It reaches such an importance that a full formulation of LNESM is given  based on it. In the last 30 years, fundamental concepts and methods have been developed  and a large number of connections have been established. A necessary requirement for the FDT is that the time-dependent dynamical variables are well defined at equilibrium. The presence of nonlinear effects or far from equilibrium dynamics may lead to situations where the FDT does not hold, the aging process in spin-glass systems being a good example .

In this letter, we present a straightforward proof of the inconsistency of the FDT for a certain class of superdiffusive processes described by a generalized Langevin equation (GLE). The surprising result here is the fact that the violation happens in the linear regime, i.e. where we expect the validity of the LNESM. The use of the FDT allows us to classify two classes of superdiffusion. The first class, which we shall call normal superdiffusion, does obey the FDT; the second class, which we shall call fast superdiffusion, does not obey the FDT. The proof is simple and we discuss as well how the diffusive process leads to an equilibrium.

Diffusion is one of the simplest processes by which a system reaches equilibrium. For normal diffusion, the process is so well known that it may be described by an equilibrium type distribution for the velocity and position of a particle. However, the strange kinetics of anomalous diffusion, intensively investigated in the last years , shows surprising results. Consequently, studying anomalous diffusion seems to be a good way to obtain the conditions of validity for the FDT.

## 2 Violation of the FDT

We shall start writing the GLE for an operator $`A`$ in the form

$$\frac{dA(t)}{dt}=_0^t\mathrm{\Gamma }(tt^{})A(t^{})𝑑t^{}+F(t),$$
(1)
where $`F(t)`$ is a stochastic noise subject to the conditions $`F(t)=0`$, $`F(t)A(0)=0`$ and

$$C_F(t)=<F(t)F(0)>=<A^2>_{eq}\mathrm{\Gamma }(t).$$
(2)
Here $`C_F(t)`$ is the correlation function for $`F(t)`$ and the brackets $`<>`$ indicate ensemble average. Eq. (2) is the famous Kubo FDT and it is quite general. In principle, the presence of the kernel $`\mathrm{\Gamma }(t)`$ allows us to study a large number of correlated processes. The main quantity is the correlation function $`C_A(t)=<A(t)A(0)>,`$ from which we can describe most of the process of interest.

We may naively expect that, by Eq. (1) and Eq. (2), a system will be driven to an equilibrium , i.e.

$$\underset{t\mathrm{}}{lim}<A^2(t)>=<A^2>_{eq}.$$
(3)
We shall see however that this is not always the case for superdiffusive dynamics. Let us define the variable

$$y(t)=_0^tA(t^{})𝑑t^{},$$
(4)
with asymptotic behavior

$$\underset{t\mathrm{}}{lim}<y^2(t)>t^\alpha .$$
(5)
For normal diffusion $`\alpha =1`$, we have subdiffusion for $`\alpha <1`$ and superdiffusion for $`\alpha >1`$. Notice that if $`A(t)`$ is the momentum of a particle with unit mass, $`y(t)`$ is its position. Using the Kubo’s definition of the diffusion constant, Morgado et al obtained a general classification for anomalous diffusion; i.e. using

$$D=\underset{z0}{lim}\stackrel{~}{C}_A(z)=\underset{z0}{lim}\frac{<A^2>_{eq}}{z+\stackrel{~}{\mathrm{\Gamma }}(z)},$$
(6)
where $`\stackrel{~}{\mathrm{\Gamma }}(z)`$ is the Laplace transform of $`\mathrm{\Gamma }(t)`$ they obtained: For a finite value of $`\stackrel{~}{\mathrm{\Gamma }}(0)0`$, normal diffusion; for $`\stackrel{~}{\mathrm{\Gamma }}(0)=0,`$ superdiffusion; and for $`\stackrel{~}{\mathrm{\Gamma }}(0)=\mathrm{}`$, subdiffusion.

Now the Laplace transform of Eq. (1) suggests a solution of the form

$$A(t)=_0^tR(tt^{})F(t^{})𝑑t^{},$$
(7)
where we have set $`A(0)=0`$, and

$$\stackrel{~}{R}(z)=\frac{1}{z+\stackrel{~}{\mathrm{\Gamma }}(z)}.$$
(8)
Squaring Eq. (7) and taking the ensemble average we obtain

$$<A^2(t)>=2_0^tR(t^{})_0^t^{}C_F(t^{}t^{\prime \prime })R(t^{\prime \prime })𝑑t^{\prime \prime }𝑑t^{}.$$
(9)
At this point, it is quite usual to perform numerical calculation . However, we shall show here that very important results can be obtained analytically. From Eq. (8), we can get a self-consistent equation for $`R(t)`$ as

$$\frac{dR(t)}{dt}=_0^t\mathrm{\Gamma }(tt^{})R(t^{})𝑑t^{}.$$
(10)
Notice from Eq. (6) and Eq. (8) that $`R(t)`$ is the normalized correlation function, i.e. $`R(t)=C_A(t)/C_A(0)`$. By using the FDT Eq. (2) and Eq.(10) we can exactly integrate Eq. (9) and obtain

$$<A^2(t)>=<A^2>_{eq}\lambda (t),$$
(11)
where

$$\lambda (t)=1R^2(t).$$
(12)
Equation. (3) is satisfied if and only if

$$\underset{t\mathrm{}}{lim}\lambda (t)=\lambda ^{}=1,$$
(13)
or equivalently

$$\underset{t\mathrm{}}{lim}R(t)=\underset{z0}{lim}z\stackrel{~}{R}(z)=\underset{z0}{lim}\frac{z}{z+\stackrel{~}{\mathrm{\Gamma }}(z)}=0.$$
(14)
Where in the first step we used the final value theorem. Again we shall comment here that if Eq. (14) does not hold, its equivalently Eq. (3) does not hold as well, and it violates the FDT Eq. (2). Recently Lee, using his recurrence relation formalism, obtained a condition similar to Eq. (14) for the ergodicity hypothesis to work. I.e. if the system keeps some memory after an infinity time, the ergodicity does not hold. We show here that it is the same condition for the validity of the FDT.

Equation (14) is satisfied for normal and subdiffusion. For superdiffusion $`lim_{z0}\stackrel{~}{\mathrm{\Gamma }}(z)=0`$, and Eq. (14) becomes

$$\underset{t\mathrm{}}{lim}R(t)=(1+\underset{z0}{lim}\frac{\stackrel{~}{\mathrm{\Gamma }}(z)}{z})^1,$$
(15)
There are two distinct limits for Eq. (15), which define two classes of superdiffusion. For the first class, $`lim_{z0}\frac{\stackrel{~}{\mathrm{\Gamma }}(z)}{z}=\mathrm{}`$ and the system obeys the FDT. The second class has $`lim_{z0}\frac{\stackrel{~}{\mathrm{\Gamma }}(z)}{z}\mathrm{}`$ and it does violate the FDT. The first class we shall call normal superdiffusion (NSD) and the second class fast superdiffusion (FSD).

Consider now the asymptotic behavior for $`\stackrel{~}{\mathrm{\Gamma }}(z)`$as

$$\stackrel{~}{\mathrm{\Gamma }}(z0)=az^\nu .$$
(16)
Is easy to see that for $`\nu <0`$ we have subdiffusion, for $`\nu =0`$ normal diffusion, and for $`\nu >0`$, superdiffusion. From the above equations we have for $`0<\nu <1`$ NSD and, finally, for $`\nu 1`$ we have FSD. There is an obvious connection between $`\nu `$ and $`\alpha `$, defined in Eq. (5), that classify the diffusion. Morgado et al  shown that $`\nu =\alpha 1`$ and consequently the FSD starts at $`\alpha 2`$, i.e., the FDT does not work for the ballistic motion and beyond. Better, the formalism of GLE + FDT works for $`0<\alpha <2`$. We shall discuss later the lower limit $`\alpha =0`$.

## 3 Ballistic Motion

The ballistic motion is at the limit of the validity of the FDT, to go beyond it is too dangerous so we shall keep working within $`\alpha =2`$. Before we give some example let us make a very important association. The force $`F(t)`$ in Eq. (1) can be obtained from a thermal bath composed of harmonic oscillations, consequently accordingly to Eq. (2) the memory can be put as

$$\mathrm{\Gamma }(t)=\rho (\omega )\mathrm{cos}(\omega t)𝑑\omega ,$$
(17)
where $`\rho `$$`(\omega )`$ is the noise density of states. The same argument used before for the Laplace transform can be used for for the Fourier transform, with the simplifying consequence $`\stackrel{~}{\mathrm{\Gamma }}(\omega )=\rho (\omega )`$. This is a great advantage, since noise density of states exist not only for systems governed by GLE, but for most of the physical systems. Consequently the MOBH conjecture reads: *If a disordered unidimensional system has $`\rho `$$`(\omega )\omega ^\nu ,`$ as $`\omega 0`$ than the diffusion exponent is*

$$\alpha =\nu +1.$$
(18)
This conjecture has been observed for the quantum disordered Heisenberg ferromagnetic chain, and is under discussion for energy propagation on the harmonic disordered chain. We can choose now the density of state to produce the diffusion we want. Consider now the noise density of states

$$\rho (\omega )=\{\begin{array}{cc}constant\hfill & \omega _1<\omega <\omega _2\hfill \\ 0\hfill & otherwise\hfill \end{array},$$
(19)
for $`\omega _1=0`$ we have the Debye density of states for a thermal noise made out of acoustic phonons. Thus, for $`\omega _1=0`$ we have normal diffusion and for any $`\omega _10`$ we have superdiffusion. This density yields

$$\mathrm{\Gamma }(t)=\beta \left[\frac{\mathrm{sin}(\omega _2t)}{t}\frac{\mathrm{sin}(\omega _1t)}{t}\right],$$
(20)
The Laplace transform of Eq. (20) gives as $`z0`$ $`\stackrel{~}{\mathrm{\Gamma }}(z)`$$``$$`z`$, consequently $`\nu =1`$ and $`\alpha =2`$, which is the ballistic limit. If we let $`\beta =\omega _2/2`$ we get $`\lambda ^{}`$ as

$$\lambda ^{}=1\left(\frac{2\omega _1\omega _2}{\omega _1+\omega _2}\right)^2.$$
(21)
Values of $`\lambda ^{}`$$``$1 show the inconsistency of the FDT because we start supposing the existence of an equilibrium value $`<A^2>_{eq}`$ and, after an infinite time, we end up with $`<A^2>_{eq}\lambda ^{}`$. Equation (21) has a parameter control $`\omega _1`$, which measures the “hole” in the density of states, and how far we are from the result predicted by the FDT.

Now we select $`A(t)=v(t)`$, the particle’s velocity, so that $`<v^2(t)>=<v^2>_{eq}\lambda (t)`$. We simulate the GLE for a set of $`10,000`$ particles starting at rest at the origin and using the memory in Eq. (20) with $`\omega _2=0.5`$ and different values of $`\omega _1`$. The results of these simulations are shown in Fig. 1, where we plot $`<v^2(t)>`$. We used the normalization $`<v^2>_{eq}=1`$, so that $`<v^2(t)>=\lambda (t)`$. Notice that $`\lambda (t)`$ does not reach a stationary value, rather it oscillates around a final average value $`\lambda _s`$. This value of $`\lambda _s`$ should be compared with $`\lambda ^{}`$ obtained from Eq. (21).

In Fig. 2 we plot $`\lambda ^{}`$ as a function of $`\omega _1`$ as in Eq. (21) with fixed $`\omega _2=0.5`$. We also plot the final average values $`\lambda _s`$ obtained from simulations for different values of $`\omega _1`$. Notice that as $`\omega _1`$ increases $`\lambda ^{}`$ decreases as expected. The agreement between simulations and Eq. (21) shows that we can predict the average value $`\lambda _s`$, even when the FDT does not work.

Now we can define $`\lambda ^{}`$$`=T^{}/T`$, where $`T^{}`$ is an effective temperature for the system. Effective temperatures different of the expected temperature $`T`$, or $`\lambda ^{}`$$`1,`$ are found in spin glasses where the FDT does not work. The first observation of such phenomena was reported Kauzmann. He noticed that if the entropy of a supercooled liquid is extrapolated below the glass temperature $`T_g`$, it becomes equal to the crystal temperature $`T_c>0`$, and in some cases even $`T_c<0`$. To avoid this paradox he suggested the existence in the supercooled liquid phase of effective spinodal temperature $`T_{sp}<`$$`T_c`$. In a recent work Rubi et al investigate the violation of the FDT, using a Fokker-Planck approach. They found temperatures $`T^{}`$ which are greater and small than $`T.`$ Ricci-Tersenghi et al and Cavagna et al performed single-spin-flip Monte Carlo simulations in square lattices with frustration and they obtained effective temperatures $`T^{}T`$. Methods for measuring those effective temperatures are discussed as well in the literature.

An oscillatory behavior similar to that found in Fig. 1 was observed by Srokowski, in his simulations using GLE. However, the kind of motion he studied is a subdiffusive motion. Using his memory we get $`\stackrel{~}{\mathrm{\Gamma }}(z)=\beta [1\mathrm{exp}(\epsilon z)/(\epsilon z)+E_1(\epsilon z)]`$, here $`\beta `$ is a constant, $`\epsilon `$ a small number, and $`E_1`$ is the exponential integral. This result gives $`lim_{z0}\stackrel{~}{\mathrm{\Gamma }}(z)z^1`$, from the above arguments we get $`\nu =1`$ and $`\alpha =0`$. We believe we can explain this strange results. Let us consider a constant memory of the form $`\mathrm{\Gamma }(t)=K,`$ if $`A(t)`$ in Eq. (1) is the velocity, than the memory term yields $`Ky`$, where $`y`$ is the position. Consequently the particle is bound to the origin by a harmonic spring and has no diffusive behavior. Indeed the Laplace transform gives $`\stackrel{~}{\mathrm{\Gamma }}(z)=K/z,`$ with $`\nu =1`$ and $`\alpha =0`$, the same as the result we obtain from Srokowski memory. We shall notice that $`\alpha =0`$ does not meaning that the motion is a harmonic type motion, rather it means it belongs to same class, the diffusion behavior of Srokowski is not a power low as in Eq. (4) probably it is slower than a power low, such as, for example, a logarithmic behavior.

For $`\alpha >2`$, the FSD cannot be described by the methods we used here. Once the FDT does not work, the GLE and the FDT together predict strange results such as a null dispersion for the dynamical variable, i.e. $`<A^2(t\mathrm{})>=0.`$ Moreover, the exponent $`\alpha `$ can be put as $`\alpha =2/D_F`$, where $`D_F`$ is the fractal dimension . Consequently $`\alpha >2`$ leads to $`D_F<1`$, which is not a full curve, but a set of points such as the Cantor set, and cannot represent a classical trajectory.

## 4 Conclusion

We discussed the stationary behavior for the mean square value of a dynamical variable $`A(t)`$ and as well the mean square displacement of the quantity’ $`y(t)=_0^tA(t^{})𝑑t^{}`$. The assymptotic behavior of $`<y^2(t)>t^\alpha `$ as $`t\mathrm{}`$, can be explained for $`0<\alpha <2.`$ We show the the superdiffusive motion must be classified in normal superdiffusive (NSD), for $`1<\alpha <2,`$ and fast superdiffusive (FSD), for $`\alpha 2`$. The FSD motion shows an inconsistency between the GLE and the FDT. This kind of superdiffusion with $`\alpha 2`$ is common in hydrodynamical processes. It is not surprising that these processes will be far from equilibrium and violate the FDT. We pointed out here how it happens and precisely where the FDT breaks down. As we have already mentioned, spin glasses seem to be a rich field for studying these phenomena. Indeed experimental  and theoretical works  have been reported in this area, confirming the violation of the FDT. As well, the effective temperature found in noncrystaline material is connected here with the FSD and the violation of the FDT. It would be very helpful if the exponent $`\alpha `$ for those diffusive processes could be measured. Another related phenomena are anomalous reaction rate and chaos synchronization, which we expect to discuss soon. Although anomalous diffusion remains as a surprising phenomena, we hope that this work will help in the centennial effort to understand diffusion and the relation between fluctuation and dissipation. A generalization of the FDT to include the FSD is necessary, what will require a deeper understanding of systems far from equilibrium.


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# On the nature of long-range contributions to pair interactions between charged colloids in two dimensions

## Abstract

We perform a detailed analysis of solutions of the inverse problem applied to experimentally measured two-dimensional radial distribution functions for highly charged latex dispersions. The experiments are carried out at high colloidal densities and under low-salt conditions. At the highest studied densities, the extracted effective pair potentials contain long-range attractive part. At the same time, we find that for the best distribution functions available the range of stability of the solutions is limited by the nearest neighbour distance between the colloidal particles. Moreover, the measured pair distribution functions can be explained by purely repulsive pair potentials contained in the stable part of the solution.

The machinery of statistical mechanics is designed to obtain information on the structure of liquids from given interparticle interaction potentials. When solving the inverse problem of statistical mechanics, one hopes to find a unique interaction potential reproducing a measured distribution function henderson74 ; rev:raja . There are, however, always obstacles such as limited range and finite accuracy of the measured distributions, but also a number of numerical difficulties. No numerical procedure is able to fit the reference distribution exactly. Therefore, in practice, the inverse problem is always ill-posed and the uniqueness of the solution is not guaranteed. The problem becomes even more complicated at high particle densities where the spatial distributions are governed by packing effects. In this case, a wide range of effective potentials is projected onto a very tight space of radial distribution functions (rdf), thus making it impossible to distinguish between the potentials of different shapes by comparing the pair distributions only.

Another problem that occurs is particularly virulent in dense suspensions of charged colloids. It is related to the fact that a colloidal system is not a simple liquid with state-independent pair-interactions, but rather a complex system in which the colloidal interaction results from integrating out the micro-ionic degrees of freedom levin02 ; rev:vlachy ; rev:loewen ; reviewBelloni00 . As a result, a description in terms of pair potentials becomes inadequate at higher volume fractions when many-body interactions between the colloids come into play. If this is the case, an inversion of the rdfs results in density-dependent pair-potentials which contain contributions of the many-body interactions and which are thus different from the true (density-independent) pair-potentials acting between the particles.

In an attempt to explore the density dependence of the effective interactions between charged colloids, we have recently made progress in the experimental as well as the theoretical approach brunner ; klein : (i) a much improved range and precision in measuring rdfs at high colloidal number densities was achieved, (ii) control of the colloidal densities became possible, and (iii) advanced inversion tools were used. In our previous papers we have focused our analysis on the behavior of the pair-potentials at short distances where ambiguities due to the inversion procedure can be safely ruled out. We have found that the pair potentials show a density-dependent deviation from the expected Yukawa form which can best be explained in terms of many-body interactions. We only mentioned that at larger distances and high densities we have found attractive parts in the pair-potential. The present paper now concentrates on the analysis of this attraction.

From the beginning, we should make a distinction between the phenomenon we discuss here and the attraction observed between charged colloids confined by two narrowly spaced glass plates ($`<20\mu m`$) or located at the air-water interface att1 ; carbajal3745 ; behrens05 ; cruz4203 ; Quesada ; han03 ; ram03 . These latter potentials were obtained at low densities for which different inversion procedures gave almost identical results. Especially the latest studies han03 ; ram03  show very clearly that pair-potentials between colloids in weakly confined suspensions are purely repulsive, while more strongly confined suspensions display attractions at the same density; so confinement is obviously an essential requirement for the observed attraction in those studies han03 ; ram03 . We did not detect any similar confinement effects since the spacing between the two glass plates of our sample cell was an order of magnitude larger than in all the other experiments han03 ; ram03  ($`>`$ 200 $`\mu m`$).

In the present work, we consider a 2D charge stabilized colloidal dispersion of $`\sigma =2.4\mu m`$ diameter polystyrene sulfonate particles taken at 2D packing fractions $`\rho \sigma ^2`$ ranging between 0.1 and 0.23, where $`\rho `$ is the particle number density in two dimensions. More precisely, we should call our system a quasi-2D system since the electric double layers around the colloids preserve their three-dimensional character while the centers of the colloids are effectively confined to a plane. The colloidal 2D rdf’s were measured as described in brunner ; klein , but with a higher spatial resolution than in the previous works. As previously, an Ornstein-Zernike equation (OZ)-based inversion routine with Percus-Yevick (PY) and hypernetted-chain (HNC) closures as well as inverse Monte Carlo method (IMC) were used to extract the effective pair potentials between the colloids from the measured rdfs LL95 ; LL97 ; lobaskin01 ; brunner ; klein .

Figure 1 shows the rdfs for the 2D latex dispersion. One can easily observe that the position of the initial peak shifts slightly towards smaller $`r`$ when the density is increased and that its height grows with the concentration. The results of the inversion are presented in Fig. 2. Since the potentials are defined by the inversion procedure up to an additive constant and thus subject to vertical shifts, it is more convenient to compare force curves, which in Fig. 2 are plotted for various concentrations, obtained using different inversion methods. In the IMC method, the cut-off radius within the inversion scheme (defined in LL95 ; lobaskin01 ; klein ) has been varied in order to study its effect on the final result. The collection of IMC curves in Fig. 2 thus gives an idea of the error produced by the cut-off. A finite cut-off also implies that different lengths of the rdf are used for the analysis. We thus model the experimental situation where the range of accessible rdfs is shortened. For comparison, we also plotted the best Yukawa fit for the IMC result at the lowest density 0.098, denoted as the ”reference Yukawa interaction” in the following (pair-potential in units of $`kT`$: $`u(r)/kT=35000\sigma \mathrm{exp}(5r/\sigma )/r`$).

The effective pair forces shown in Fig. 2 display a very steep repulsive part at short distances, whereas their long-range part beyond $`2.5\sigma `$ is close to zero. The potentials extracted from the OZ-based method with PY and HNC closures differ form each other. The HNC result approaches the reference Yukawa derivatives, while the PY forces stay closer to the IMC data. At densities above 0.187 for HNC no meaningful solution of the OZ based method could be found. Some of the curves are slightly attractive at larger separations. The depth of the minimum reaches $`0.25kT`$ for the potential and $`0.2\sigma kT`$ for the force. At the highest density, the uncertainty of the result is fairly large in the long-range part. It is important to note that the distances, at which the force reaches zero, correspond roughly to the position of the main peak of the rdf at $`r\rho ^{1/2}`$ (arrows in Fig. 2 indicate the mean interparticle distance $`\rho ^{1/2}`$). This may be seen in Fig. 3 where we compare the mean distance with (i) the distance of the first peak in the rdf and (ii) the distance where the force reaches zero.

The important new message of Fig. 2 is that the effective pair-potential decomposes into two parts: a short-ranged and cut-off-independent repulsive part and a long-ranged part, which can show an attraction. This attraction depends sensitively on the chosen cut-off. We call the cross-over point dividing the potential into a cut-off-dependent and a cut-off-independent part the ”branching point” because beyond this point a noticeable branching of the different IMC curves sets in. Fig. 3 demonstrates that the position of this branching point scales with the density, and that it is always at shorter distances than the point of zero force. The force value, at which it starts, characterizes the sensitivity threshold of the inversion procedure in use. We have to conclude that the limitations of the inversion procedure allows us to make firm statements only about the short-ranged repulsive parts of the pair-potential, but not about the ”attractive” forces observed at larger distances. We stress that at distances smaller than the branching point, the effective forces are clearly seen to be less repulsive than expected for a Yukawa-like interaction, an effect which increases with the concentration. This feature, observed also in 3D suspensions jureEPL ; jurejpcm ; jureJCP , is discussed in brunner ; klein ; jureJCP  in terms of a macroion shielding effect russ ; this result is obviously not affected by the uncertainty of the inversion procedure.

The fact of branching manifests the apparent degeneration of the solution to the direct problem, i.e., the calculation of the rdf. The consequences of this degeneration of the problem at hand are further illustrated by Fig. 4, which demonstrates the insensitivity of the structure to the long-range part of the effective pair potential. We show two potentials obtained from inverting the $`g(r)`$ measured at $`\rho \sigma ^2=0.187`$, using a cut-off at $`3\sigma `$ and $`8\sigma `$, together with the rdfs generated from these potentials. To facilitate comparison between the range of both the potentials and the distribution functions, we present both quantities in the same plot. While the potentials show a significant discrepancy, the difference between calculated rdfs is smaller than the statistical uncertainty (the sum of relative deviations form the reference rdf did not exceed 0.5% in both cases) and show an excellent agreement with the experimental data. The potential with the short cut-off turns to zero at $`r>3\sigma `$ while the long cut-off leads to a minimum of about $`0.25kT`$ at $`r=2.5\sigma `$. This corroborates our conclusions (pointed out above) that the features of the effective pair interaction in a distance regime beyond the first layer of neighboring particles cannot be resolved for the present system. Certainly, these conclusions do not apply to dilute systems where the effective potential is close to the potential of mean force; then the inversion gives unambiguous results behrens05 ; han03 ; ram03 .

One should note that for the observations made in this work, the geometry of the system is essential. In all the mentioned quasi-2D colloidal dispersions, only the colloidal particles are confined by the external forces while the ionic clouds remain essentially three-dimensional. A certain fraction of counterions escapes into the bulk and thus does not participate in the in-layer screening, which is confirmed by the extremely large Debye screening length (about 500 nm) obtained for these systems. As the double layers thicken, we have a chance to probe their nonlinear parts and the many-body contributions to the interparticle interaction russ . For comparison, in an unconstrained suspension of the same particles at volume fraction of 0.1 (giving a similar mean interparticle distance), the deviation of the full electrostatic potential from its far-field Debye-Hückel asymptote would be less than 5% already at $`r=1.5\sigma `$, while in our 2D system we still see significant deviation from the Yukawa shape even at $`r2\sigma `$.

Despite the apparent failure of our efforts to find the unique solution of the inverse problem, this study still arrives at a useful result. As it is seen in Fig. 4, we were able to reproduce the rdf to a very high accuracy using only the short-range part of the effective potential. We compare in Fig. 4 the rdf obtained using the reference Yukawa potential with that using the IMC result. One can see that the model with the Yukawa potential predicts the rdf notably worse. The deviation from the reference rdf in this case is caused by the too strong repulsion at the mean interparticle distance. Based on the comparison to the IMC curves that give excellent fits, one can impose a simple correction on the reference Yukawa potential to improve the agreement with the experimental rdf. The Yukawa potential can be truncated at the position of the main rdf peak and then shifted down so that the new potential is zero at and beyond this distance. Since the position of the peak scales as it is shown in Fig. 3, the new effective potential reflects the density change. This idea of using a truncated Yukawa potential as a model for colloidal pair-potentials has been tested in more detail in jureJCP ; jurejpcm .

It is also instructive to have a look at the osmotic coefficients of our colloidal suspension. These coefficients have been obtained for $`\rho \sigma ^2=0.187`$ from the virial equation, where we used the various potentials discussed above. The IMC potential with a long cut-off ($`r=12.5\sigma `$) gives 1.35 while the potential with the shorter cut-off ($`r=3\sigma `$) leads to a much larger osmotic coefficient of 3.93, which is somewhat lower than that for the reference Yukawa potential which is 4.48. The agreement between the results of the latter two, on the one hand, and the large difference to the result of the long cut-off potential, on the other hand, marks a trend that does not match our observations made in Fig. 4 where the two cut potentials agree while showing differences to the rdf of the reference Yukawa potential. As for the structure factor (see Fig. (5)), one again observes the opposite trend: the two cut potentials lead to almost identical results, which are clearly different from the structure factor one obtains using the pure Yukawa potential. This applies, especially, to the $`q0`$ behavior. For $`S(q)|_{q0}`$ we find 0.074 and 0.066 for the potentials with the longer and the shorter cut-offs, respectively, and 0.054 for the Yukawa potential. Thus, although with the cut-off procedure we obtained improvement over the Yukawa potential in all studied properties, there arises a potential dilemma: corrections of the pair-potentials leading to improvements concerning the structure of the liquid may spoil a possible agreement on the thermodynamic side. In other words, the contribution of the many-body interactions to the effective pair potential strongly depends on the property one uses to detect these contributions louis02 . In view of this fact, one could consider alternative ways to correct the effective potential, for example, one which would correct not for the structure (compressibility) but for the equation of state.

We close with the statement that the best available structure data yet do not provide sufficient accuracy for finding the unique solution of the inverse problem for two-dimensional colloidal dispersions at high densities. Although we are able to deduce the pair potential at short distances ($`r<\rho ^{1/2}`$), the limited accuracy of the rdfs do not provide unambiguous information about the long-range part of the pair-potential ($`r>\rho ^{1/2}`$). To narrow the range of the possible solutions, we suggest applying an additional constraint on the potential, i.e. to choose the potential that is equal to zero beyond the first nearest neighbor layer. This cut-off procedure is justified by the form of the pair potential, which is measured at low densities where the many-body effects are minimal and thus is closest to the true pair potential. We have shown that this choice produces satisfactory pair distributions and improves description of thermodynamic properties.

Authors thank David Grier for the valuable comments on the manuscript. VL thanks the Swiss National Science Foundation for financial support during his stay in the University of Fribourg.


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# Hopf Algebras of Dimension 𝑝𝑞

## 0 Introduction

Let $`p`$ be an odd prime and $`k`$ an algebraically closed field of characteristic 0. If $`H`$ is a semisimple Hopf algebra of dimension $`p^2`$ over $`k`$, then $`H`$ is isomorphic to $`k[𝐙_{p^2}]`$ or $`k[𝐙_p\times 𝐙_p]`$ by \[Mas96\]. A more general result for semisimple Hopf algebras of dimension $`pq`$, where $`p`$, $`q`$ are odd primes, is obtained by \[EG98\]. In \[Ng02\], the author proved that non-semisimple Hopf algebras of dimension $`p^2`$ over $`k`$ are Taft algebras and hence completed the classification of Hopf algebras of dimension $`p^2`$. However, there is no known example of non-semisimple Hopf algebras of dimension $`pq`$, with $`p<q`$. In fact, it is shown in \[AN01\] and \[BD02\] that there is no non-semisimple Hopf algebras over $`k`$ of dimension 15, 21, 35, 55, 77, 65, 91 or 143.

By \[Ng02\], if $`pq`$ are odd primes and $`H`$ is a non-semisimple Hopf algebra with antipode $`S`$ of dimension $`pq`$, then $`S^{4p}=id_H`$ and $`\text{Tr}(S^{2p})=p^2d`$ for some odd integer $`d`$. In this paper, we prove that $`dpq(mod4)`$. As a consequence, we prove that if $`p`$, $`q`$ are twin primes, any Hopf algebra of dimension $`pq`$ over $`k`$ is semisimple. Recently, Etingof and Gelaki also announce a even more general result \[EG03\] which covers the cases when $`p<q2p+1`$.

## 1 Notation and Preliminaries

Throughout this paper, $`pq`$ are odd primes, $`k`$ denotes an algebraically closed field of characteristic 0, and $`H`$ denotes a finite-dimensional Hopf algebra over $`k`$ with antipode $`S`$. Its comultiplication and counit are, respectively, denoted by $`\mathrm{\Delta }`$ and $`\epsilon `$. We will use Sweedler’s notation \[Swe69\]:

$$\mathrm{\Delta }(x)=x_{(1)}x_{(2)}.$$

A non-zero element $`aH`$ is called group-like if $`\mathrm{\Delta }(a)=aa`$. The set of all group-like elements $`G(H)`$ of $`H`$ is a linearly independent set, and it forms a group under the multiplication of $`H`$. For the details of elementary aspects for finite-dimensional Hopf algebras, readers are referred to the references \[Swe69\] and \[Mon93\].

Let $`\lambda H^{}`$ be a non-zero right integral of $`H^{}`$ and $`\mathrm{\Lambda }H`$ a non-zero left integral of $`H`$. There exists $`\alpha \text{Alg}(H,k)=G(H^{})`$, independent of the choice of $`\mathrm{\Lambda }`$, such that $`\mathrm{\Lambda }a=\alpha (a)\mathrm{\Lambda }`$ for $`aH`$. Likewise, there is a group-like element $`gH`$, independent of the choice of $`\lambda `$, such that $`\beta \lambda =\beta (g)\lambda `$ for $`\beta H^{}`$. We call $`g`$ the distinguished group-like element of $`H`$ and $`\alpha `$ the distinguished group-like element of $`H^{}`$. Then we have a formula for $`S^4`$ in terms of $`\alpha `$ and $`g`$ \[Rad76\]:

$$S^4(a)=g(\alpha a\alpha ^1)g^1\text{for }aH,$$
(1.1)
where $``$ and $``$ denote the natural actions of the Hopf algebra $`H^{}`$ on $`H`$ described by

$$\beta a=a_{(1)}\beta (a_{(2)})\text{and}a\beta =\beta (a_{(1)})a_{(2)}$$

for $`\beta H^{}`$ and $`aH`$. If $`\lambda `$ and $`\mathrm{\Lambda }`$ are normalized, there are formulae for the trace of any linear endomorphism on $`H`$.

###### Theorem 1.1

\[Rad90, Theorem 1\] Let $`H`$ be a finite-dimensional Hopf algebra with antipode $`S`$ over the field $`k`$. Suppose that $`\lambda `$ is a right integral of $`H^{}`$, and that $`\mathrm{\Lambda }`$ is a left integral of $`H`$ such that $`\lambda (\mathrm{\Lambda })=1`$. Then for any $`f\text{End}_k(H)`$,

$`\text{Tr}(f)`$ $`=`$ $`{\displaystyle \lambda (S(\mathrm{\Lambda }_{(2)})f(\mathrm{\Lambda }_{(1)}))}`$
$`=`$ $`{\displaystyle \lambda \left((Sf)(\mathrm{\Lambda }_{(2)})\mathrm{\Lambda }_{(1)}\right)}`$
$`=`$ $`{\displaystyle \lambda \left((fS)(\mathrm{\Lambda }_{(2)})\mathrm{\Lambda }_{(1)}\right)}.`$
$`\mathrm{}`$

Following \[Ng02, Section 2\], the index of $`H`$ is the least positive integer $`n`$ such that

$$S^{4n}=id_H\text{and}g^n=1.$$

Suppose that $`H`$ is a finite-dimensional Hopf algebra of odd index $`n>1`$, and that $`\omega k`$ is a primitive $`n`$th of unity. Since $`g^n=1`$ and $`\alpha `$ is an algebra map, $`\alpha (g)`$ is a $`n`$th root of unity. There exists a unique element $`x(\omega ,H)𝐙_n`$ such that

$$\alpha (g)=\omega ^{x(\omega ,H)}.$$

Following the notation in \[Ng02\], we let

$$H_{a,i,j}^\omega =\{uH|S^2(u)=(1)^a\omega ^iu\text{ and }ug=\omega ^ju\}$$

for any $`(a,i,j)𝐙_2\times 𝐙_n\times 𝐙_n`$. Since the $`r(g)\text{End}_k(H)`$, defined by $`r(g)(a)=ag`$ for $`aH`$, commutes with $`S^2`$, we have

$$H=\underset{𝐚𝒦_n}{}H_𝐚^\omega $$
(1.2)
where $`𝒦_n`$ denotes the group $`𝐙_2\times 𝐙_n\times 𝐙_n`$.

Using the eigenspace decomposition of $`H`$ in (1.2), the diagonalization of a left integral $`\mathrm{\Lambda }`$ of $`H`$ admits the following form (cf. \[Ng02\]),

$$\mathrm{\Delta }(\mathrm{\Lambda })=\underset{𝐚𝒦_n}{}\left(u_𝐚v_{𝐚+𝐱}\right)$$
(1.3)
where $`u_𝐚v_{𝐚+𝐱}H_𝐚^\omega H_{𝐚+𝐱}^\omega `$ and $`𝐱=(0,x(\omega ,H),x(\omega ,H))`$ in $`𝒦_n`$.

In the sequel, we will call the expression in equation (1.3) the normal form of $`\mathrm{\Delta }(\mathrm{\Lambda })`$ associated with $`\omega `$. We will simply write $`u_𝐚v_{𝐚+𝐱}`$ for the sum $`u_𝐚v_{𝐚+𝐱}`$ in the normal form of $`\mathrm{\Delta }(\mathrm{\Lambda })`$.

Let $`E_𝐚^\omega `$, $`𝐚𝒦_n`$, be the set of orthogonal projections associated with the decomposition (1.2). Then

$$dim(H_𝐚^\omega )=\text{Tr}(E_𝐚^\omega )$$

and we have the following lemma.

###### Lemma 1.2

Let $`H`$ be a finite-dimensional Hopf algebra with the antipode $`S`$ of odd index $`n>1`$ over $`k`$, and $`\omega k`$ a primitive $`n`$th root of unity. Let $`x=x(\omega ,H)𝐙_n`$ and $`𝐱=(0,x,x)`$. Then we have

$$dim(H_𝐚^\omega )=dim(H_{𝐱𝐚}^\omega )$$

for all $`𝐚𝒦_n`$.

Proof. Let $`\mathrm{\Lambda }`$ be a left integral for $`H`$ and let $`\lambda `$ be a right integral for $`H^{}`$ such that $`\lambda (\mathrm{\Lambda })=1`$. Using the normal form of $`\mathrm{\Delta }(\mathrm{\Lambda })`$ associated with $`\omega `$ in (1.3) and Theorem 1.1, we have

$$\text{Tr}(E_𝐚^\omega )=\underset{𝐛𝒦_n}{}\lambda \left(S(v_{𝐛+𝐱})E_𝐚^\omega (u_𝐛)\right)=\lambda \left(S(v_{𝐚+𝐱})u_𝐚\right).$$

By Theorem 1.1 again, we also have

$$\text{Tr}(E_{𝐚+𝐱}^\omega )=\underset{𝐛𝒦_n}{}\lambda \left(S(E_{𝐚+𝐱}^\omega (v_{𝐛+𝐱}))u_𝐛\right)=\lambda \left(S(v_{𝐚+𝐱})u_𝐚\right).$$

Therefore, $`\text{Tr}(E_𝐚^\omega )=\text{Tr}(E_{𝐱𝐚}^\omega )`$. Since $`dim(H_𝐚^\omega )=\text{Tr}(E_𝐚^\omega )`$ for any $`𝐚𝒦_n`$, the result follows. $`\mathrm{}`$

###### Theorem 1.3

\[Ng02\] Let $`H`$ be a Hopf algebra of dimension $`pq`$ over $`k`$ with antipode $`S`$, where $`pq`$ are odd primes. Then the index of $`H`$ and the order of $`S^4`$ are equal to $`p`$, and $`\text{Tr}(S^{2p})=p^2d`$ for some odd integer $`d`$.
$`\mathrm{}`$

###### Lemma 1.4

Suppose that $`H`$ is a non-semisimple Hopf algebra of dimension $`pq`$ over $`k`$ where $`pq`$ are odd primes, and that $`\omega k`$ is a primitive $`p`$th root of unity. Let $`g`$ and $`\alpha `$ be the distinguished group-like elements of $`H`$ and $`H^{}`$ respectively. If $`g`$ is non-trivial, then the integer $`d`$ in Theorem 1.3 is given by

$$dim(H_{0,i,j}^\omega )dim(H_{1,i,j}^\omega )=d$$

for all $`i,j𝐙_p`$. Moreover, if both $`g`$ and $`\alpha `$ are not trivial, then

$$dim(H_{a,i,j^{}}^\omega )=dim(H_{a,i,j}^\omega )$$

for any $`a𝐙_2`$ and $`i,j,j^{}𝐙_p`$.

Proof. If $`\alpha `$ is trivial and $`g1`$, then by \[Ng02, Lemma 4.3\],

$$dim(H_{0,i,j}^\omega )dim(H_{1,i,j}^\omega )=d.$$

If both $`g`$ and $`\alpha `$ are non-trivial, then by the proof of \[Ng02, Proposition 5.3\], $`H`$ is isomorphic to the biproduct

$$R\times B$$
(1.4)
as Hopf algebras (cf. \[Rad85\]) where $`B=k[g]`$ and $`R`$ is a right $`B`$-comodule subalgebra of $`H`$. It is shown in \[AS98, section 4\] that $`R`$ is invariant under $`S^2`$. Moreover, in the identification $`HRB`$ given by multiplication, one has

$$S^2=Tid_B$$
(1.5)
where $`T`$ is the restriction of $`S^2`$ on $`R`$. Let

$$R_{a,i}=\{xR|S^2(x)=(1)^a\omega ^ix\}$$

for any $`(a,i)𝐙_2\times 𝐙_p`$. It follows from the proof of \[Ng02, Proposition 5.3\] that

$$dim(R_{0,i})dim(R_{1,i})=d.$$

By (1.4),

$$H_{a,i,j}^\omega =R_{a,i}e_j$$

for all $`(a,i,j)𝒦_p`$ where $`e_j`$ is the central idempotent of $`B`$ such that $`e_jg=\omega ^je_j`$. Thus,

$$dim(H_{a,i,j}^\omega )=R_{a,i}$$

for all $`(a,i,j)𝒦_p`$ and hence

$$dim(H_{0,i,j}^\omega )dim(H_{1,i,j}^\omega )=d.$$

$`\mathrm{}`$

## 2 Proofs of Main Results

###### Lemma 2.1

Let $`H`$ be a finite-dimensional Hopf algebra with antipode $`S`$ of odd index $`n>1`$ over $`k`$, and $`\omega k`$ a primitive $`n`$th root of unity. Let $`\mathrm{}𝐙_n`$ such that $`2\mathrm{}=x(\omega ,H)`$. Then

$$dim(H_{1,\mathrm{},\mathrm{}}^\omega )$$

is even.

Proof. Let $`V`$ be space of all $`fH^{}`$ such that $`f(u)=0`$ for $`uH_{a,i,j}^\omega `$ whenever $`(a,i,j)(1,\mathrm{},\mathrm{})`$. Obviously, $`V`$ is isomorphic to $`(H_{1,\mathrm{},\mathrm{}}^\omega )^{}`$ and so $`dim(V)=dim(H_{1,\mathrm{},\mathrm{}}^\omega )`$. Let $`\mathrm{\Lambda }`$ be a non-zero left integral of $`H`$ and

$$\mathrm{\Delta }(\mathrm{\Lambda })=\underset{𝐚𝒦_n}{}u_𝐚v_{𝐚+𝐱}$$

the normal form of $`\mathrm{\Delta }(\mathrm{\Lambda })`$ associated with $`\omega `$ where $`𝐱=(0,2\mathrm{},2\mathrm{})`$. Then

$$(f,h)=(fh)\mathrm{\Delta }(\mathrm{\Lambda })$$

defines a non-degenerate bilinear form on $`H^{}`$. Let $`fV`$ such that $`(f,h)=0`$ for all $`hV`$. For any $`h^{}H^{}`$, there exists $`hV`$ such that $`h^{}(u)=h(u)`$ for all $`uH_{1,\mathrm{},\mathrm{}}^\omega `$. Thus

$$(f,h^{})=\underset{𝐚𝒦_n}{}f(u_𝐚)h^{}(v_{𝐚+𝐱})=f(u_{1,\mathrm{},\mathrm{}})h^{}(v_{1,\mathrm{},\mathrm{}})=(f,h)=0.$$

By the non-degeneracy of $`(,)`$, $`f=0`$. Therefore, $`(,)`$ induces a non-degenerate bilinear form on $`V`$. Using \[Rad94, Theorem 3(d)\], we have

$$\mathrm{\Delta }^{op}(\mathrm{\Lambda })=\underset{(a,i,j)𝒦_n}{}(1)^a\omega ^{ij}\left(u_{a,i,j}v_{a,2\mathrm{}i,2\mathrm{}j}\right).$$

Therefore, for any $`f,hV`$,

$$(h,f)=(fh)\mathrm{\Delta }^{op}(\mathrm{\Lambda })=f(u_{1,\mathrm{},\mathrm{}})h(v_{1,\mathrm{},\mathrm{}})=(f,h).$$

Hence, $`V`$ admits a non-degenerate alternating form and so $`dim(V)`$ is even. $`\mathrm{}`$

If $`H`$ is a finite-dimensional Hopf algebra of index $`n>1`$, we define

$`H_{}`$ $`:=`$ $`\{uH|S^{2n}(u)=u\},`$
$`H_+`$ $`:=`$ $`\{uH|S^{2n}(u)=u\}.`$
###### Corollary 2.2

Suppose $`H`$ is a finite-dimensional Hopf algebra with antipode $`S`$ of odd index $`n>1`$. Then, the subspace $`H_{}`$ is of even dimension.

Proof. Let $`\omega k`$ be a $`n`$th of unity and $`\mathrm{}𝐙_n`$ such that $`2\mathrm{}=x(\omega ,H)`$. We then have

$$H_{}=\underset{i,j𝐙_n}{}H_{1,i,j}^\omega =H_{1,\mathrm{},\mathrm{}}^\omega \left(\underset{\genfrac{}{}{0pt}{}{\mathrm{some}i,j𝐙_n}{(i,j)(\mathrm{},\mathrm{})}}{}H_{1,i,j}^\omega H_{1,2\mathrm{}i,2\mathrm{}j}^\omega \right).$$

It follows from Corollary 1.2 and Lemma 2.1, $`dim(H_{})`$ is even. $`\mathrm{}`$

###### Theorem 2.3

Let $`H`$ be a non-semisimple Hopf algebra with antipode $`S`$ of dimension $`pq`$ where $`pq`$ are odd primes. Then

$$\text{Tr}(S^{2p})=p^2d\text{and}dpq(mod4).$$

Proof. By Theorem 1.3, $`H`$ is of index $`p`$ and $`\text{Tr}(S^{2p})=p^2d`$ for some odd integer $`d`$. Since

$$dim(H_+)+dim(H_{})=pq$$

and

$$\text{Tr}(S^{2p})=dim(H_+)dim(H_{})=p^2d,$$

we have

$$dim(H_{})=p(qpd)/2.$$

By Corollary 2.2, $`p(qpd)0(mod4)`$ or $`dpq(mod4)`$ . $`\mathrm{}`$

###### Theorem 2.4

For any pair of twin primes $`p<q`$, if $`H`$ is a Hopf algebra of dimension $`pq`$, then $`H`$ is semisimple.

Proof. Suppose there is a non-semisimple Hopf algebra $`H`$ of dimension $`pq`$. By \[LR88\], $`H^{}`$ is also non-semisimple. Since $`dim(H)`$ is odd, by \[LR95, Theorem 2.1\], $`H`$ and $`H^{}`$ can not be both unimodular. By duality, we may simply assume that $`H^{}`$ is not unimodular. It follows from Theorem 1.3 that $`|G(H)|=p`$ and so

$$dim(C)p$$

where $`C`$ is the coradical of $`H`$. If $`dim(C)=p`$, then $`H`$ is pointed and hence, by \[Şte97, Corollary 4\], $`H`$ is semisimple. Therefore, $`dim(C)>p`$ and so we have

$$\text{Tr}(S^{2p}|_{H/C})(pqdim(C))>pq+p=p^2p.$$

It follows from \[LR88, Lemma 3.2\] that

$$\text{Tr}(S^{2p}|_C)p.$$

Thus, we have

$$\text{Tr}(S^{2p})=\text{Tr}(S^{2p}|_C)+\text{Tr}(S^{2p}|_{H/C})>p^2.$$
(2.1)
Since $`pq1(mod4)`$, by Theorem 2.3,

$$\text{Tr}(S^{2p})=p^2$$

but this contradicts (2.1). $`\mathrm{}`$

Acknowledgement

The author would like thank P. Etingof for his useful suggestion for Theorem 2.4 and informing me his recent work \[EG03\] with S. Gelaki.


text:
# A complete set of covariants of the four qubit system

## 1 Introduction

The invariant theory of fourth rank hypermatrices (or quadrilinear forms) over a two-dimensional complex vector space, already considered at the end of the nineteenth century, has experienced recently a regain of interest, mainly due to its potential applications to the understanding of entanglement in four qubit systems . We shall give here the first complete solution to the problem of describing the polynomial covariants, an investigation started by Le Paige as early as 1881 . The theory was further advanced by C Segre in 1922 , using only geometric methods which led him close to a complete classification of the orbits. Such a complete classification was obtained only recently by Verstratete et al. , by exploiting the local isomorphism between $`SO_4`$ and $`SL_2\times SL_2`$, which permits a reduction of the problem to the classification of complex symmetric matrices up to orthogonal transformations.

A complete picture would require a description of the orbit closures as algebraic varieties and an understanding of their ordering with respect to inclusion. In classical invariant theory, such descriptions were usually given in terms of invariants and covariants. The main result of  was a complete description of the algebra of polynomial functions $`f(a_{ijkl})`$ in the components of a four qubit state

$$|\mathrm{\Psi }=\underset{i,j,k,l=0}{\overset{1}{}}a_{ijkl}|i|j|k|l$$
(1)
which are invariant under the natural action of the so-called SLOCC111for Stochastic Local Operations assisted by Classical Communication, see . group $`G=SL(2,)^{\times 4}`$ on the local Hilbert space $`=V^4`$, where $`V=^2`$.

One motivation for this investigation was to test on the four qubit case Klyachko’s proposed definitions of entanglement and complete entanglement . These consist in identifying entangled states as being precisely those for which at least one SLOCC polynomial invariant is not zero, and completely entangled states as the vectors of minimal norm in closed SLOCC orbits, which are unique up to local unitary transformations.

Klyachko’s definition of complete entanglement seems to be supported by the recent numerical experiments of Verstraete et al. . Indeed, these authors propose a numerical algorithm converging to a normal form, which, in the case of a stable state, is a state of minimal norm in its SLOCC orbit $`𝒪`$, and otherwise in the unique closed orbit contained in the closure $`\overline{𝒪}`$. Thus, in both cases, the normal form is a completely entangled state in the sense of .

We take the opportunity to point out that, as conjectured in , the normal form is indeed unique up to local unitary transformations 222 The results implying this conjecture, as well as the necessary background in Geometric Invariant Theory, are collected in : the Kempf-Ness criterion (theorem 6.18) proves the result in the case of a closed orbit, and by the corollary of theorem 4.7, there is a unique closed orbit in the closure of an arbitrary orbit..

In , the polynomial invariants were constructed by means of the classical notion of a covariant. If we interpret our state $`|\mathrm{\Psi }`$ as a quadrilinear form

$$f(𝐱,𝐲,𝐳,𝐭)=\underset{i,j,k,l=0}{\overset{1}{}}a_{ijkl}x_iy_jz_kt_l$$
(2)
on $`V\times V\times V\times V`$, a covariant of $`A`$ is a multi- homogeneous $`G`$-invariant polynomial in the form coefficients $`a_{ijkl}`$ and in the original variables $`x_i,y_j,z_k,t_l`$.

Since the spaces $`S^\mu (V)`$ ($`\mu ^4`$) of homogeneous polynomials of multidegree $`\mu `$ in $`𝐱,𝐲,𝐳,𝐭`$ exhaust all finite dimensional representations of $`G`$, a covariant of degree $`d`$ in the $`a_{ijkl}`$ and $`\mu `$ in the variables can be regarded as a $`G`$-equivariant map $`S^d()S^\mu (V)`$ from the space $`S^d()`$ of homogeneous polynomials of degree $`d`$ in $`A`$ to the irreducible representation $`S^\mu (V)`$. Such a map is determined by the image of a highest weight vector, so that covariants are in one to one correspondence with highest weight vectors in $`S^d()`$, these being known as semi-invariants in the classical language (cf. ).

The covariants form an algebra, which is naturally graded with respect to $`d`$ and $`\mu `$. We denote by $`𝒞_{d;\mu }`$ the corresponding graded pieces. The knowledge of their dimensions $`c_{d;\mu }`$ is equivalent to the decomposition of the character of $`S^d()`$ into irreducible characters of $`G`$, and the knowledge of a basis of $`𝒞_{d;\mu }`$ allows one to write down a Clebsch-Gordan series with respect to $`G`$ for any polynomial in the $`a_{ijkl}`$. Also, it is known that the equations of any $`G`$-invariant closed subvariety of the projective space $`()`$ are given by the simultaneous vanishing of the coefficients of some covariants.

Finally, let us point out a connection with the approach of  and local unitary invariants. The spaces $`S^\mu (V)`$, and hence the $`𝒞_{d;\mu }`$ are also Hilbert spaces in a natural way. If $`\mathrm{\Psi }_{d;\mu }^\alpha `$ is a linear basis of $`𝒞_{d;\mu }`$, the scalar products $`\mathrm{\Psi }_{d;\mu }^\alpha |\mathrm{\Psi }_{d;\mu }^\beta `$ (taken with respect to the variables, the coefficients $`a_{ijkl}`$ being treated as scalars) form a basis of the space of $`U(2)^{\times 4}`$ invariants of degree $`2d`$ (that is, $`d`$ in $`A`$ and $`d`$ in $`\overline{A}`$), and the $`\mathrm{\Psi }_{d;\mu }^\alpha |\mathrm{\Psi }_{e;\mu }^\beta `$ form a basis of the space of $`SU(2)^{\times 4}`$ invariants of bidegree $`(d,e)`$ in $`(A,\overline{A})`$. Such expressions are used for example in , in the case of three qubits.

## 2 Summary of method and results

A minimal generating set consisting of 170 covariants is found by means a computer search through iterated transvectants (see section 3), guided by the knowledge of the Hilbert series (see section 4), and simplified by taking into account some special properties of multilinear forms. The following table gives the number of covariants of degree $`d`$ in $`A`$ and multidegree $`\lambda `$ in the variables, where $`\lambda `$ is in nondecreasing order. There are similar covariants for each of the $`n_\lambda `$ permutations $`\mu `$ of the degrees. For example, in degree 5, we have 12 covariants which are cubic in one variable and linear in the other three, and one quadrilinear covariant.

$$\begin{array}{cccccccccccccc}& & & & & & & & & & & & & \\ \lambda \backslash d& n_\lambda & 1& 2& 3& 4& 5& 6& 7& 8& 9& 10& 11& 12\\ & & & & & & & & & & & & & \\ 0000& 1& & 1& & 2& & 1& & & & & & \\ & & & & & & & & & & & & & \\ 1111& 1& 1& & 2& & 1& & & & & & & \\ & & & & & & & & & & & & & \\ 2200& 6& & 1& & 1& & 1& & & & & & \\ & & & & & & & & & & & & & \\ 2220& 4& & & & 2& & 2& & 2& & & & \\ & & & & & & & & & & & & & \\ 3111& 4& & & 1& & 3& & 3& & 1& & & \\ & & & & & & & & & & & & & \\ 3311& 6& & & & & & & 1& & 2& & 1& \\ & & & & & & & & & & & & & \\ 4000& 4& & & & 1& & & & 1& & & & \\ & & & & & & & & & & & & & \\ 4200& 12& & & & & & 1& & 1& & 1& & \\ & & & & & & & & & & & & & \\ 5111& 4& & & & & & & 1& & 2& & 1& \\ & & & & & & & & & & & & & \\ 6000& 4& & & & & & & & & & & & 1\end{array}$$

## 3 Multiple transvectants

Transvectants, or Cayley’s Omega-process, are the basic tools for constructing complete systems of covariants, and play a key rôle in Gordan’s and Hilbert’s proofs that the ring of covariants is finitely generated. The notion of a transvectant extends with little modifications to forms in several series of variables, and appears to have been first exploited by Le Paige  in the case of binary trilinear forms, and by Peano , who computed the complete systems for forms of bidegrees $`(1,1)`$, $`(2,1)`$ and $`(2,2)`$ in two independent binary variables. Complete systems for bidegrees $`(3,1)`$ and $`(4,1)`$ have been given by Todd , and, to the best of our knowledge, the only forms in more that two binary variables for which the complete system is known are the $`(1,1,1)`$  and the $`(2,1,1)`$, due to Gilham . The geometry of the quadrilinear form is discussed by Segre  but no attempt is made to describe the covariants.

If $`f`$ and $`g`$ are forms in the binary variable $`𝐱=(x_1,x_2)`$, we identify their tensor product $`fg`$ with the polynomial $`f(𝐱^{})g(𝐱^{\prime \prime })`$ in two independent binary variables $`𝐱^{}`$, $`𝐱^{\prime \prime }`$. Following , the multiplication map $`fgfg`$ is denoted by $`\mathrm{tr}`$. So, $`\mathrm{tr}(f(𝐱^{})g(𝐱^{\prime \prime }))=f(𝐱)g(𝐱)`$.

The Cayley operator $`\mathrm{\Omega }_𝐱`$ acts on such a tensor product by the differential operator

$$\mathrm{\Omega }_𝐱=\left|\begin{array}{cc}\frac{}{x_1^{}}& \frac{}{x_1^{\prime \prime }}\\ \frac{}{x_2^{}}& \frac{}{x_2^{\prime \prime }}\end{array}\right|$$
(3)
If $`f`$ and $`g`$ are two $`p`$-tuple forms in $`p`$ independent binary variables $`𝐱_i`$, one defines for any $`(i_1,i_2,\mathrm{},i_p)^p`$ a multiple transvectant of $`f`$ and $`g`$ by

$$(f,g)^{i_1i_2\mathrm{}i_p}=\mathrm{tr}\mathrm{\Omega }_1^{i_1}\mathrm{\Omega }_2^{i_2}\mathrm{}\mathrm{\Omega }_p^{i_p}f(𝐱_1^{},\mathrm{},𝐱_p^{})g(𝐱_1^{\prime \prime },\mathrm{},𝐱_p^{\prime \prime }),$$
(4)
where $`\mathrm{\Omega }_i=\mathrm{\Omega }_{𝐱_i}`$, and $`\mathrm{tr}`$ acts on all variables by $`𝐱_i^{},𝐱_i^{\prime \prime }𝐱_i`$.

It can be proved that the complete system of covariants of any number of forms can be reached in a finite number of steps by building iterated transvectants, starting with the ground forms.

## 4 The Hilbert series

The (multivariate) Hilbert series for the algebra of covariants is defined by

$$h(t,u_1,u_2,u_3,u_4)=\underset{d,\mu }{}c_{d;\mu }t^d𝐮^\mu ,$$
(5)
where $`c_{d;\mu }`$ is the dimnension of the space of homogeneous covariants which are of degree $`d`$ in the $`a_{ijkl}`$ and of multidegree $`\mu `$ in the variables. Let

$$S=\underset{i=1}{\overset{4}{}}(1u_i^2)\underset{\alpha \{1,1\}^4}{}(1𝐮^\alpha t)^1.$$
(6)
Here $`S`$ has to be considered as the formal power series obtained by expansion with respect to the variable $`t`$. Let $``$ be the linear operator acting on a formal series in $`t,𝐮`$ by leaving unchanged every monomial $`t^d𝐮^\mu `$ with $`\mu ^4`$, and annihilating those with $`u`$-exponent having some negative coordinate. It follows from standard considerations about the characters of $`G`$ that $`h=S`$.

By successive decompositions into partial fractions (with respect to $`u_1`$, next $`u_2,u_3,u_4`$) we have computed this series, which guided us in the search for the covariants. The numerator is too large to be printed, but if one substitutes $`u_1=u_2=u_3=u_4=u`$, one finds after simplification $`h=P/Q`$, where the numerator $`P`$ is

$`1u^2t+\left(3u^42u^2\right)t^2+\left(u^6+4u^4\right)t^3`$
$`+\left(10u^4u^2\right)t^4+\left(4u^82u^6+2u^4\right)t^5`$
$`+\left(2u^{10}+6u^82u^6+8u^4\right)t^6+\left(2u^{10}+6u^8\right)t^7`$
$`+\left(8u^{12}+u^{10}+13u^82u^6+4u^4\right)t^8`$
$`+\left(8u^{12}u^{10}+12u^8u^6\right)t^9`$
$`+\left(2u^{14}13u^{12}+13u^82u^6\right)t^{10}`$
$`+\left(u^{14}12u^{12}+u^{10}+8u^8\right)t^{11}`$
$`+\left(4u^{16}+2u^{14}13u^{12}u^{10}+8u^8\right)t^{12}`$
$`+\left(6u^{12}2u^{10}\right)t^{13}+\left(8u^{16}+2u^{14}6u^{12}2u^{10}\right)t^{14}`$
$`+\left(2u^{16}+2u^{14}+4u^{12}\right)t^{15}+\left(u^{18}10u^{16}\right)t^{16}`$
$`+\left(4u^{16}u^{14}\right)t^{17}+\left(2u^{18}3u^{16}\right)t^{18}+u^{18}t^{19}u^{20}t^{20}`$
and the denominator $`Q`$ is

$`(1tu^2)(1tu^4)(1t^2)(1t^2u^2)^2(1t^2u^4)^3`$
$`\times (1t^4)(1t^4u^2)(1t^4u^4)(1t^6).`$
The algebra of covariants is Cohen-Macaulay (see, e.g., ). This means that it is a free module of finite rank over a subalgebra generated by a finite familly of homogeneous, algebraically independent elements $`f_1,\mathrm{},f_k`$. Then $`k`$ is the Krull dimension of the algebra of covariants (the maximum number of algebraically independent elements) and $`h(t,t,t,t,t)`$ has a pole at $`t=1`$, of order $`k`$. We found in this way that $`k=12`$.

When substituting $`u_i=0`$, the Hilbert series of the invariants is recovered.

## 5 A fundamental set of covariants

The fundamental covariants are tabulated in A. They are denoted by symbols $`X_{pqrs}^m`$, in which the letter $`X`$ indicates the degree in the form coefficients $`a_{ijkl}`$ (1 for $`A`$, 2 for $`B`$, etc.), the subscripts $`ijkl`$ indicate the degrees in the variables $`𝐱,𝐲,𝐳,𝐭`$, and the optional exponent $`m`$ serves to distinguish between covariants having the same degrees.

The only covariant of degree $`1`$ is the ground form $`f=A_{1111}`$. In degree two, we have one invariant, the basic hyperdeterminant $`H=\frac{1}{2}B_{0000}`$, which is defined in general for all multilinear form with an even number of variables (see  for some applications), and six biquadratic forms such as $`B_{2200}`$. In degree 3, we find two quadrilinear forms and four cubico-trilinear covariants. There are three other invariants, which occur in degree 4 ($`D_{0000}^1`$, $`D_{0000}^2`$) and 6 ($`F_{0000}`$). The maximal degree is 12, where we find four binary sextics.

We see that some of the covariants are of a type for which the invariant theory is well understood (binary forms of degree 4 and 6, biquadratic forms), or are again quadrilinear forms. Other are of essentially unexplored types (3111, 2220, 4200, 3311, 5111).

Naturally, the covariants of a covariant are again covariants (although not necessarily irreducible). Some of these are discussed in C.

Let us now sketch the application to the description of the orbit closures. The normal forms obtained by Verstraete et al.  are

$`G_{abcd}`$ $`=`$ $`{\displaystyle \frac{a+d}{2}}(|0000+|1111)+{\displaystyle \frac{ad}{2}}(|0011+|1100)`$
$`+{\displaystyle \frac{b+c}{2}}(|0101+|1010)+{\displaystyle \frac{bc}{2}}(|0110+|1001)`$
$`L_{abc_2}`$ $`=`$ $`{\displaystyle \frac{a+b}{2}}(|0000+|1111)+{\displaystyle \frac{ab}{2}}(|0011+|1100)`$
$`+c(|0101+|1010)+|0110`$
$`L_{a_2b_2}`$ $`=`$ $`a(|0000+|1111)+b(|0101+|1010)`$
$`+|0110+|0011`$
$`L_{ab_3}`$ $`=`$ $`a(|0000+|1111)+{\displaystyle \frac{a+b}{2}}(|0101+|1010)`$
$`+{\displaystyle \frac{ab}{2}}(|0110+|1001)`$
$`+{\displaystyle \frac{i}{\sqrt{2}}}(|0001+|0010+|0111+|1011)`$
$`L_{a_4}`$ $`=`$ $`a(|0000+|0101+|1010+|1111)`$
$`+(i|0001+|0110i|1011)`$
$`L_{a_20_{3\overline{1}}}`$ $`=`$ $`a(|0000+|1111)+(|0011+|0101+|0110)`$
$`L_{0_{5\overline{3}}}`$ $`=`$ $`|0000+|0101+|1000+|1110`$
$`L_{0_{7\overline{1}}}`$ $`=`$ $`|0000+|1011+|1101+|1110`$
$`L_{0_{3\overline{1}}0_{3\overline{1}}}`$ $`=`$ $`|0000+|0111`$
where in our notation a ket $`|ijkl`$ is to be identified with the monomial $`x_iy_jz_kt_l`$. The invariants $`B_{0000}`$, $`D_{0000}^1`$, $`D_{0000}^2`$ and $`F_{0000}`$ are shown in  to separate the normal forms $`G_{abcd}`$, $`L_{abc_2}`$, $`L_{ab_3}`$, $`L_{a_2b_2}`$, $`L_{a_4}`$ and $`L_{a_20_{3\overline{1}}}`$. But they vanish for $`L_{0_{5\overline{3}}}`$, $`L_{0_{7\overline{1}}}`$ and $`L_{0_{3\overline{1}}0_{3\overline{1}}}`$. The knowledge of the fundamental set of covariants is more than sufficient to separate the last three forms. Indeed,

$`C_{3111}(L_{0_{5\overline{3}}})=`$ $`2(x_2y_2z_1t_1x_1y_2z_1t_1)`$ (7)
$`D_{2200}(L_{0_{5\overline{3}}})=`$ $`0`$ (8)
$`C_{3111}(L_{0_{7\overline{1}}})=`$ $`2x_2(y_1z_1t_2+y_1z_2t_12y_2z_1t_1)`$ (9)
$`D_{2200}(L_{0_{7\overline{1}}})=`$ $`16x_2^2z_1z_2`$ (10)
$`C_{3111}(L_{0_{3\overline{1}}0_{3\overline{1}}})=`$ $`0`$ (11)
$`D_{2200}(L_{0_{3\overline{1}}0_{3\overline{1}}})=`$ $`0`$ (12)
From this, it is not difficult (although somewhat tedious) to obtain the equations of the closures of the orbits, and to study the inclusions between them. This will be left for a future paper on the subjet, in which we expect to be able to produce first a better choice of the fundamental covariants (with greater geometrical or physical significance).

## 6 Rational covariants

The algebra of rational covariants is simpler than the algebra of polynomial covariants. It is a field of rational functions over 12 homogeneous independent generators. A way to compute a fundamental set of rational semi-invariants, consists in using the so-called associated forms . Let $`F`$ be the polynomial obtained from the ground form by applying the following series of substitutions

$`x_1`$ $`a_{0000}x_1a_{1000}x_2,`$ $`x_2a_{0000}x_2,`$
$`y_1`$ $`a_{0000}y_1a_{0100}y_2,`$ $`y_2a_{0000}y_2,`$
$`z_1`$ $`a_{0000}z_1a_{0010}z_2,`$ $`z_2a_{0000}z_2,`$
$`t_1`$ $`a_{0000}t_1a_{0001}t_2,`$ $`t_2a_{0000}t_2.`$
The semi-invariants which are the sources of the associated forms are the coefficients of the monomials $`x_iy_jz_kt_l`$ in $`F`$, divided by $`a_{0000}^{9ijkl}`$ We obtain in this way a list of semi-invariants which are the sources of some polynomial covariants given below. Here, $`H=\frac{1}{2}(f,f)^{1111}`$, $`b_{xy}=\frac{1}{2}(f,f)^{0011}`$, etc. are as in .

$$\begin{array}{cc}& \\ \text{Source }c_\alpha & \text{Covariant }𝒞_\alpha \\ & \\ c_{0000}& 1\\ c_{1000}& 0\\ c_{0100}& 0\\ c_{0010}& 0\\ c_{0001}& 0\\ c_{0011}& b_{xy}\\ c_{0101}& b_{xz}\\ c_{0110}& b_{xt}\\ c_{1001}& b_{yz}\\ c_{1010}& b_{yt}\\ c_{1100}& b_{zt}\\ c_{0111}& C_{3111}\\ c_{1011}& C_{1311}\\ c_{1101}& C_{1131}\\ c_{1110}& C_{1113}\\ c_{1111}& Hf^2b_{xy}b_{zt}b_{xz}b_{yt}b_{xt}b_{yz}\end{array}$$

The $`12`$ homogeneous independent generators of the field of rational covariants are the $`11`$ non-trivial associated forms above, together with the ground form $`f`$. Actually, the last one ($`𝒞_{1111}`$) can be advantageously replaced by $`H`$.

Now, each covariant can be written as a rational function in these $`12`$ generators. It suffices to make the substitutions

$$a_{ijkl}𝒞_{ijkl}f^{1(i+j+k+l)}$$
(13)
in the source of the covariant, where $`𝒞_\alpha `$ is the covariant with source $`c_\alpha `$.

For example, the source of $`D_{4000}`$ is

$`2a_{0111}a_{0100}a_{0000}a_{0011}4a_{0111}a_{0010}a_{0001}a_{0010}`$
$`a_{0000}^2a_{0111}^2+2a_{0111}a_{0000}a_{0001}a_{0110}`$
$`+2a_{0111}a_{0000}a_{0010}a_{0101}+2a_{0110}a_{0001}a_{0011}a_{0100}`$
$`a_{0001}^2a_{0110}^2+2a_{0110}a_{0001}a_{0010}a_{0101}`$
$`4a_{0110}a_{0011}a_{0000}a_{0101}+2a_{0101}a_{0010}a_{0011}a_{0100}`$
$`a_{0010}^2a_{0101}^2a_{0011}^2a_{0100}^2`$
and the above substitutions give

$`D_{4000}`$ $`={\displaystyle \frac{1}{𝒞_{0000}^2}}(𝒞_{0111}^2+4𝒞_{0110}𝒞_{0011}𝒞_{0101})`$ (14)
$`={\displaystyle \frac{1}{f^2}}(C_{3111}^2+4b_{xt}b_{xy}b_{xz}).`$
This yields a syzygy

$$f^2D_{4000}+C_{3111}^2+4b_{xy}b_{xz}b_{xt}=0.$$
(15)
## 7 Conclusion

It is remarkable that the investigation of the fine structure of the four qubit system has led to the first complete solution of a mathematical problem which had already been considered as early as 1881 . This problem was among the very few ones which were out of reach of the computational skills of the classical invariant theorists, though accessible to a computer treatment. The number of fundamental covariants, here 170, is not, however, the highest ever found 333 For example, Turnbull obtained in 1910 a system of 784 forms for the case of three ternary quadratics, and in 1947, Todd proved that 603 of them formed a complete minimal system., and we expect to be able to produce in the near future a human readable proof, together with a better choice of the generators, i.e., to find, at least for the lowest degrees, generators with a transparent geometrical interpretation.

A complete description of the ring of covariants should in principle include a generating set of the syzygies. However, we can see from the Hilbert series that this is a hopeless task, as it is already for the previously known specializations. We have computed all the syzygies up to degree 7, and formula (13) allows one to find at least one syzygy for each covariant which is not one of the $`𝒞_\alpha `$.

Turning back to the issue of entanglement, we see that we have now at our disposal all the possible building blocks for the construction of entanglement measures for systems with no more than four qubits. It is to be expected that further investigations will allow one to select among them the most relevant ones, and that the analysis of their geometric significance will give a clue for the general case.

## Appendix A Fundamental covariants

$$\begin{array}{cc}\text{Degree 2}& \text{Degree 3}\\ \begin{array}{cc}& \\ \text{Symbol}& \text{Transvectant}\\ & \\ B_{0000}& (f,f)^{1111}\\ & \\ B_{2200}& (f,f)^{0011}\\ B_{2020}& (f,f)^{0101}\\ B_{2002}& (f,f)^{0110}\\ B_{0220}& (f,f)^{1001}\\ B_{0202}& (f,f)^{1010}\\ B_{0022}& (f,f)^{1100}\end{array}& \begin{array}{cc}& \\ \text{Symbol}& \text{Transvectant}\\ & \\ C_{1111}^1& (f,B_{2200})^{1100}\\ C_{1111}^2& (f,B_{2020})^{1010}\\ & \\ C_{3111}& (f,B_{2200})^{0100}\\ C_{1311}& (f,B_{2200})^{1000}\\ C_{1131}& (f,B_{2020})^{1000}\\ C_{1113}& (f,B_{2002})^{1000}\end{array}\end{array}$$

Degree 4

$$\begin{array}{cc}\begin{array}{cc}& \\ \text{Symbol}& \text{Transvectant}\\ & \\ D_{0000}^1& (f,C_{1111}^1)^{1111}\\ D_{0000}^2& (f,C_{1111}^2)^{1111}\\ & \\ D_{2200}& (f,C_{3111})^{1011}\\ D_{2020}& (f,C_{1111}^1)^{0101}\\ D_{2002}& (f,C_{3111})^{1110}\\ D_{0220}& (f,C_{1311})^{1101}\\ D_{0202}& (f,C_{1311})^{1110}\\ D_{0022}& (f,C_{1131})^{1110}\end{array}& \begin{array}{cc}& \\ \text{Symbol}& \text{Transvectant}\\ & \\ D_{4000}& (f,C_{3111})^{0111}\\ D_{0400}& (f,C_{1311})^{1011}\\ D_{0040}& (f,C_{1131})^{1101}\\ D_{0004}& (f,C_{1113})^{1110}\\ & \\ D_{2220}^1& (f,C_{1311})^{0101}\\ D_{2220}^2& (f,C_{1111}^1)^{0001}\\ D_{2202}^1& (f,C_{1113})^{0011}\\ D_{2202}^2& (f,C_{1311})^{0110}\\ D_{2022}^1& (f,C_{1113})^{0101}\\ D_{2022}^2& (f,C_{1111}^1)^{0100}\\ D_{0222}^1& (f,C_{1113})^{1001}\\ D_{0222}^2& (f,C_{1311})^{1100}\end{array}\end{array}$$

Degree 5

$$\begin{array}{cc}& \\ \text{Symbol}& \text{Transvectant}\\ & \\ E_{1111}& (f,D_{2200})^{1100}\\ & \\ E_{3111}^1& (f,D_{2200})^{0100}\\ E_{3111}^2& (f,D_{2202}^1)^{0101}\\ E_{3111}^3& (f,D_{2022}^2)^{0011}\\ E_{1311}^1& (f,D_{2200})^{1000}\\ E_{1311}^2& (f,D_{0202})^{0001}\\ E_{1311}^3& (f,D_{0220})^{0010}\\ E_{1131}^1& (f,D_{0222}^1)^{0101}\\ E_{1131}^2& (f,D_{2022}^2)^{1001}\\ E_{1131}^3& (f,D_{2020})^{1000}\\ E_{1113}^1& (f,D_{2022}^1)^{1010}\\ E_{1113}^2& (f,D_{2022}^2)^{1010}\\ E_{1113}^3& (f,D_{0004})^{0001}\end{array}$$

Degree 6

$$\begin{array}{cc}\begin{array}{cc}& \\ \text{Symbol}& \text{Transvectant}\\ & \\ F_{0000}& (f,E_{1111})^{1111}\\ & \\ F_{2200}& (f,E_{3111}^1)^{1011}\\ F_{2020}& (f,E_{1111})^{0101}\\ F_{2002}& (f,E_{1113}^1)^{0111}\\ F_{0220}& (f,E_{1311}^1)^{1101}\\ F_{0202}& (f,E_{1113}^3)^{1011}\\ F_{0022}& (f,E_{1113}^1)^{1101}\\ & \\ F_{2220}^1& (f,E_{1311}^1)^{0101}\\ F_{2220}^2& (f,E_{1311}^2)^{0101}\\ F_{2202}^1& (f,E_{3111}^2)^{1010}\\ F_{2202}^2& (f,E_{3111}^3)^{1010}\\ F_{2022}^1& (f,E_{1113}^1)^{0101}\\ F_{2022}^2& (f,E_{1113}^2)^{0101}\\ F_{0222}^1& (f,E_{1131}^1)^{1010}\\ F_{0222}^2& (f,E_{1131}^2)^{1010}\end{array}& \begin{array}{cc}& \\ \text{Symbol}& \text{Transvectant}\\ & \\ F_{4200}& (f,E_{3111}^1)^{0011}\\ F_{4020}& (f,E_{3111}^2)^{0101}\\ F_{4002}& (f,E_{3111}^2)^{0110}\\ F_{0420}& (f,E_{1311}^3)^{1001}\\ F_{0402}& (f,E_{1311}^2)^{1010}\\ F_{0042}& (f,E_{1131}^1)^{1100}\\ F_{2400}& (f,E_{1311}^1)^{0011}\\ F_{2040}& (f,E_{1131}^1)^{0101}\\ F_{2004}& (f,E_{1113}^1)^{0110}\\ F_{0240}& (f,E_{1131}^1)^{1001}\\ F_{0204}& (f,E_{1113}^1)^{1010}\\ F_{0024}& (f,E_{1113}^1)^{1100}\end{array}\end{array}$$

Degree 7

$$\begin{array}{cc}\begin{array}{cc}& \\ \text{Symbol}& \text{Transvectant}\\ & \\ G_{3111}^1& (f,F_{2200})^{0100}\\ G_{3111}^2& (f,F_{4002})^{1001}\\ G_{3111}^3& (f,F_{2202}^1)^{0101}\\ G_{1311}^1& (f,F_{0402})^{0101}\\ G_{1311}^2& (f,F_{2200})^{1000}\\ G_{1311}^3& (f,F_{0202})^{0001}\\ G_{1131}^1& (f,F_{0222}^1)^{0101}\\ G_{1131}^2& (f,F_{0222}^2)^{0101}\\ G_{1131}^3& (f,F_{2040})^{1010}\\ G_{1113}^1& (f,F_{2022}^1)^{1010}\\ G_{1113}^2& (f,F_{2022}^2)^{1010}\\ G_{1113}^3& (f,F_{0202})^{0100}\end{array}& \begin{array}{cc}& \\ \text{Symbol}& \text{Transvectant}\\ & \\ G_{5111}& (f,F_{4002})^{0001}\\ G_{1511}& (f,F_{0402})^{0001}\\ G_{1151}& (f,F_{2040})^{1000}\\ G_{1115}& (f,F_{0024})^{0010}\\ & \\ G_{3311}& (f,F_{2400})^{0100}\\ G_{3131}& (f,F_{2022}^2)^{0001}\\ G_{3113}& (f,F_{4002})^{1000}\\ G_{1331}& (f,F_{0240})^{0010}\\ G_{1313}& (f,F_{0402})^{0100}\\ G_{1133}& (f,F_{2022}^2)^{1000}\end{array}\end{array}$$

Degree 8

$$\begin{array}{cc}\begin{array}{cc}& \\ \text{Symbol}& \text{Transvectant}\\ & \\ H_{4000}& (f,G_{5111})^{1111}\\ H_{0400}& (f,G_{1311}^1)^{1011}\\ H_{0040}& (f,G_{1151})^{1111}\\ H_{0004}& (f,G_{1113}^3)^{1110}\\ & \\ H_{2220}^1& (f,G_{1311}^1)^{0101}\\ H_{2220}^2& (f,G_{1311}^2)^{0101}\\ H_{2202}^1& (f,G_{3111}^3)^{1010}\\ H_{2202}^2& (f,G_{1113}^2)^{0011}\\ H_{2022}^1& (f,G_{1113}^1)^{0101}\\ H_{2022}^2& (f,G_{1113}^2)^{0101}\\ H_{0222}^1& (f,G_{1131}^1)^{1010}\\ H_{0222}^2& (f,G_{1131}^2)^{1010}\end{array}& \begin{array}{cc}& \\ \text{Symbol}& \text{Transvectant}\\ & \\ H_{4200}& (f,G_{5111})^{1011}\\ H_{4020}& (f,G_{5111})^{1101}\\ H_{4002}& (f,G_{5111})^{1110}\\ H_{0420}& (f,G_{1311}^1)^{1001}\\ H_{0402}& (f,G_{1313})^{1011}\\ H_{0042}& (f,G_{1151})^{1110}\\ H_{2400}& (f,G_{1311}^1)^{0011}\\ H_{2040}& (f,G_{1151})^{0111}\\ H_{2004}& (f,G_{1113}^1)^{0110}\\ H_{0240}& (f,G_{1151})^{1011}\\ H_{0204}& (f,G_{1113}^1)^{1010}\\ H_{0024}& (f,G_{1113}^1)^{1100}\end{array}\end{array}$$

Degree 9

$$\begin{array}{cc}\begin{array}{cc}& \\ \text{Symbol}& \text{Transvectant}\\ & \\ I_{3111}& (f,H_{4020})^{1010}\\ I_{1311}& (f,H_{2220}^1)^{1010}\\ I_{1131}& (f,H_{0240})^{0110}\\ I_{1113}& (f,H_{2004})^{1001}\\ & \\ I_{5111}^1& (f,H_{4020})^{0010}\\ I_{5111}^2& (f,H_{4002})^{0001}\\ I_{1511}^1& (f,H_{0402})^{0001}\\ I_{1511}^2& (f,H_{2400})^{1000}\\ I_{1151}^1& (f,H_{0240})^{0100}\\ I_{1151}^2& (f,H_{0042})^{0001}\\ I_{1115}^1& (f,H_{2004})^{1000}\\ I_{1115}^2& (f,H_{0024})^{0010}\end{array}& \begin{array}{cc}& \\ \text{Symbol}& \text{Transvectant}\\ & \\ I_{3311}^1& (f,H_{2220}^1)^{0010}\\ I_{3311}^2& (f,H_{2220}^2)^{0010}\\ I_{3131}^1& (f,H_{4020})^{1000}\\ I_{3131}^2& (f,H_{2220}^1)^{0100}\\ I_{3113}^1& (f,H_{2004})^{0001}\\ I_{3113}^2& (f,H_{2022}^1)^{0010}\\ I_{1331}^1& (f,H_{0240})^{0010}\\ I_{1331}^2& (f,H_{2220}^1)^{1000}\\ I_{1313}^1& (f,H_{0204})^{0001}\\ I_{1313}^2& (f,H_{0222}^1)^{0010}\\ I_{1133}^1& (f,H_{0024})^{0001}\\ I_{1133}^2& (f,H_{0222}^1)^{0100}\end{array}\end{array}$$

$$\begin{array}{cc}\text{Degree 10}& \\ \begin{array}{cc}& \\ \text{Symbol}& \text{Transvectant}\\ & \\ J_{4200}& (f,I_{5111}^1)^{1011}\\ J_{4020}& (f,I_{5111}^1)^{1101}\\ J_{4002}& (f,I_{3113}^1)^{0111}\\ J_{0420}& (f,I_{1331}^1)^{1011}\\ J_{0402}& (f,I_{1511}^1)^{1110}\\ J_{0042}& (f,I_{1133}^1)^{1101}\\ J_{2400}& (f,I_{1511}^1)^{0111}\\ J_{2040}& (f,I_{3131}^1)^{1101}\\ J_{2004}& (f,I_{3113}^1)^{1110}\\ J_{0240}& (f,I_{1331}^1)^{1101}\\ J_{0204}& (f,I_{1115}^1)^{1011}\\ J_{0024}& (f,I_{1115}^1)^{1101}\end{array}& \begin{array}{c}\text{Degree 11}\\ \begin{array}{cc}& \\ \text{Symbol}& \text{Transvectant}\\ & \\ K_{3311}& (f,J_{4200})^{1000}\\ K_{3131}& (f,J_{4020})^{1000}\\ K_{3113}& (f,J_{4002})^{1000}\\ K_{1331}& (f,J_{0420})^{0100}\\ K_{1313}& (f,J_{0402})^{0100}\\ K_{1133}& (f,J_{0042})^{0010}\\ & \\ K_{5111}& (f,J_{4200})^{0100}\\ K_{1511}& (f,J_{2400})^{1000}\\ K_{1151}& (f,J_{2040})^{1000}\\ K_{1115}& (f,J_{2004})^{1000}\end{array}\end{array}\end{array}$$

Degree 12

$$\begin{array}{cc}& \\ \text{Symbol}& \text{Transvectant}\\ & \\ L_{6000}& (f,K_{5111})^{0111}\\ L_{0600}& (f,K_{1511})^{1011}\\ L_{0060}& (f,K_{1151})^{1101}\\ L_{0006}& (f,K_{1115})^{1110}\end{array}$$

## Appendix B Syzygies

The method of associated forms presented in Section 6 gives all the syzygies up to degree 5. In degree 6, one can check that, for example, the following two syzygies

$`D_{0000}^2f^2+2D_{0000}^1f^2\frac{3}{2}B_{2200}B_{0022}B_{0000}`$
$`+\frac{3}{2}B_{2020}B_{0202}B_{0000}\frac{9}{2}D_{2200}B_{0022}`$
$`4(C_{1111}^2)^2\frac{9}{2}D_{0022}B_{2200}8C_{1111}^1C_{1111}^2`$
$`+\frac{9}{2}D_{0220}B_{2002}+\frac{9}{2}D_{2002}B_{0220}`$ $`=0`$
$`(C_{1111}^1)^2+\frac{3}{4}D_{0000}^1f^2\frac{9}{8}B_{2200}B_{0022}B_{0000}`$
$`+\frac{9}{8}B_{2020}B_{0202}B_{0000}\frac{9}{4}D_{2200}B_{0022}`$
$`+\frac{9}{8}D_{0202}B_{2020}2(C_{1111}^2)^2\frac{9}{4}D_{0022}B_{2200}`$
$`2C_{1111}C_{1111}\frac{3}{2}D_{2020}B_{0202}`$
$`+\frac{9}{8}D_{0220}B_{2002}+\frac{9}{8}D_{2002}B_{0220}`$ $`=0`$
cannot be obtained by this method.

The second order syzygies arise in degree 7 and type $`(5333)`$.

## Appendix C Invariants of the covariants

As already mentioned, the next step in the study of the four qubit system should be to find geometrical interpretations of the simplest covariants. Partial information is already available, as some of the fundamental covariants are of known types, for which the invariant theory is reasonably well understood. Among these, the most important ones are certainly the six biquadratic forms $`b_{uv}`$. A double binary form $`g(𝐮,𝐯)`$ of bidegree $`(m,n)`$ is usually interpreted as defining a space curve, lying of the projective quadric $`XTYZ=0`$, which may be parametrized by

$$\left(\begin{array}{cc}X& Y\\ Z& T\end{array}\right)=\left(\begin{array}{cc}u_2v_2& u_2v_1\\ u_1v_2& u_1v_1\end{array}\right),$$
(16)
so that $`𝐮`$ and $`𝐯`$ parametrize the rectilinear generatrices. Such a curve has generically $`m`$ intersections with the generatrices of one system, and $`n`$ with generatrices of the other one. The covariants $`b_{uv}`$ can therefore be interpreted as six space quartics. It turns out that these have the same discriminant, which is proportional to the hyperdeterminant used in . The nonvanishing of the hyperdeterminant is therefore the condition for these curves to be elliptic. On the normal forms of , it is easy to check that one has three isomorphisms $`(b_{xy})(b_{zt})`$, $`(b_{xz})(b_{yt})`$ and $`(b_{xt})(b_{yz})`$. Geometric interpretations of the complete system of covariants of such forms of bidegree $`(2,2)`$ (which is due to Peano ) are available in the works of Kasner  and Turnbull .

Other double binary forms of the same type occur as covariants in degrees 4 and 6.

There are also some simple binary forms among the covariants. Quartics, whose invariant theory is completely understood, occur in degree 4 and 8. We have already used the fact that the common discriminant of the quartics in degree 4 was the hyperdeterminant . The fundamental covariants in degree 12, the highest degree, are four binary sextics, whose invariant of degree 2 is again the hyperdeterminant, as can be seen from the normal forms

$`L_{6000}`$ $`=`$ $`144V(a^2,b^2,c^2,d^2)(x_1^4x_2^4)x_1x_2`$ (17)
$`L_{0600}`$ $`=`$ $`96V(a^2,b^2,c^2,d^2)(y_1^4y_2^4)y_1y_2`$ (18)
$`L_{0060}`$ $`=`$ $`288V(a^2,b^2,c^2,d^2)(z_1^4z_2^4)z_1z_2`$ (19)
$`L_{0006}`$ $`=`$ $`96V(a^2,b^2,c^2,d^2)(t_1^4t_2^4)t_1t_2`$ (20)
where $`V`$ denotes the Vandermonde determinant. One can see from this example that the normal forms of  are simple enough to allow the complete calculation of all the fundamental covariants. It is also interesting to observe that under the specialization $`G_{abcd}`$ of , the covariants $`b_{uv}`$ come directly in Kasner’s normal form

$$k(u_1^2v_1^2+u_2^2v_2^2)+l(u_1^2v_2^2+u_2^2v_1^2)+4mu_1u_2v_1v_2$$
(21)
and that the three quadrilinear covariants occuring in degrees 3 and 5 are also in normal form. Indeed,

$`C_{1111}^1=`$ $`\frac{a_1+d_1}{2}x_1y_1z_1t_1+\frac{a_1d_1}{2}x_1y_1z_2t_2`$
$`+\frac{b_1+c_1}{2}x_1y_2z_1t_2+\frac{b_1c_1}{2}x_1y_2z_2t_1`$
$`+\frac{b_1c_1}{2}x_2y_1z_1t_2+\frac{b_1+c_1}{2}x_2y_1z_2t_1`$
$`+\frac{a_1d_1}{2}x_2y_2z_1t_1+\frac{a_1+d_1}{2}x_2y_2z_2t_2,`$
where

$`a_1`$ $`=`$ $`3a^3ad^2ab^2ac^2`$
$`b_1`$ $`=`$ $`bc^2ba^2bd^2+3b^3`$
$`c_1`$ $`=`$ $`b^2c+3c^3ca^2cd^2`$
$`d_1`$ $`=`$ $`a^2d+3d^3db^2dc^2,`$
and

$`C_{1111}^2=`$ $`\frac{a_2+d_2}{2}x_1y_1z_1t_1+\frac{a_2d_2}{2}x_1y_1z_2t_2`$
$`+\frac{b_2+c_2}{2}x_1y_2z_1t_2+\frac{b_2c_2}{2}x_1y_2z_2t_1`$
$`+\frac{b_2c_2}{2}x_2y_1z_1t_2+\frac{b_2+c_2}{2}x_2y_1z_2t_1`$
$`+\frac{a_2d_2}{2}x_2y_2z_1t_1+\frac{a_2+d_2}{2}x_2y_2z_2t_2,`$
where

$`a_2`$ $`=`$ $`2ab^2+2ac^2+2ad^2+6dbc`$
$`b_2`$ $`=`$ $`2ba^2+2bd^2+2bc^2+6cad`$
$`c_2`$ $`=`$ $`2b^2c+6bad+2ca^2+2cd^2`$
$`d_2`$ $`=`$ $`2a^2d+6abc+2db^2+2dc^2`$
and finally

$`E_{1111}=`$ $`\frac{a_3+d_3}{2}x_1y_1z_1t_1+\frac{a_3d_3}{2}x_1y_1z_2t_2`$
$`+\frac{b_3+c_3}{2}x_1y_2z_1t_2+\frac{b_3c_3}{2}x_1y_2z_2t_1`$
$`+\frac{b_3c_3}{2}x_2y_1z_1t_2+\frac{b_3+c_3}{2}x_2y_1z_2t_1`$
$`+\frac{a_3d_3}{2}x_2y_2z_1t_1+\frac{a_3+d_3}{2}x_2y_2z_2t_2,`$
where

$`a_3`$ $`=`$ $`8(a^3d^2c^2a^3b^2a^3+ac^2d^2+ab^2c^2+ab^2d^2)`$
$`b_3`$ $`=`$ $`8(b^3c^2+bc^2d^2+bc^2a^2b^3d^2+ba^2d^2b^3a^2)`$
$`c_3`$ $`=`$ $`8(ca^2d^2+a^2b^2c+cb^2d^2b^2c^3c^3d^2c^3a^2)`$
$`d_3`$ $`=`$ $`8(db^2c^2+a^2b^2d+a^2c^2da^2d^3c^2d^3b^2d^3)`$
On another hand, it seems that nothing is known about quadruple binary forms of multidegree $`(3,1,1,1)`$, and the first thing to be done now is probably to set up a convenient geometric representation of such forms.

## References