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# Conductance of metallic carbon nanotubes dipped into a metal

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## Abstract

We calculate the conductance variation of several metallic carbon nanotubes as their end is being dipped into a liquid metal electrode, where experiments have shown an achievable conductance close to $`2e^2/h`$. The calculated conductance for a (40,40) nanotube indicates that the current flows almost entirely through the $`\pi `$ mode, and not the $`\pi ^{}`$ mode. The calculation also predicts that for narrower nanotubes ($`1nm`$ in diameter), in a ’weak coupling’ regime, the saturation of both $`\pi `$ and $`\pi ^{}`$ modes should be observable. An experiment is proposed to verify this point.
Accepted for publication in Phys.Rev.B rapid communications

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A recent experiment  measured the conductance of carbon nanotubes  dipped into liquid metals, reporting long plateus of conductance close to $`2e^2/h=1G_0`$ (1 quantum of conductance) in a staircase shape. These plateus are due to the dipping of consecutive nanotubes into the liquid metal. Conduction is generally accepted to take place through the outermost wall in this case. In principle, two modes are available for this conduction to occur, namely the $`\pi `$ and $`\pi ^{}`$ modes, and a conductance of $`2G_0`$ might be available. The fact that only $`1G_0`$ was reported was puzzling. A subsequent calculation  for a (10,10) nanotube into a jellium, with a close jellium-carbon distance of $`d=0.7\AA `$, suggested that conduction might be taking place via the $`\pi ^{}`$ mode, the $`\pi `$ mode being totally reflected. However, neither the conductance dependence with dipped length, nor larger diameters or different carbon-metal separations were investigated in ref. . A later study by Anantram , performed in a flat geometry, argued that the conductance might be taking place via the $`\pi `$ mode instead. However, the conductances for each of the two modes were not shown separately there, and the geometry was different from that in ref. .

Here, for the first time, we address the problem of how the conductance varies with dipped length as the tube is inserted into the metal, and how it saturates to an asymptotic value. Our study is for nanotubes up to 5.5 nm in diameter i.e. (40,40) (the experiment used diameters $`5nm`$). We also consider the influence of the carbon-metal separation. Despite the (10,10) case basically yields the same result as ref.  for $`d=0.7\AA `$, our analysis shows that the narrow (10,10) nanotube with a short carbon-metal separation is not an adequate description of the experimental case. Rather, a conduction via the $`\pi `$ mode (and not the $`\pi ^{}`$) is obtained for the wider diameter tubes. The results are compatible with experimental conductance curves, and in disagreement with previous theoretical suggestion. Nevertheless, the symmetry of the scattered electrons’ wave functions in the metal region is a rapidly oscillating one in all cases, in full agreement with the result in ref. . An experimental verification will be proposed at the end of the paper.

In order to study the conductance dependence with dipped length, $`l`$, we use two different configurations that allow a better insight into the physical process. The ”semi-infinite tube configuration”, shown in fig.1a, corresponds to a semi-infinite tube that is perpendicularly dipped a distance $`l`$ into a semi-infinite metal. The ”infinite tube configuration”, fig.1b, corresponds to an infinite tube, traversing a slab of metal of width $`l`$. The slab is infinite in the $`x`$ and $`y`$ directions. The experimental situation is most similar to the semi-infinite configuration. However, the infinite configuration is useful because we can calculate not just the total conductance, but also how much current goes into the metal and how much travels through to the other side.

The metal electrons are regarded as free, with a Fermi energy of 7.13 eV corresponding to the free electron density of Hg. The free-electron versus Bloch-wave character of mercury has been discussed in ref. , and we will not enter that issue here. A cylindrical boundary to the free electrons is set at a separation $`d`$ from the nanotube’s carbon atoms (fig.1), and cylindrical coordinates are used to take full advantage of the symmetry. This allows consideration of a single nanotube inserted in the metal, and avoids spurious periodicities in the calculation. The electrons at the nanotube are treated in an atomic orbital basis, and the tunneling matrix elements (see ref.  for instance) from the carbon atoms to the electronic states in the metal are calculated for each case. The nanotubes are undoped, with the Fermi level determined by the charge neutrality condition for the isolated nanotube.

Results of conductance versus dipped length for two different nanotubes will be shown: a (40,40) corresponding to the diameter used in the experiments, and a narrower (10,10). The Green function technique allows us to treat the semi-infinite metal and the infinite and semi-infinite nanotubes straightforwardly. Using the Green functions, the conductances are also readily calculated . Calculation of the partial conductances for the $`\pi `$ and $`\pi ^{}`$ modes is straightforwardly performed, since the isolated nanotube’s Green functions for the two modes are completely independent (for non-capped nanotubes). A basis transformation is applied to the atomic ring of the nanotube located just near the metal surface on its outer side, yielding the Green function for the independent $`\pi `$ and $`\pi ^{}`$ modes of the non-submerged part of the nanotube, $`g_{\pi ,\pi }`$ and $`g_{\pi ^{},\pi ^{}}`$, with $`g_{\pi ,\pi ^{}}=0`$. The Green function elements for the other modes are purely real at the Fermi level and do not contribute to the current. This Green function is then coupled to the submerged part of the nanotube, and the conductance from the two independent electron sources ($`\pi `$ and $`\pi ^{}`$) into the metal can be calculated by eqs.11-13 of ref. . The measurable conductance is just the sum of the $`\pi `$ and $`\pi ^{}`$ conductances.

All magnitudes in the problem are well known quantities, except for $`d`$, defined as the distance between the carbon nanotube and the jellium edge (in ref. $`d`$ was chosen to be $`0.7\AA `$, which is the covalent radius of the carbon atom). Therefore we have performed calculations for different values of $`d`$. Comparison with experimental results might allow an estimation of the best suited value of $`d`$. Despite the physical meaning of $`d`$ is clear, it is difficult to establish a direct relation between its numerical value and an average C-Hg atom distance, if a full atomic description of the system were made instead of using a jellium. For the sake of comparison, if such non-jellium calculation would be made in the future, the imaginary part of the self energy at $`E_F`$ due to the metal, projected onto a carbon atom’s $`p`$ orbital perpendicular to it, is $`0.5eV`$ for $`d=1.5\AA `$.

First of all, let us study nanotubes in the diameter range used in the experiments, $`5nm`$. For a 5.5 nm diameter armchair nanotube, i.e.(40,40), and $`d=1.5\AA `$, we plot the conductance of the two modes as a function of the penetration length $`l`$, in fig.2-left. The $`\pi `$ mode conductance increases in an oscillatory fashion, saturating to near $`0.95G_0`$ when the nanotube is dipped deep enough into the metal. The amplitude of the superimposed oscillations vanishes with increasing dipped length. On the other hand, the conductance of the $`\pi ^{}`$ mode is smaller than $`0.1G_0`$ in the range from 0 to $`120\AA `$ dipped length. The calculated conductance for the smaller radius nanotube -(10,10)- is shown in the same figure (fig.2-right). Now, the $`\pi `$ and $`\pi ^{}`$ modes saturate to $`0.88`$ and $`0.95G_0`$ respectively, both close to $`1G_0`$, but the $`\pi ^{}`$ mode saturates noticeably slower than the $`\pi `$ mode.

In order to better understand these saturations, let us take a look at the conductance in the ’infinite’ configuration. This allows us to see a qualitative difference between the $`\pi `$ and the $`\pi ^{}`$ modes. The conductance of the modes are splitted into two components: conductance to the metal and conductance ’through’ the nanotube, to the other side, without leaking into the metal. The sum of the two conductances, $`\sigma _{total}`$ is also shown. The quantity $`1G_0\sigma _{total}`$ tells us the fraction of electrons that are reflected for that particular mode. Taking as an example the (10,10) nanotube, we first consider a very close metal-nanotube separation corresponding to $`d=1\AA `$ (fig.3a). The total $`\pi `$ conductance is small in this case ($`0.4G_0`$), implying that $`60\%`$ of the current from this mode is reflected (for $`d=0.7\AA `$ we obtain $`80\%`$ reflection). Furthermore, all the conductance corresponds to electrons leaking into the metal. On the other hand, the total conductance for the $`\pi ^{}`$ mode is practically $`1G_0`$, thus $`\pi ^{}`$ electrons are almost not reflected. However, they do not tunnel into the metal easily, and even for $`l=120\AA `$ still $`70\%`$ of the $`\pi ^{}`$ electrons tunnel through without leaking into the metal. This completely agrees with the results of . This kind of behavior is representative of a ’strong coupling regime’. A weak coupling regime is shown in fig.3b, where a larger nanotube metal separation ($`d=3.5\AA `$) has been considered. Now the total $`\pi `$ conductance is $`1G_0`$. As $`d`$ increases, a bigger fraction of the electrons tunnel into the metal instead of travelling through. The $`\pi ^{}`$ electrons, as before, do not tunnel into the metal so easily and need a longer $`l`$ than the $`\pi `$ electrons to leak out. Such a $`\pi ^{}`$ saturation length is of hundreds of $`\AA `$ for the (10,10) nanotube case, but is presumably longer than thousands of $`\AA `$ for the (40,40) and larger diameter nanotubes. From the infinite configuration results one concludes that, in a strong coupling regime, the $`\pi `$ mode gets completely reflected, but the $`\pi ^{}`$ mode still tunnels through with very little leakage into the metal; in a weak coupling regime, none of the modes is reflected, but they have very different leakage characteristic lengths, the $`\pi ^{}`$ mode being slower. In the case of large diameter nanotubes, this characteristic length is long enough not to be observable experimentally. The reason for the reflection of the $`\pi `$ mode in the strong coupling regime is related to the phenomenon of ”maximum saturation conductance” studied in a different context in ref. . This phenomenon states that, for a finite size contact, the conductance increases as we increase the contact strength from zero, up to a certain value, after which the conductance decreases if the contact strength is further increased. In our case this can be understood as follows: in the strong coupling regime, chemical interaction is taking place between the nanotube and the metal, such that the properties of the dipped carbon atoms are very different from those of the non-dipped atoms. Therefore, electrons trying to enter from the non-dipped nanotube part into this new system are mostly reflected. The inability of the $`\pi ^{}`$ mode to leak into the metal makes it more insensible to strong coupling than the $`\pi `$ mode. We stress the fact that bigger radius nanotubes have larger saturation lengths for the $`\pi ^{}`$ electrons, in all coupling regimes. By extrapolation of the results up to $`200\AA `$, we conclude that the saturation length of the $`\pi ^{}`$ mode at a (40,40) nanotube is, in all regimes, longer than thousands of $`\AA `$. The fact that the conductance curves experimentally reported in ref. saturate in lengths shorter than $`100nm`$ leads us to think that the mode observed in the experiments would be the $`\pi `$ mode, in a weak coupling regime ($`d>1.2\AA `$).

In the case of undoped nanotubes the $`\pi `$ and $`\pi ^{}`$ modes are degenerated at $`k_z=k_F^{nanot}`$. We did not systematically study the effect of doping the nanotubes on the conductance. Nevertheless, we verified that changing the Fermi level of the nanotube up or down makes the saturation length of the $`\pi `$ mode shorter or longer respectively, and has the opposite effect on the saturation length of the $`\pi ^{}`$ mode. A shift of $`0.2eV`$ changed the $`\pi `$ mode saturation length by about a factor of 2. However these shifts do not change any of the qualitative behaviors obtained, and the $`\pi `$ mode saturates considerably faster than the $`\pi ^{}`$ mode in all cases.

Aiming at a better understanding of the tunneling process into the metal, we have studied the contribution of different electronic modes of the metal to the conductance. In cylindrical coordinates the wavefunctions satisfying the boundary condition $`\psi _{rr_0+d^+}0`$ for an infinitely extended metal in the $`z`$ direction, are proportional to

$`\psi _{n,E,k_z}^{s(c)}(z,\theta ,r)e^{ik_zz}\mathrm{\Theta }_n^{s(c)}(\theta )R_{n,E,k_z}(r)`$ (1)
where

$`\mathrm{\Theta }_n^s=\mathrm{sin}(n\theta ),\mathrm{\Theta }_n^c=\mathrm{cos}(n\theta ),`$ (2)
$`k_z`$ is the wavevector in the axial direction (i.e. parallel to the tube), $`r_0`$ is the nanotube’s redius, and $`R_{n,E,k_z}(r)`$ is a function involving Bessel functions of the first and second kind. It is easy to show that the nanotube’s $`\pi `$ mode electrons can only couple to metal wavefunctions with two different kinds of angular dependence, $`\mathrm{\Theta }(\theta )`$: either $`\mathrm{\Theta }_n^c=0`$ or $`\mathrm{\Theta }_n^c=n_{chir}`$, for an $`(n_{chir},n_{chir})`$ nanotube. On the other hand, the $`\pi ^{}`$ mode electrons can only couple to metal wavefunctions of one type of angular dependence: $`\mathrm{\Theta }_n^s=n_{chir}`$. We checked that this is true by calculating the conductance to the metal when only wavefunctions of one particular angular dependence are kept, obtaining a null conductance in all but the three cases mentioned. If we now look at the available density of states very close to the edge of the metal at the Fermi level, for each particular angular dependence type, we find that it is much bigger in the case of $`\mathrm{\Theta }_{n=0}`$ than for $`\mathrm{\Theta }_{n=n_{chir}}`$ (see fig.4). In fact, in the limiting case of $`n_{chir}\mathrm{}`$, the d.o.s. for $`\mathrm{\Theta }_{n=n_{chir}}`$ is zero for energies smaller than $`9.4eV`$, corresponding to a free electron band shifted by $`\mathrm{}^2k_c^2/2m`$ with a wavevector component of $`k_c0.73a_0`$ in the circumpherencial direction. The fact that the nanotube radius is finite makes it possible for electrons with $`n=n_{chir}`$ to still be able to reach the nanotube. The larger the radius, the smaller the available d.o.s. of the $`n=n_{chir}`$ electrons at the Fermi level, in relation to the $`n=0`$ electrons’ d.o.s. This might induce one to think that electrons from the nanotube would mainly flow to $`n=0`$ electrons in the metal. However, this is not the case. When we artificially remove all metal states with $`n0`$, the resulting conductance is smaller than $`0.3G_0`$ in all cases, for any value of $`d`$. There is a geometrical reason for this, based on the fact that the coupling between the metal $`n=0`$ states at the Fermi level and the nanotube $`\pi `$ states almost cancels out when the dipped length is larger than three nanotube unit cells (still a fraction of the current is able to leak into the metal, despite this cancellation, due to the metal surface which breaks the translational symmetry). This cancellation takes place when summing terms in the axial direction, $`z`$, and is caused by the different periods of oscillation of the metal and nanotube states in the axial direction. Such a cancellation does not occur for tunneling into the $`n=n_{chir}`$ states of the metal. We explicitly checked that indeed the conductance is carried mostly by these states, and the contribution of the $`n=0`$ states is less than a $`10\%`$. This is consistent with the rapidly oscillatory character of the conducting states at the metal reported in reference . Nevertheless, tuneling to these states comes mostly from the nanotube’s $`\pi `$ electrons, rather than the $`\pi ^{}`$ electrons, for large radius nanotubes. The reason for an easier tunneling from the $`\pi `$ than from the $`\pi ^{}`$ mode into the metal $`n=n_{chir}`$ states seems to be the following. Most metal states with $`n=n_{chir}`$ have higher energy than the $`\pi `$ and $`\pi ^{}`$ states of the nanotube, at any value of the $`k_z`$ axial wavevector. Therefore, nanotube states are pushed down upon interaction with the $`n=n_{chir}`$ metal states. The $`\pi ^{}`$ band is quite uniformly pushed down at every $`k_z`$, because the energy of these states increases with $`k_z`$, same as the metal states, thus their energy difference is rather constant as a function of $`k_z`$. However, the $`\pi `$ band states decrease in energy with increasing $`k_z`$. This behaviour is the opposite of that of the metal states to which they can couple to. As a result, $`\pi `$ states with smaller $`k_z`$ interact more strongly with the metal states than those with larger $`k_z`$. This results in an effective flattening of the band at the submerged part of the nanotube, with the consequent enhancement of the density of states, thus enhancing the tunneling rate of these electrons. Obviously, if the interaction is too strong, the band is totally pushed below the Fermi level, and the $`\pi `$ electrons are reflected, as suggested in ref. . However, as we have seen, the dipping lengths required for the $`\pi ^{}`$ mode to reach a conductance of $`1G_0`$ in large radius nanotubes are far too long to agree with experimental evidence.

The reasonably short saturation distance of the $`\pi ^{}`$ mode of the (10,10) nanotube in the weak coupling regime implies that in this case one would be able to observe a conductance of $`2G_0`$, composed of a fast saturation to $`1G_0`$ superimposed to a slower saturation reaching $`2G_0`$ in several tens or hundreds of nm. We propose performing an experiment similar to that carried out in ref.  but with smaller diameter nanotubes around 1nm or less. This would enable one to determine whether a ”weak coupling” is actually the experimental case for these tubes. Reporting a fast saturation to $`1G_0`$ plus a slower saturation to $`2G_0`$ would mean that we are in the ”weak coupling” regime, the first saturation corresponding to the $`\pi `$ mode and the second one to the $`\pi ^{}`$. On the other hand, in case of a strong coupling regime, the expected conductance would be at most $`1G_0`$. We are aware that carrying out such an experiment with small diameter nanotubes might encounter many experimental difficulties, and is not a trivial task.

In summary, we have shown how the conductance varies as a nanotube is dipped into a free electron metal with a Fermi energy of 7.13eV. We identify two qualitatively different possibilities, solely depending on the nanotube-metal spacing: 1) weak coupling, in which conduction takes place via the $`\pi `$ mode, saturating to $`1G_0`$, while the $`\pi ^{}`$ mode saturates more slowly and is not detectable for nanotube diameters around $`5nm`$ or wider; 2) strong coupling, in which the $`\pi `$ mode is almost totally reflected, and the $`\pi ^{}`$ mode still does not leak to the metal in lengths much longer than 10nm. We conclude that the experimental situation most likely belongs to the weak coupling regime, and thus the reported $`1G_0`$ conductance is carried by the $`\pi `$ mode, and not the $`\pi ^{}`$ mode. The saturation length of the $`\pi ^{}`$ conductance gets shorter for nanotubes of smaller diameter. This would allow one to observe the consecutive saturation of the $`\pi `$ and $`\pi ^{}`$ modes in a range of tens of nanometers, if an experiment were performed using $`1nm`$ diameter nanotubes.

We are indebted to M.P. Anantram from NASA-Ames for fruitful discussions. We acknowledge Prof. J.P.Lu for his support of the joint research program between NASA Ames and University of North Carolina at Chapel Hill.


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# Duality transformations and temperature inversion symmetry

## 1 Duality transformations and temperature inversion <br>symmetry

In a recently published paper Fukushima and Ohta  discussed the relationship between the Casimir effect  and the Stefan-Boltzmmann $`T^4`$-law or Planck’s radiation law. In particular they discussed the explict conversion from the Casimir energy density to the $`T^4`$-law. The bottom line in Fukushima and Ohta’s paper is that there is a correspondence between the Casimir energy density at zero temperature and the Stefan-Boltzmann free energy density at $`T=T_{eff}`$, where $`T_{eff}`$ is an effective temperature that depends on the geometrical features of the experimental setup. Fukushima and Ohta correctly argued that the effective temperature cannot be regarded as a genuine temperature. This is so because the effective temperature does not satisfy the fundamental thermodynamical relation

$$\frac{s}{u}=\frac{1}{T},$$
(1)
where $`s`$ and $`u`$ are the entropy and energy density, respectively. In fact, there is not a true thermodynamics associated with the effective temperature. The effective temperature is introduced through duality transformations. The duality transformations in the context of Ref.  are obtained by writing the Casimir energy density and pressure as integrals that are formally similar to their thermodynamic counterparts. For the original Casimir’s setup these transformations read

$$2\mathrm{}\frac{1}{T};pu.$$
(2)
These transformations are supposed to be related to a dual symmetry exhibited by the Helmholtz free energy. This dual symmetry is called temperature inversion symmetry and the conditions for its existence in the Casimir effect were well established by Ravndal and Tollefsen . In the case of the Casimir effect for two perfectly conducting square parallel plates of side $`L`$ kept at a distance $`\mathrm{}`$ from each other with $`L\mathrm{}`$ , the temperature inversion symmetry can be expressed by

$$\left(2\pi \xi \right)^4F\left(\frac{1}{4\pi ^2\xi }\right)=F\left(\xi \right),$$
(3)
where $`F`$ is the free energy and $`\xi :=T\mathrm{}/\pi `$.

Suppose, however, that $`\xi `$ assumes extremely large values. Then starting from the free energy density at zero temperature, i.e.: the Casimir energy density, and making use of (3) it is possible to obtain the Stefan-Boltzmann $`T^4`$ law, where $`T`$ is a true temperature, that is, it is not dependent on the geometrical features of the system and obeys definition (1). There are, however, two physical ways of obtaining the Stefan-Boltzmann law. One is to take the very high temperature limit, $`T\mathrm{}`$, in which case the distance between the plates is kept constant and (3) yields

$$\frac{F\left(T\mathrm{}\right)}{\mathrm{}L^2}=\left(2T\mathrm{}\right)^4\frac{\pi ^2}{2^3\times 90\mathrm{}^4}=\frac{\pi ^2T^4}{45}.$$
(4)
The other way is to set the plates very far apart, that is, $`\mathrm{}\mathrm{}`$, while the temperature is kept constant. In this case from (3) again we obtain

$$\frac{F\left(T\right)}{\mathrm{}L^2}=\left(2T\mathrm{}\right)^4\frac{\pi ^2}{2^3\times 90\mathrm{}^4}=\frac{\pi ^2T^4}{45}.$$
(5)
Notice that in contrast with the first case, in the second case the Stefan-Boltzmann law is obtained for arbitrary temperature. If the duality transformations are supposed to be valid at any temperature, for arbitrary separation $`\mathrm{}`$, then as shown in Ref.  we can write the Casimir energy density as a Stefan-Boltzamnn energy density at an effective temperature. But this is in contradiction with the above remarks concerning the behavior of the free energy density under temperature inversion symmetry. For arbitrary $`T`$, only in the limit $`\mathrm{}\mathrm{}`$ does the free energy becomes proportional to $`T^4`$. The solution to this puzzle is to realize that temperature inversion symmetry and the transformations given by (2) are unrelated.

Nevertheless, the method of obtaining the Casimir energy and pressure employed by Fukushima and Ohta is interesting and valuable in itself and it is worthwhile to provide one more example of its usefulness. In the next section we will show how to obtain relations similar to (2) in the case of two parallel surfaces on which we impose Dirichlet boundary conditions on one surface and Neumann boundary conditions on the other. Since the boundary conditions are not symmetrical, this particular Casimir system does not exhibit temperature inversion symmetry , see, however,  for a way of circunventing this limitation.

## 2 Transformations for the repulsive Casimir force

In order to establish relations similar to (2) for the repulsive electromagnetic Casimir effect it is convenient to follow closely Ref. .

Consider a pair of parallel infinite plates one of which is perfectly conducting ($`ϵ\mathrm{}`$) and placed at $`z=0`$, while the other is infinitely permeable ($`\mu \mathrm{}`$) and placed at $`z=\mathrm{}`$. This setup was considered for the first time by Boyer  who showed in the framework of random electrodynamics that the distorted vacuum energy is positive and that results in a repulsive force per unit area between the plates. The simplicity of this geometrical setup allow us to simulate the electromagnetic problem by a scalar massless field. The boundary conditions then read: $`\varphi (t,x,y,z=0)`$ and $`_z\varphi (t,x,y,z=\mathrm{})=0`$. The eigenvalues labeling the normal modes of the field in the $`𝒪𝒵`$ direction are

$$k_z=\frac{\pi }{\mathrm{}}\left(n+\frac{1}{2}\right),$$
(6)
where $`nN1=\{0,1,2,\mathrm{}\}`$. The normal modes in the $`𝒪𝒳`$ and $`𝒪𝒴`$ directions are continous, i.e.: $`k_x,k_y`$. The unregularized vacuum energy is given by

$$E=\mathrm{}cL^2\frac{dk_xdk_y}{\left(2\pi \right)^2}\underset{nN1}{}K_n,$$
(7)
where

$$K_n=\sqrt{k_{}^2+\frac{\pi ^2}{\mathrm{}^2}\left(n+\frac{1}{2}\right)^2},$$
(8)
with $`k_{}:=\sqrt{k_x^2+k_y^2}`$. The discrete sum in (7) can be replaced by the integral representation

$$I(k_x,k_y)=\frac{dq}{2\pi }\underset{nN1}{}\frac{2q^2}{q^2+K_n^2},$$
(9)
as can be easily verified with the help of the residue theorem. The vacuum energy can be written

$$E=\mathrm{}cL^2\frac{dk_xdk_y}{\left(2\pi \right)^2}I(k_x,k_y).$$
(10)
Now we define $`z=\mathrm{}\sqrt{q^2+K_n^2}`$ and make use of

$$\frac{\mathrm{tanh}z}{z}=\underset{nN1}{}\frac{2}{z^2+\frac{\pi ^2}{\mathrm{}^2}\left(n+\frac{1}{2}\right)^2},$$
(11)
therefore and write

$`I(k_x,k_y)`$ $`=`$ $`{\displaystyle \frac{dq}{2\pi }\mathrm{}q^2\frac{\mathrm{tanh}\left(\mathrm{}\sqrt{q^2+k_{}^2}\right)}{\sqrt{q^2+k_{}^2}}}`$ (12)
$`=`$ $`{\displaystyle \frac{dq}{2\pi }\frac{\mathrm{}q^2}{\sqrt{q^2+k_{}^2}}}+{\displaystyle \frac{dq}{2\pi }\frac{2\mathrm{}q^2}{\sqrt{q^2+k_{}^2}\left(e^{2\mathrm{}\sqrt{q^2+k_{}^2}}+1\right)}}.`$
The first term and the second terms in (12) can be treated exactly as in  and after subtracting the continous part we end up with a Casimir energy density given by

$`u`$ $`=`$ $`{\displaystyle \frac{1}{\mathrm{}}}{\displaystyle \frac{d^3k}{\left(2\pi \right)^3}ln\left(1+e^{2\mathrm{}q}\right)}`$
$`=`$ $`{\displaystyle \frac{1}{2\mathrm{}\pi ^2}}{\displaystyle _0^{\mathrm{}}}𝑑qq^2\mathrm{ln}\left(1+e^{2\mathrm{}q}\right)`$
$`=`$ $`{\displaystyle \frac{7}{8}}{\displaystyle \frac{\pi ^2}{720\mathrm{}^4}},`$
The Casimir pressure is

$`p={\displaystyle \frac{\left(\mathrm{}u\right)}{\mathrm{}}}`$ $`=`$ $`2{\displaystyle \frac{d^3q}{\left(2\pi \right)^3}\frac{q}{e^{2\mathrm{}q}+1}}`$
$`=`$ $`{\displaystyle \frac{1}{\pi ^2}}{\displaystyle _0^{\mathrm{}}}𝑑q{\displaystyle \frac{q^3}{e^{2\mathrm{}q}+1}}`$
$`=`$ $`{\displaystyle \frac{7}{8}}{\displaystyle \frac{\pi ^2}{240\mathrm{}^4}},`$
where we have used the result

$$_0^{\mathrm{}}\frac{dxx^{\nu 1}}{e^{\mu x}+1}=\frac{1}{\mu ^\nu }\left(12^{1\nu }\right)\mathrm{\Gamma }\left(\nu \right)\zeta \left(\nu \right),$$

with $`\mathrm{}\mu >0`$ and $`\mathrm{}\nu >1`$. The relevant (for our purposes) thermodynamical functions now are the ones derived from the fermionic partition function for a neutrino gas in thermal equilibrium with a heat reservoir at temperature $`T`$ and chemical potential equal to zero

$$p=f=2T\frac{d^3q}{\left(2\pi \right)^3}\mathrm{ln}\left(1+e^{q/T}\right),$$
(15)
and

$$u=\frac{p/T}{\left(1/T\right)}=2\frac{d^3q}{\left(2\pi \right)^3}\frac{q}{e^{q/T}+1}.$$
(16)
Where $`f`$ is the free energy density and is the thermal energy density. Notice that apart from an all-important algebraic sign the ratio between the Casimir pressure for Boyer’s setup and the Casimir pressure for the conducting plates setup is the same as the ratio between the pressure for a massless neutrino gas and a photon gas, namely, $`7/8`$. It is easily seen that in this example the transformations similar to (2) are

$$2\mathrm{}\frac{1}{T},pup.$$
(17)
The transformations (17) above also lead to an effective temperature that depends on the geometrical features of this Casimir system and does not obey the fundamental relation given by (1).

## 3 Conclusions

In this brief paper we argued that a distinction between temperature inversion symmetry and the so-called duality transformations must be made. In particular we have shown in an example that it is possible to find transformations between spatial extension and temperature and between energy density and pressure in a system that does not exhibit temperature inversion symmetry. It seems that a deeper understanding of the temperature inversion symmetry depends on knowledge of the structure of the euclidean manifold and its symmetry group $`O(4)`$, even though as mentioned in  topological structures in euclidean space cannot always be construed as physical objects in minkowskian spacetime. It must be strongly emphasized also that the temperature inversion symmetry does more than connect the zero and the very high temperature limits. In particular, since (3) holds for arbitrary temperature, from a low temperature approximation to the Casimir effect at finite temperature we can write the high temperature one, and thus we can evaluate corrections to the Stefan-Boltzmann term that depend on the boundary conditions imposed on the electromagnetic field.


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# Model of the mixed state of type-II superconductors in high magnetic fields

## References


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# Testing Theories of Fermion Masses

## 1  Theoretical framework : top - down approach

We consider theories in four dimensions with a high energy desert up to a physical threshold $`M^{}`$ with $`M_{pl}M^{}M_G`$, the GUT scale. Above $`M^{}`$ we assume a fundamental theory (such as string theory) from which the effective low energy theory is derived with boundary conditions at $`M^{}`$. Below $`M^{}`$ we have two possibilities -

* $`M^{}M_G`$ and we have a SUSY GUT below. In this case, the relevant boundary conditions for low energy phenomenology are defined at $`M_G`$.
* Or we have the minimal SUSY spectrum below $`M^{}`$ with relevant boundary conditions there.

The latter possibility is the default when talking of string unification. I focus on the former possibility in the rest of this talk.

### 1.1 SUSY GUT with boundary conditions at $`M_G`$

In this case we have three types of boundary conditions specifying the parameters for gauge couplings, Yukawa couplings and soft SUSY breaking at $`M_G`$.

* Gauge couplings $`\alpha _i=\alpha _G\mathrm{for}i=1,\mathrm{},3`$.

This is a tree level relation in a GUT. A good fit to the low energy data already requires one loop threshold corrections; hence these corrections, predominantly from the GUT breaking and Higgs sectors of the theory, are observable and thus constrain GUTs.
* Yukawa couplings

Schematically we assume

$`Y=`$ $`\left(\begin{array}{ccc}0& ϵ^{}& 0\\ ϵ^{}& ϵ& ϵ\\ 0& ϵ& 1\end{array}\right)`$ (4)
where $`ϵ,ϵ^{}/ϵ`$ are small parameters. One generally (with or without GUTs) assumes some family symmetry; whether it is a permutation, U(1), or non-abelian SU(2), SU(3), or discrete non-abelian symmetry D(3). Family symmetries are needed for several reasons:

+ they reduce the number of fundamental parameters;
    + they can explain the hierarchy of fermion masses;
    + they can suppress flavor violation, such as $`\mu e\gamma `$;
    + they are necessary to suppress dimension 5 baryon number violating operators responsible for nucleon decay, i.e. they explain the small Yukawa-like couplings appearing in these dimension five operators. Or they can be used (in theories without GUTs) to forbid, with U(1) or baryon parity, dimension 5 baryon number violating operators all together;
    + and they can eliminate any other undesirable effects of Planck scale physics.

In general, there are three Yukawa matrices given by

$`Y_k=`$ $`\left(\begin{array}{ccc}0& D_kϵ^{}& 0\\ \widehat{D}_kϵ^{}& C_kϵ& B_kϵ\\ 0& \widehat{B}_kϵ& A_k\end{array}\right)`$ (8)
with ($`k=u,d,e`$). The parameters $`A,B,\widehat{B},C,D,\widehat{D}`$ are arbitrary, order one complex coefficients; fit to the data.
* SUSY breaking

For example, in the CMSSM we have $`m_0,M_{1/2},A_0,\mathrm{tan}\beta ,sign(\mu )`$. In other SUSY breaking scenaria (such as, GMSB, AMSB, $`\stackrel{~}{g}`$MSB, … ) we have a different set of SUSY breaking parameters. The main point is that simple mechanisms for SUSY breaking have a small number of arbitrary parameters; hence they can be predictive.

## 2  Precision Electroweak Data : including fermion masses and mixing angles

The precision electroweak data for testing theories beyond the standard model includes, in addition to the electroweak data used for testing the standard model, fermion masses and mixing angles.

* SM (CMSSM) Precision Data

$$\begin{array}{cc}M_Z=91.188(0.091)\hfill & M_W=80.419(0.080)\hfill \\ G_\mu 10^5=1.1664(0.0012)\hfill & \alpha _{EM}^1=137.04(0.14)\hfill \\ \alpha _s(M_Z)=0.1181(0.002)\hfill & \rho _{new}10^3=0.20(1.1)\hfill \\ B(bs\gamma )10^4=2.96(0.35)\hfill & \end{array}$$
* BSM Precision Data

$$\begin{array}{cc}M_t=174.3(5.1)\hfill & m_b(m_b)=4.20(0.20)\hfill \\ M_bM_c=3.4(0.2)\hfill & m_c(m_c)=1.25(0.10)\hfill \\ m_s(2\mathrm{G}\mathrm{e}\mathrm{V})=110(35)\hfill & m_d/m_s=0.050(0.010)\hfill \\ Q=22.7(0.8)\hfill & \\ M_\tau =1.777(0.0018)\hfill & M_\mu =0.10566(0.00011)\hfill \\ M_e10^3=0.5110(0.00051)\hfill & \\ |V_{us}|=0.2196(0.0023)\hfill & |V_{cb}|=0.0402(0.0019)\hfill \\ |V_{ub}/V_{cb}|=0.090(0.025)\hfill & \\ ϵ_K10^3=2.28(0.013)\hfill & \widehat{B}_K=0.85(0.15)\hfill \end{array}$$

I have included only a subset of the SM precision data. This is the subset we have used in our analysis . Instead of the complete set of standard model data we have added the thirteen observables associated with charged fermion masses and mixing angles. With regards to the BSM precision data, $`M(m)`$ refer to pole ($`\overline{MS}`$ running) masses. $`M_bM_c`$ has smaller theoretical uncertainties than $`m_c(m_c)`$. This is because one can use HQEFT to relate the difference to $`M_BM_D`$ with renormalon effects cancelling. Hence we have used the former rather than the latter. $`Q`$ is the Kaplan- Manohar- Leutwyler ellipse parameter defined by

$$\frac{m_u^2}{m_d^2}+\frac{1}{Q^2}\frac{m_s^2}{m_d^2}=1.$$

Note, this is the best known relation among the three light quark masses. The experimental results $`X_k^{exp}`$ ($`\sigma _k`$) are given above. These are for the most part taken from the PDG 2000. We have however used only the lower half of the PDG range for $`m_s`$; as suggested by recent lattice results. Finally, in those cases where the experimental uncertainty is less than 0.1% we assume a numerical error of 0.1% for $`\sigma _k`$. We then define a $`\chi ^2`$ function given by

$$\chi ^2=\underset{k=1}{\overset{N}{}}(X_k^{exp}X_k^{th})^2/\sigma _k^2.$$

### 2.1  Global $`\chi ^2`$ fits

We fit the data by minimizing the $`\chi ^2`$ function using the program Minuit. For the most part, the parameters we vary are defined at the GUT scale, except for $`\mu `$ and $`\mathrm{tan}\beta `$ defined at $`M_Z`$. We choose boundary conditions at $`M_G`$ given by

$``$ $`\alpha _1=\alpha _2\alpha _G`$, $`\alpha _3=\alpha _G(1+ϵ_3)`$ (where $`ϵ_3`$, parametrizing the one loop threshold corrections to gauge coupling unification, is a free parameter);

$``$ a model dependent parametrization of Yukawa couplings; and

$``$ soft SUSY breaking parameters which we take to be universal squark and slepton masses - $`m_{16}`$, universal gaugino masses - $`M_{1/2}`$, universal cubic scalar coupling - $`A_0`$, non-universal $`H_u,H_d`$ masses, $`\mu `$ and $`\mathrm{tan}\beta (M_Z)`$.

We use two loop renormalization group running from $`M_G`$ to $`M_Z`$ within the MSSM. We include one loop threshold corrections to fermion masses and electroweak observables at $`M_Z`$. Below $`M_Z`$ we use 3 loop QCD + 1 loop QED running. Electroweak symmetry breaking is obtained self-consistently using the one loop improved Higgs potential, including $`m_t^4`$ and $`m_b^4`$ corrections with an effective 2 Higgs doublet model defined below $`M_{stop}`$ . Finally the $`\chi ^2`$ function includes (for three families) 20 low energy observables.

Our analysis is in the same spirit as the global fits of the standard model (or MSSM) to precision electroweak data , although we use only a subset of the electroweak data. In the rest of this talk I focus on our recent analysis , including only the third generation quark and lepton masses.

## 3  SO(10) Yukawa unification for third generation and threshold corrections at $`M_Z`$

In the simplest version of $`SO_{10}`$ the Yukawa couplings for the third generation are all equal at $`M_G`$, i.e. $`\lambda _b=\lambda _t=\lambda _\tau =\lambda _{\nu _\tau }=\lambda `$. The low energy values of the top, bottom and $`\tau `$ couplings depend solely on the value of $`M_G`$, $`\alpha _G`$ and $`\lambda `$. The first two are already fixed by gauge coupling unification, hence we need only one low energy observable to fix $`\lambda `$. We use the ratio $`m_b/m_\tau `$. We then use $`m_\tau =\lambda _\tau \frac{v}{\sqrt{2}}cos\beta `$ to fix the value of $`\beta `$; $`v`$ is fixed by electroweak data. Finally we obtain one prediction for $`m_t=\lambda _t\frac{v}{\sqrt{2}}sin\beta 170\pm 20\mathrm{GeV}`$ .

### 3.1 Weak scale threshold corrections - large $`tan\beta `$

This beautiful result is however spoiled by potentially large weak scale threshold corrections proportional to $`\mathrm{tan}\beta `$ . By far the largest corrections come from SUSY mass insertions given by $`\delta m_b\delta m_b^{\stackrel{~}{g}}+\delta m_b^{\stackrel{~}{\chi }}`$ where $`\delta m_b^{\stackrel{~}{g}}\frac{\mu m_{\stackrel{~}{g}}tan\beta }{m_{\stackrel{~}{b}}^2}`$ and $`\delta m_b^{\stackrel{~}{\chi }}\frac{\mu A_ttan\beta }{m_{\stackrel{~}{t}}^2}`$. These corrections can be as large as $`50`$ %; however good fits require $`\delta m_b<2`$%.

Note that when $`\delta m_b^{\stackrel{~}{g}}>0`$ ($`\mu >0`$, in our convention), then $`\delta m_b^{\stackrel{~}{\chi }}<0`$. Recent data favors $`\mu >0`$. For example, the process $`bs\gamma `$ is obtained by similar graphs with a photon insertion. In this case the chargino term typically dominates and has opposite sign to the SM and charged Higgs contributions for $`\mu >0`$, thus reducing the branching ratio. This is a good thing, since the standard model plus charged Higgs contribution is typically larger than the experimental value. Thus $`\mu <0`$ is problematic. Also the sign of the SUSY contribution to the anomalous magnetic moment of the muon is correlated with the sign of $`\mu `$. Recent BNL results favor $`\mu >0`$ .

Pierce et al.  and Baer et al.  find Yukawa unification only when $`\delta m_b^{\stackrel{~}{g}}<0`$ and hence poor fits for $`bs\gamma `$. On the other hand we find good fits for $`\delta m_b^{\stackrel{~}{g}}>0`$ . What is going on?

In the past, we have neglected the small “wavefunction renormalisation” corrections to $`\delta m_b`$. These corrections, $`\delta m_b^{log}`$, are not proportional to $`\mathrm{tan}\beta `$ nor to $`A_t`$ or $`m_{\stackrel{~}{g}}`$. They are only logarithmically dependent on SUSY particle masses. They are however positive and about 6%. They thus have to be cancelled in order to find good fits to the bottom mass. Note, the corrections to the top and $`\tau `$ mass are small. In the present analysis  we include all one loop threshold corrections  to quark, charged lepton masses and electroweak observables.

We find Yukawa unification possible only in a narrow region of soft SUSY breaking parameter space.

In this region of parameter space with large $`\mathrm{tan}\beta `$ we need large $`m_{16},A_0`$ and smaller $`\mu ,M_{1/2}`$. A large negative value of $`A_0`$ serves two purposes:

* it enhances the chargino contribution and
* it induces large splitting between $`\stackrel{~}{t}_1\stackrel{~}{t}_2`$.

Both effects go towards enhancing $`\delta m_b^{\stackrel{~}{\chi }}`$ compared to $`\delta m_b^{\stackrel{~}{g}}+\delta m_b^{log}`$. In addition large values of $`m_{16}`$ enable the largest possible splitting of $`\stackrel{~}{t}_{1,\mathrm{\hspace{0.33em}2}}`$ while maintaining a positive stop mass squared.

This range of parameters is however consistent with electroweak symmetry breaking only if the $`H_u,H_d`$ masses are split. We have considered two possible ways of splitting the Higgs masses we refer to as $`D_X`$ term splitting and universal scalar masses.

$`D_X`$ splitting

In this case we have $`m_{(H_u,H_d)}^2=m_{10}^22D_X`$, $`m_{(Q,\overline{u},\overline{e})}^2=m_{16}^2+D_X`$ and $`m_{(\overline{d},L)}^2=m_{16}^23D_X`$. Unfortunately, since $`D_X>0`$ we find $`m_{\stackrel{~}{b}}^2<<m_{\stackrel{~}{t}}^2`$ which is bad.

Universal scalar masses

In the other case we have $`m_{(H_u,H_d)}^2=m_{10}^22\mathrm{\Delta }m_H^2`$, and $`m_{(Q,\overline{u},\overline{e})}^2=m_{(\overline{d},L)}^2=m_{16}^2`$. We now find $`m_{\stackrel{~}{t}}^2<<m_{\stackrel{~}{b}}^2`$ which is just what is needed, i.e. good.

In figure 1 we give contours of constant $`\chi ^2`$ as a function of $`\mu ,M_{1/2}`$ with $`m_{16}=1500`$ and $`2000`$ GeV. All other parameters have been varied in order to minimize $`\chi ^2`$. In figure 2 we show $`m_b(m_b)`$ and $`\delta m_b`$ contours as a function of $`\mu ,M_{1/2}`$ with $`m_{16}=2000`$ GeV. By comparing the two figures, it is clear that $`\chi ^2`$ is smallest when $`\delta m_b<2`$%. The best fits are obtained with $`A_01.9m_{16}`$ and $`m_{10}1.4m_{16}`$.

In a more complete theory including all three generations, we would be able to calculate the anomalous magnetic moment of the muon $`a_\mu ^{NEW}`$ and the proton lifetime. Here we show results obtained in a particular 3 family model (see Blazek, S.R. and Tobe ). We find $`a_\mu ^{NEW}`$ is less than the recent BNL measurement $`a_\mu ^{NEW}=43\pm 16\times 10^{10}`$ In fact $`a_\mu ^{NEW}`$ decreases with increasing $`m_{16}`$. With a minimum value of $`m_{16}1200`$ GeV, necessary for reasonable fits, we find $`a_\mu ^{NEW}16\times 10^{10}`$.

The proton lifetime, on the other hand, increases as $`m_{16}`$ increases. It can be consistent with the most recent Super K preliminary results , but only if we allow for the three quark matrix element $`\beta `$ between a proton state and the vacuum to be of order 0.5 $`\times \beta _{lattice}`$ .

## 4  Conclusion

In conclusion, theories beyond the standard model are strongly constrained by precision electroweak data, which now includes fermion masses and mixing angles. As an example, we have discussed SO(10) Yukawa unification. We find that good fits constrain the soft SUSY breaking parameters to a narrow region given by $`m_{16}1200`$ GeV, $`A_01.9m_{16}`$, and $`m_{10}1.4m_{16}`$. This then implies significant predictions for Higgs and SUSY particle masses. See the talk of R. Dermíšek in these proceedings for further details.

Figure 3: $`a_\mu ^{NEW}`$ and the proton lifetime plotted as a function of $`\mu ,M_{1/2}`$ for $`m_{16}=2000`$ GeV.


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# Kinetics of macroion coagulation induced by multivalent counterions

## I Introduction

Water solutions of strongly charged particles (macroions) with multivalent counterions with large charge $`Z`$ ($`Z`$-ions) are important in physics, chemistry, biology, chemical engineering and environmental science. Colloidal particles, charged membranes, double helix DNA, actin and other polyelectrolytes are examples of different macroions. Multivalent metallic ions, dendrimers, charged micelles, short DNA helices or other short PE can play the role of $`Z`$-ions.

We concentrate here on strongly asymmetric solutions in which size and charge of macroions are much larger than those of $`Z`$-ions. As the simplest example, we consider macroions as negatively charged rigid spheres with charge $`Q`$ and radius $`R`$ in solution with compact positive $`Z`$-ions with the size $`aR`$ and charge $`1ZQ`$. This can be a solution of positive latex particles with very short DNA helicesGrant ; Gotting  or hematite particles with polyacrylic acidBuffle .

In such solutions, each sphere adsorbs many $`Z`$-ions. They strongly repel each other at the surface of the sphere and form a strongly correlated two-dimensional liquid reminding Wigner crystal. When a new $`Z`$-ion approaches this liquid, it repels nearest $`Z`$-ions, creates a correlation hole or an oppositely charged image, which provides attraction of $`Z`$-ion to the surfacePerel99  in addition to what mean field theories predict. Therefore, when concentration of $`Z`$-ions, $`c`$, reaches some critical value $`c_0(s)`$, (which depends on concentration of macroions particles $`s`$) the net charge of each macroion, $`Q^{}`$, (which includes all adsorbed $`Z`$-ions) flips its signNguyen . On Fig. 1 the “neutrality” line $`c_0(s)`$ is shown in plane ($`s`$, $`c`$) together with two signs of $`Q^{}`$ which it separates.

Correlations between $`Z`$-ions on the sphere surface also lead to another interesting effect. The correlation energy per $`Z`$-ion is lower at higher $`Z`$-ion concentration. This means when two spheres touch each other, at the place of contact where the $`Z`$-ion concentration doubles, correlation energy is gainedRouzina . This energy gain leads to an attraction between spheres which is stronger than van der Waals forces and makes possible their coagulation. Coagulation is a key part of many industrial processes such as paper production, extraction of minerals, proteins and other macroions from solutions, or treatment of waste waters. On the other hand, there are many other cases where coagulation should be avoided. Delivery of short modified DNA molecules DNA adsorbed on the surface of positively charged latex particles is a good exampleGrant ; Gotting .

Because colloidal solutions are stable due to the Coulomb repulsion between particles, coagulation is usually achieved by a large concentration of monovalent salt, which screens out these charges. When the concentration of salt grows beyond the coagulation threshold nothing new happens and macroions stay coagulated. If, instead of monovalent salt, we deal with $`Z`$-ions (add Z:1 salt) then charge inversion changes this situation. Coagulation happens only in the range of concentrations, which is close to the neutrality line (shown by gray in Fig. 1), so that the Coulomb repulsion is so weak that the free energy is gained when spheres touch each other. Thus when, say, the concentration of $`Z`$-ions, $`c`$, grows at fixed $`s`$, coagulation happens at some critical concentration, $`c_c`$, while at a larger concentration, $`c_d`$, aggregates of spheres dissolve, because spheres acquire large positive net charge. In our previous paperNguyen , we derived expressions for $`c_c(s)`$ and $`c_d(s)`$. These curves are plotted on Fig. 1. Remarkably, phase diagrams of this type were discovered experimentally more than half a century ago for complexes of strongly oppositely charged proteinsdeJong . However, in Ref. deJong,  only the charge of large aggregates of macroions (coacervate droplets) was measured and the net charge of a single macroion was not discussed. No explanation was proposed for charge inversion of aggregates. In Ref. Nguyen,  we suggested an equilibrium theory of the phase diagram of Fig. 1 and showed that aggregates of spheres and isolated spheres change sign of their net charge at the same line $`c_0(s)`$.

In this paper we go beyond equilibrium statistical physics and study kinetics for different domains of the phase diagram. There are two main slow processes in the problem: charge inversion and coagulation. The first one is slow in the upper left area of the phase diagram when free macroions are strongly overcharged. In this case, the growth rate of the macroion positive charge is limited by a large repulsive Coulomb barrier for new $`Z`$-ions. Activation above this barrier is necessary for a $`Z`$-ion to come close enough to macroion in order to feel attraction to its image in the strongly correlated liquid (SCL) of already adsorbed $`Z`$-ions.

In the coagulation domain surrounding the neutrality line charges of macroions are relatively small so that charge inversion is a fast process. On the other hand, coagulation of macroions can be very slow and take hours. Suppose we mix latex spheres with $`Z`$-ions in such concentrations that the corresponding point is in the gray area of the phase diagram and watch how the mass of aggregates grows as a function of time. Although the net charge $`Q^{}`$ in the gray area is smaller than the bare charge $`Q`$, its absolute value can be much larger than $`Z`$ and the Coulomb barrier of repulsion of two macroions can be much larger than the barrier for charge inversion, which is created by the Coulomb interaction of a $`Z`$-ion with the macroion net charge $`Q^{}`$. Therefore, in this paper, we assume $`Z`$-ions are always in equilibrium and study the kinetics of macroion coagulation only.

We first concentrate on the short time kinetics in which doublets of macroions appear. We calculate the Coulomb barrier between two approaching macroions as a function of the distance from the neutrality line. We measure this distance by the variable

$$U=\frac{k_BT}{Ze}\mathrm{ln}\left[1+\frac{cc_0(s)}{c_0}\right],$$
(1)
where the critical concentration

$$c_0(s)=c_0+sN_i.$$
(2)
Here $`N_i`$ is the number of $`Z`$-ions needed to neutralize one sphere. The concentration $`c_0`$ is the concentration of free $`Z`$-ions which is in equilibrium with neutralized spheres. It is equal toPerel99  $`c_s\mathrm{exp}(\mu _{SCL}/k_BT)`$, where $`c_s`$ is the three dimensional concentration of the surface layer of the SCL of $`Z`$-ions and $`\mu _{SCL}`$ is the chemical potential of $`Z`$-ions in SCL. It is negative and $`|\mu _{SCL}|k_BT`$ so that $`c_0`$ is very small.

In Ref. Nguyen, , the net charge of the sphere was shown to be proportional to $`U`$ near the neutrality line:

$$Q^{}=CU,$$
(3)
where $`C`$ is the capacitance of the macroion coated by the ”metallic film” of SCL of $`Z`$-ions. For a sphere $`C=\epsilon R`$, where $`\epsilon `$ is dielectric constant of water. Because $`U`$ depends on the correlation chemical potential $`\mu _{SCL}`$ of $`Z`$-ions in the SCL, we call it the correlation voltage. From Eq. (1), one sees that if $`c>c_0(s)`$ spheres are overcharged (positive), while in the opposite case $`c>c_0(s)`$ they are undercharged (negative). Detail derivation of Eq. (3) can be found in Sec. II of Ref. Nguyen,  (See Eq. (26) of this reference).

Our main result is that the height of the Coulomb barrier between two spheres is

$$V_{max}=\alpha CU^2.$$
(4)
where $`\alpha `$ is a numerical factor of the order of unity (at week screening, $`\alpha =0.3`$, at very strong screening, $`\alpha =1`$). Thus the rate $`\nu `$ at which doublets appear has the form

$$\nu (U)=\nu _0\mathrm{exp}(\alpha CU^2/k_BT).$$
(5)
Exponential factor of Eq. (5) is, of course, the probability of activation above the Coulomb barrier between two macroions.

Eq. (4) suggests that the Coulomb barrier between aggregates increases as their size grows. This leads to the decreasing sticking probability between two aggregates as their size increases. This, in turn, leads to the slowing down of the growth of the aggregate size with time. We call this the “self-regulated” aggregation and show that in this case an aggregate size increases only as a logarithmic function of time

$$(t)_1\mathrm{ln}(t/t_1),$$
(6)
where the size and time constant $`_1`$ and $`t_1`$ will be given in Sec. III. To the best of our knowledge, this logarithmic behaviour is reported for the first time.

However, “self-regulated” aggregation cannot continue forever. When aggregates are so large that their time of activation above the Coulomb barrier is longer than the time for one macroion to desorb from an aggregate, one enters a Lifshitz-Slezov (LS) regime of coagulation where the aggregate size increases linearly with time with a very long time constant. In this regime, aggregates gains size by adsorbing free spheres which desorb from other aggregates.

Screening can diminish the Coulomb barrier substantially. At strong screening, the LS regime may never be reached. Instead the height of Coulomb barrier saturates when the aggregate size reaches the screening length $`r_s`$. In this case, the “self-regulated” aggregation is followed by the reaction limited aggregation where Coulomb barrier is constant for any aggregates with size greater than $`r_s`$ and the average aggregate size increases roughly quadratically in time.

There have been various experiments studying the kinetic of macroion coagulation induced by $`Z`$-ions, such as latex particles complexed with short DNA segmentsGrant  or hematite particles complexed with polyacrylic acidBuffle . In both experiments, the author observed an exponential increase in the rate of coagulation when the neutrality line is approached. At the same time, as the $`Z`$-ions concentration increases across this line, the electrophoretic mobility of the macroions changes sign suggesting a charge inversion effect. When $`Z`$-ions concentration are much larger or smaller than the neutrality composition, macroions are under- or overcharged and the Coulomb barrier exponentially diminishes their sticking probability. These results are in qualitative agreement with Eq. (5). However, instead of $`\mathrm{ln}[\nu (U)]U^2`$, the authors of Ref. Buffle,  observed a plateau in the aggregation rate around the neutrality point $`U=0`$. This may be due to the limited time resolution of the experiment at the initial fast stage of coagulation.

The paper is organized as following. In Secs. II and IV, we study the kinetic barrier for two approaching macroion with spherical shape and rod-like shape at a given $`Z`$-ion concentration. In section III, we discuss different stages of macroion coagulation, namely how the coagulation rate crossovers from a diffusion limited regime to the new “self-regulated” regime and finally to LS regime. In the conclusion, we summarize our results.

## II Coulomb potential barrier between two approaching spheres

Let us start by calculating the Coulomb barrier between two approaching spheres. Because the charge of each sphere is not fixed but self-adjusts (by releasing or absorbing $`Z`$-ions) according to their positions, one has to calculate self-consistently the Coulomb repulsion between spheres and their charges at a given separation. The capacitor charging picture of Eq. (3) offers a very convenient way of doing this. Indeed, the voltage $`U`$ depends only on the concentration of bulk $`Z`$-ions and the surface charge density of the spheres (through the chemical potential $`\mu _{SCL}`$) and, therefore, is constant for a given $`c`$ and sphere surface charge density $`\sigma `$. Because the SCL of $`Z`$-ions on the macroion surface behaves as a metal, one can view the system of spheres and their aggregates as a system of conductors under a constant charging potential $`U`$. Thus, one can calculate the net charge of not only spheres but also their aggregate of any size by using the appropriate capacitance $`C_{\mathrm{aggregate}}`$ instead of $`C`$. In the same way, the kinetic Coulomb potential barrier between any two aggregates can also be calculated.

Because, $`Z`$-ions are much more mobile than spheres, the process of charging up the spheres is much faster than coagulation and at any instance during the coagulation process, the $`Z`$-ions distribution is in equilibrium. With this assumption, one can write the Coulomb interaction energy between two spheres when they are at distance $`r`$ from each other as:

$$V(r)=\frac{C_{11}(r)+2C_{12}(r)+C_{22}(r)}{2}U^2\epsilon RU^2,$$
(7)
where $`C_{11}(r)`$, $`C_{22}(r)`$ and $`C_{12}(r)`$ are, respectively, the self capacitances of the spheres 1 and 2 and their mutual capacitance. The capacitance of an isolated sphere of is $`\epsilon R`$.

When dealing with a system under constant charging potential, the free energy $`F(r)`$ of the system must include the work of the source (in our case, the population of free $`Z`$-ions) to maintain this potential

$$F(r)=V(r)\underset{i,j=1}{\overset{2}{}}C_{ij}(r)U^2=V(r).$$
(8)
It is the lowering in the free energy compared to the reference system of two completely neutralized spheres with the rest of $`Z`$-ions free.

The capacitance $`C_{11}`$, $`C_{22}`$ and $`C_{12}`$ has been calculated for two spherical conductorsSmythe :

$$C_{11}(r)=C_{22}(r)=\epsilon R\mathrm{sinh}\beta \underset{n=1}{\overset{\mathrm{}}{}}\mathrm{sinh}^1[(2n1)\beta ],$$
(9)
$$C_{12}(r)=\epsilon R\mathrm{sinh}\beta \underset{n=1}{\overset{\mathrm{}}{}}\mathrm{sinh}^1(2n\beta ),$$
(10)
where $`\beta >0`$ satisfies $`\mathrm{cosh}\beta =r/2R`$.

Substituting Eqs. (9) and (10) into Eq. (7), one can easily find the cost in the free energy $`V(r)`$ in moving two spheres from infinity to the distance $`r`$. The result is plotted by the solid line in Fig. 2. For comparison, the potential barrier for the case when the spheres keep their charge $`q^{}=C(\mathrm{})U=\epsilon RU`$ fixed when approaching each others is also plotted. The maximum of the potential barrier is located very close to the distance $`r=2R`$ where two spheres touch each other and is equal to

$$V_{max}0.3\epsilon RU^2.$$
(11)
As one can see, at the maximum of the potential barrier, the self adjustment of the sphere charge reduces this barrier height by about 40% compared to the barrier of $`0.5\epsilon RU^2`$ one would get if the sphere charges were kept fixed upon approaching.

Due to this Coulomb barrier, the expression for the rate at which spheres come to each other to form doublets contains an exponential factor related to the probability of activation above this barrier as shown in Eq. (5).

In the above calculation, it is assumed the Coulomb potential is unscreened. In reality, there is always a finite concentration of monovalent salt in water solution, which leads to the screening of Coulomb interaction at distance larger than the Debye-Hückel screening length $`r_s`$. If $`r_s`$ is larger than the averaged distance between $`Z`$-ions at the surface of an aggregate, the correlation between $`Z`$-ions remains unscreened. Therefore, the concentration $`c_0`$, and correspondingly, the charging potential $`U`$ remain constant. Thus, in this regime, screening influences the process of coagulation only through the change in the capacitance of each sphere.

When the radius of the aggregate is smaller than the screening radius, $`R<r_s`$, the Coulomb interaction is not screened when the aggregates touch each other, therefore the above result remains valid. In the opposite case, when $`R>r_s`$, the capacitance of each isolated aggregate is that of a plane capacitor with thickness $`r_s`$ and area $`4\pi R^2`$, $`C_{1,2}(\mathrm{})=\epsilon R^2/r_s`$. Using this planar capacitor approximation, it is not difficult to estimate the change in the total capacitance of the system when the two aggregates touch each other. Indeed, simple geometric calculation gives the reduction in the area of the planar capacitor when the two spherical aggregates touch each other is $`4\pi Rr_s`$. Thus the change in the capacitance of the system is $`\mathrm{\Delta }C=C_{11}+2C_{12}+C_{22}C_1(\mathrm{})C_2(\mathrm{})=\epsilon R`$. Thus, in this case the maximum of the potential barrier is

$$V_{max}=\epsilon RU^2,(R>>r_s).$$
(12)
Comparing this results with Eq. (11), one sees that, beside a numerical factor, screening does not affect the height of the potential barrier between two approaching spheres as long as $`r_s`$ is larger than the average distance between $`Z`$-ions on the spheres.

## III Later stages of coagulation

In previous sections, we discussed the kinetic barrier when two macroions approach each other to form a doublet. This fast process happens at the initial stage of coagulation where the concentration of free macroions is large. Doublets coagulate with free macroions or other doublets to form bigger macroions aggregates. This section deals with later stages of coagulation.

The problem of coagulation is generally complicated and can be solved exactly only in special cases. However, the main physics can be captured if one works with the dominant aggregate size $`(t)`$ (with concentration $`N(t)`$) at a given time assuming this typical aggregates carry all the mass of the macroions.

Let us start from the initial stage of coagulation when the aggregate size are small, so that at small enough $`U`$ (close to the neutrality line) the Coulomb barrier between aggregates is smaller than $`k_BT`$. In this case, the Coulomb barrier of Eq. (11) has little effect and the probability of sticking for two aggregates is of the order of unity. This is the regime of the well-known diffusion limited aggregation. The concentration of the typical size aggregates decreases as inverse of timecolloid :

$$N(t)=\frac{s}{1+t/\tau _{\mathrm{diff}}}s\frac{\tau _{\mathrm{diff}}}{t}\mathrm{for}t\tau _{\mathrm{diff}},$$
(13)
where $`\tau _{\mathrm{diff}}\eta /k_BTs`$, $`s`$ is the initial concentration of free macroions and $`\eta `$ is the viscosity of water. Thus, the rate of coagulation in this early stage is relatively constant independent of $`U`$ and equal to the rate of coagulation at the neutrality line where the charging potential $`U`$ is exactly zero and there is no Coulomb barrier.

The regime of diffusion limited aggregation stops when the typical size of the macroion aggregates reaches such a size that the Coulomb barrier is larger than $`k_BT`$. Using Eq. (11), one sees that this regime is reached when the typical size equal

$$_1k_BT/\epsilon U^2.$$
(14)
Assuming an aggregate has a fractal dimension $`d_f`$ (in practical situation, $`d_f2`$) so that the number of spheres in it is $`(/R)^{d_f}`$, the time at which $`_1`$ is reached is

$$t_1=\tau _{\mathrm{diff}}(k_BT/\epsilon U^2R)^{d_f}.$$
(15)
When $`t>t_1`$, the Coulomb barrier $`V_{max}\epsilon U^2`$ has to be taken into account. In this regime, the dominant contribution to the rate of coagulation comes from the tunneling of aggregates through the Coulomb barrier. The change in the concentration of typical aggregates obeys the equationcolloid :

$$\frac{dN(t)}{dt}=\kappa D^2N^2\mathrm{exp}(V_{max}/k_BT)$$
(16)
where the numerical factor has been dropped on the right hand side and the factor $`\kappa `$ satisfies $`\kappa ^2=(d^2V(r)/dr^2)_{max}/2k_BT`$. Since the typical width of the Coulomb barrier is $``$, $`\kappa \sqrt{V_{max}/^2k_BT}`$. Using the Stoke formula, $`Dk_BT/\eta `$, one can solve Eq. (16) assuming that the typical size aggregates consume all the mass of the macroions:

$$=_1(N_1/N)^{1/d_f},$$
(17)
where $`N_1=N(t_1)`$. The concentration of typical size aggregates in this regime decreases logarithmically with time:

$$N(t)N_1\left[\mathrm{ln}\left(\frac{tt_1}{t_1d_f}+e\right)\right]^{d_f}$$
(18)
where $`N_1=N(t_1)`$. Eq. (6) for the size of the typical aggregates can be obtained easily using the relationship (17).

As of our knowledge, this slow logarithmic kinetics was never reported in literature. It is the result of the increase in Coulomb barrier when aggregate size grows. This diminishes their sticking probability, which in turn slows down the kinetics from the linear size increase to a logarithmic one. We thus call this regime “self-regulated” aggregation.

In the regimes we considered so far, the increase in the aggregate mass is caused by a collision between two aggregates of size $`(t)`$. When the typical aggregate size becomes very large, the Coulomb barrier between two approaching aggregates becomes so high that the corresponding coagulation rate (which is proportional to $`\mathrm{exp}(V_{max}/k_BT)`$) becomes very small, a different and faster aggregate growth mechanism, namely the Lifshitz-Slezov (LS) one, comes into play. In this mechanism, the large aggregates do not collide into each other and the primary mechanism for aggregate growth is no longer due to real space diffusion. Instead, the change in their size is provided by the releasing and adsorbing of spheres which have much smaller kinetic barriers. This mechanism provides a faster coagulation process because the binding energy of a sphere in a very large aggregate and the Coulomb barrier between a very large aggregate and a sphere are finite and do not depend on the aggregate size. One can think of LS mechanism as a diffusion in size spaceLS . Interestingly, the concentration of typical size aggregates in this mechanism also decreases as inverse of time

$$N(t)\tau _{\mathrm{LS}}/t,$$
(19)
where the time constant $`\tau _{\mathrm{LS}}`$ is much longer than $`\tau _{\mathrm{diff}}`$ because it is proportional to the concentration of free macroions in solution

$$\tau _{\mathrm{LS}}\mathrm{exp}(E/k_BT)$$
(20)
Here $`E`$ is the binding energy of a sphere in an aggregate which does not depend on the aggregate size.

One can easily find the size of the typical aggregate at which LS mechanism is important by comparing the detaching time $`\tau _{LS}`$ of a small macroion from the aggregates with the activation time for two aggregates to go through the Coulomb barrier which is of the order $`\mathrm{exp}(\epsilon U^2/k_BT)`$. This gives

$$\epsilon U^2=E.$$
(21)
Thus the typical size at which LS regime starts is:

$$_2=E/\epsilon U^2.$$
(22)
A phase diagram of different regimes of coagulation is shown in Fig. 3. With increasing time, $``$ grows along a vertical line starting from $`=R`$. Below the dotted line which represents $`_1(U)`$, the coagulation is diffusion limited and the aggregate mass increases with time linearly as $`t/\tau _{\mathrm{diff}}`$. Above the solid line which represents $`_2`$, the coagulation process is of LS nature and the aggregate mass also increases linearly with time $`t/\tau _{\mathrm{LS}}`$. In between these two lines is regime of “self-regulated” aggregation. In this regime, the aggregate size increases logarithmically.

Above, we dealt with the unscreened Coulomb potential between two aggregates. This is valid if the screening length of the solution is very large ($`r_s>_2`$). For smaller screening length, when the typical aggregate size reaches $`r_s`$, due to the fractal nature of aggregates, the Coulomb barrier stops increasingfootnote . In this case, LS regime cannot be reached. One goes from the “self regulated” regime to the regime of reaction limited aggregation with constant Coulomb barrier and almost zero probability of macroion detaching from the aggregates. One can calculate the change in the concentration $`N`$ in this regime using the Eq. (16).

Denote by $`t_s`$ the time at which the typical aggregate size reaches $`r_s`$ (from Eq. (6), $`t_st_1\mathrm{exp}(\epsilon r_sU^2/k_BT)`$). At $`t>t_s`$, the exponential factor in Eq. (16) becomes constant, $`\mathrm{exp}(\epsilon r_sU^2/kBT)`$, and so does the factor $`\kappa `$. The solution of this equation shows a fast decrease in the concentration of typical aggregates with time:

$$N(t)=N(t_s)\left[1+\frac{tt_s}{\tau _{\mathrm{react}}}\frac{d_f1}{d_f}\right]^{d_f/(1d_f)},$$
(23)
where $`\tau _{\mathrm{react}}`$ is an exponentially long time constant:

$$\tau _{\mathrm{react}}=\frac{\eta }{k_BTN(t_s)}\frac{\mathrm{exp}(\epsilon r_sU^2/k_BT)}{\sqrt{\epsilon r_sU^2/k_BT}}.$$

In a typical situation, $`d_f2`$, the number of spheres in the typical aggregates (which is inversely proportional to $`N`$) increases as $`t^2`$. Although this is a very fast kinetic, it is still slower than an exponential growth of the cluster size suggested recentlyRLA ; Witten . We currently do not have a clear understanding of the origin of this theoretical result.

At even smaller screening length, $`r_s<_1`$, the Coulomb barrier between two aggregates never becomes larger than $`k_BT`$ and one always stays in the regime of diffusion limited aggregation.

The evolution of the typical aggregate size as a function of time is plotted in Fig. 4 for $`r_s<_2`$.

## IV Aggregations of rod-like polymers

In this section, we would like to discuss the kinetic barrier for the coagulation process when the role of macroion is played by a rigid polyelectrolyte (PE), such as DNA. We assume the length of PE molecules is smaller than its persistence length so that each can be considered as rigid rod. Due to the anisotropy of this problem, there is a number of different paths of aggregation of rods.

The authors of Ref. Liu,  studied the kinetic barrier between two approaching rods as a function of their orientation when the rods approach each other in the direction perpendicular to their bodies (Fig. 5a). We believe the kinetic barrier associated with this way of approaching is too large because of their large electrostatic repulsion when placed side by side, especially when the screening of solution is week. In this section, we propose another path of approaching of two rigid rods which has a lower kinetic barrier. Namely, the two rods approach in such a way that their centers of mass lie on a line parallel to their longer axes (See Fig. 5b). One can easily see that, in this way, charges of the rods are kept further from each other than in Fig. 5a. Thus for the paths of Fig. 5b, the kinetic barrier between the rods is lower.

We can calculate the Coulomb barrier between two approaching rods as in Sec. II, starting from the idea that both rods are under constant charging voltage $`U`$. The capacitance of a metallic rods of length $`L`$ and radius $`a`$ is $`C=\epsilon L/2\mathrm{ln}(L/a)`$ for a weakly screening solution ($`r_s>>L`$) and is $`C=\epsilon L/2\mathrm{ln}(r_s/a)`$ for stronger screening ($`L>>r_s>>a`$). Thus the change in the capacitance of the system when the two rods ends start touching other is $`\mathrm{\Delta }C\epsilon L/\mathrm{ln}^2(L/a)`$ for the weak screening case, and is $`\mathrm{\Delta }C\epsilon r_s/\mathrm{ln}^2(r_s/a)`$ for stronger screening.

As the rods start to overlap, the short range attraction between the rods starts to come into play, which partially compensate the increases in Coulomb repulsion and reduced the kinetic barrier. If the length of the overlap segment is $`x`$ and if the attraction energy is $`ϵ`$ per unit length, the free energy of the system can be written as $`\mathrm{\Delta }C(x)U^2xϵ`$, which is $`x(\epsilon LU^2/\mathrm{ln}(L/a)ϵ)`$ for the weak screening case and is $`x(\epsilon LU^2/\mathrm{ln}(r_s/a)ϵ)`$ for the strong screening case. Because, in the final stage when the two rods lie parallel to each other, the attraction energy is assumed to win over their Coulomb repulsion, $`ϵ>\epsilon LU^2/\mathrm{ln}(r_s/a)`$, one easily sees that when the rods start to overlap, total energy start to decrease. Thus the maximum of the potential barrier is at about the distance at which the rods start to overlap.

$$V_{max}\{\begin{array}{cc}\epsilon LU^2/\mathrm{ln}^2(L/a)\hfill & \mathrm{for}r_s>L\hfill \\ \epsilon r_sU^2/\mathrm{ln}^2(r_s/a)\hfill & \mathrm{for}r_s<L.\hfill \end{array}$$
(24)
Obviously, this potential barrier is much smaller than that in the case the rods approach each other in the direction perpendicular to their length. In the latter case, the maximum of the potential barrier is at the distant where they touch each other side by side and is equal to $`\epsilon LU^2/\mathrm{ln}(L/a)`$ for $`r_s>L`$, and $`\epsilon LU^2/\mathrm{ln}(r_s/a)`$ for $`r_s<L`$.

At later stages of aggregation, collinear approaches should dominate as well. This can explain why in many real and numerical experiments, very elongated structures are seen.

## V Conclusion

In this paper, we provide a general framework for calculation of the Coulomb potential between two macroions in solution of multivalent counterions and study various stages in the coagulation of macroions. The capacitance interpretation of Eq. (3) proves to be very useful in calculating the net charge of any macroions and aggregates of any shape. It also helps to easily calculate the Coulomb barrier between two approaching macroions. Using this equation, we are able to calculate and compare different paths of coagulation for rod-like macroions.

We discuss several stages of coagulation in time. In low salt, the coagulation process goes from a diffusion limited regime to a “self-regulated” regime and finally to the regime Lifshitz-Slezov kinetic. In the “self-regulated” regime, as the aggregate size increases, their Coulomb barrier increases diminishing their sticking probability and slowing down the kinetic. As a result, the aggregate size increases as a slow logarithmic function of time instead of the standard linear relationship. At higher salt concentration, Coulomb barrier is screened and stop increasing after the aggregates reach a certain size (of the order of the screening length $`r_s`$). In this case, Lifshitz-Slezov regime cannot be reached. Instead, one reaches a reaction limited regime where the Coulomb barrier is constant and the aggregate size increases quadratically in time. At very high salt concentration, one even cannot reach the reaction limited aggregation regime and always stays in the regime of diffusion limited aggregations.

###### Acknowledgements.

The authors are grateful to A. Yu. Grosberg and S. Stoll for useful discussions. This work is supported by NSF No. DMR-9985785.


text:
# Coronal loop hydrodynamics

## 1 Introduction

Solar flares are very complex phenomena. They emit in a wide range of wavelengths, including radio, optical, UV and X-rays. They involve many physical effects such as, for instance, chromospheric evaporation, magnetic field reconnection and material ejection.

There have been many examples of hydrodynamic models of flaring plasma confined in solar coronal loops: for a list of such models and some recent developments see Peres (2000). In this context Peres et al. (1987) modeled the X-ray emission of the well-studied solar flare, which occurred on November 12 1980 at 17:00UT. In particular, they used the Palermo-Harvard hydrodynamic loop model (Peres et al. (1982), thereafter PH), to give an interpretation of the phenomena involved in this event. The modeled light curves were successfully compared with those observed in some X-ray lines with the XRP on board SMM in a raster region covering the flaring coronal loop.

The numerical resolution in the transition region (TR), however, was not sufficient for a proper comparison with the EUV observations. Most EUV lines, in fact, are formed at temperatures below $`10^6\mathrm{K}`$. Using the new version of the PH code (Betta et al. (1997)), having appropriate spatial resolution, here we revisit the modeling of this well-studied flare. In section 2 we describe the hydrodynamic loop model; in section 3 we introduce our new simulations; in section 4 we compare the PH code numerical calculations with the observed line light curves; in section 5 we summarize our conclusions.

## 2 The flaring loop model

The PH code (Peres et al. (1982)) solves the one-fluid time-dependent differential equations of mass, momentum and energy conservation for the plasma confined in a solar magnetic loop, using a finite-difference numerical scheme. The model is one-dimensional, since the plasma is confined inside a semicircular flux tube where bulk motion and heat flow occur only along the magnetic field lines. The present version of the PH code (Betta et al. (1997)) can solve an asymmetric loop (e.g. Reale et al. (2000)), however MacNeice et al. (1985) inferred that the flare X-ray emission of the Nov 12 1980 flare was symmetric respect to the apex, and therefore we limit to model half a loop. We also assume ionization and thermal equilibrium between ions and electrons and that the flux tube keeps its geometric shape. The equations are solved with proper accuracy along the loop and during the entire flare evolution, since a regridding algorithm adapts the spatial grid whenever and wherever needed. The adaptive grid allows to reach very high spatial resolutions (as small as $`1\mathrm{m}`$) using a variable number of grid points ($`300600`$).

We consider the same loop parameters used in Peres et al. (1987), which were inferred from an accurate analysis of the H$`\alpha `$ and X-ray images.

The flare event is simulated by switching on a very strong impulsive heating $`𝒬`$. We use the formulation

$$𝒬(s,t)=H_s+H_0f(t)h(s)$$

where $`s`$ is the coordinate parallel to the magnetic field lines, $`t`$ is time, $`H_s`$, uniform and constant, balances ordinary coronal losses, while the second term in the right handside represents the impulsive heating. This term may be due to current dissipation. Its spatial and temporal dependencies are separated into two factors. In general we allow for various functional forms for $`f(t)`$ and $`h(s)`$. Here we assume that the spatial term $`h(s)`$ has a Gaussian form of half-width $`\sigma `$ and center $`s_0`$; $`f(t)`$ is a constant function for the first 180s and then decays exponentially with an e-folding time of 60s.

We repeat the following simulations:

* heating applied at the top of the loop;
* heating applied in a small region near the foot-points.

We compute the line emission from the temperature and density of the plasma along the loop obtained with the PH code, using the software ASAP written by Maggio et al. (1994) in IDL.

## 3 Numerical results

The hydrodynamics of the coronal plasma subject to a strong flaring heating has already been described extensively in previous papers in the literature. Here we dwell on the most important details.

The evolution of the temperature and the density at the top of the loop are shown in Fig. 1. In the first minute of evolution, the coronal temperature increases from roughly 3 to 21 $`\mathrm{MK}`$, for the model in which the energy is applied at the loop top (simulation A), and to around $`15\mathrm{MK}`$ for the model in which the energy is applied at the base of the TR (simulation B). During the early flare we find the largest differences between the two models.

In both simulations A and B, the coronal density increases while the impulsive heating is on. After 200s of the simulations, the hydrogen density at the top of the loop is of the order of $`10^{17}\mathrm{m}^3`$. In the pre-flare conditions the plasma hydrogen density at the top of the loop was instead $`\mathrm{7\; 10}^{15}\mathrm{m}^3`$.

As the coronal temperature increases, the conductive front propagates through the TR (the latter at the same time becomes steeper and steeper), and the chromospheric plasma warms up and, after $`15`$s, expands rapidly toward the corona (”chromospheric evaporation”).

In simulation A, velocities at temperatures above $`10^6\mathrm{K}`$ are always toward the loop top after the first 24s and until the impulsive heating is active, i.e until 360s. In $`30`$s since the beginning of this simulation, the plasma velocity is $`300\mathrm{k}\mathrm{m}\mathrm{s}^1`$ in the corona. On the other hand, when the heating is applied at the base of the loop (simulation B), the plasma is pushed up since the very beginning and reaches velocities $`400\mathrm{k}\mathrm{m}\mathrm{s}^1`$ after 20s.

In both simulations a descendant flow of material occurs in the chromosphere, below the region being ablated and evaporated; there the plasma pressure is much lower than the pressure of the plasma evaporated in the corona and the material is shocked and compressed toward the bottom; velocities have much lower values than coronal ones. This process is generally called ”chromospheric condensation” (Fisher (1987)).

As the plasma starts to evaporate, in both simulations the plasma temperature progressively increases along the whole loop; the emission measure at any temperature increases (as well as the EUV flux). The TR moves along the loop toward the foot-points during the whole heating phase. After 240s, when the impulsive heating has decreased to around 1/3 of its maximum value, the corona starts to cool and the TR moves gradually back to its initial position.

The simulations have been run to describe the plasma evolution for many minutes after the end of the heating. The loop cools and the coronal density decreases until a thermal instability (Field (1965)) occurs: then the whole loop cools very rapidly and reaches typical chromospheric values ($`10^4\mathrm{K}`$). As a uniform and constant heating term ($`H_s`$) is present in the equations, the whole loop returns approximately to its stationary pre-flare equilibrium after $`3000`$s. The entire cycle - until the whole coronal atmosphere returns exactly to the hydrostatic pre-flare conditions and the velocities decrease to negligible values - takes a few hours.

## 4 Light curves

This flare has been described by MacNeice et al. (1985) and Cheng & Pallavicini (1988) (CP88, thereafter). We now summarize the most important features for a better comprehension of what is discussed in the following.

It started at 17:00 UT and lasted less than 20 minutes. Four of the five instruments on board SMM registered the event: the Hard X-ray Burst Spectrometer (HXRBS), the Hard X-ray Imaging Spectrometer (HXIS), the X-ray Polychromator (XRP) and the Ultra-Violet Spectrometer and Polarimeter (UVSP). We concentrate on the observations made with the XRP (Acton et al. (1980)) and with the UVSP (Woodgate et al. (1980)). In Peres et al. (1987) the light curves from the whole raster in the X-ray lines observed with the XRP were compared with the results of the previous version of the PH code. An extensive analysis and interpretation of the hot component of this flare as well as of the spatial heating distribution and evolution was also included in that paper. During this flare the FCS instrument of the XRP registered spectroheliograms in six different resonance lines of some H-like ions or He-like: O viii 18.97 Å ($`T\mathrm{3\; 10}^6\mathrm{K}`$); Ne ix 13.45 Å ($`T\mathrm{4\; 10}^6\mathrm{K}`$); Mg xi 9.17 Å ($`T\mathrm{6.5\; 10}^6\mathrm{K}`$); Si xiii 6.65 Å ($`T10^7\mathrm{K}`$); S xv 5.04 Å ($`T\mathrm{1.55\; 10}^7\mathrm{K}`$); Fe xxv 1.85 Å ($`T\mathrm{7\; 10}^7\mathrm{K}`$). These lines covered most of the coronal temperature range.

There are no qualitative differences between the light curves synthesized with the new and the previous version of the PH code, except the disappearance of the numerical noise which affected the results at the lowest coronal temperatures. Therefore we confirm that the previous simulations carried out by Peres et al. (1987) are adequate to model the X-ray line light curves.

Here we focus most of our attention on the UVSP data. This spectrometer had spectral resolution 1150-3600 Å and spatial resolution better than $`2\mathrm{a}\mathrm{r}\mathrm{c}\mathrm{s}\mathrm{e}\mathrm{c}`$. The raster range was $`256\times 256\mathrm{a}\mathrm{r}\mathrm{c}\mathrm{s}\mathrm{e}\mathrm{c}^2`$. The UVSP collected images of this event with a field of view of $`120\times 120\mathrm{a}\mathrm{r}\mathrm{c}\mathrm{s}\mathrm{e}\mathrm{c}^2`$ and pixels of $`10\times 10\mathrm{a}\mathrm{r}\mathrm{c}\mathrm{s}\mathrm{e}\mathrm{c}^2`$ (i.e. $`7250\times 7250\mathrm{k}\mathrm{m}^2`$ on the Sun). Observations continued until the emitted flux increased considerably; since that moment ($``$17:00:06 UT), rasters (a complete raster lasted $`15`$s) were alternated to spectral scans in two different lines, which lasted 30s, with spectral resolution 0.3Å. These two lines, simultaneously recorded in two separate detectors, are

* Fe xxi 1354.1 Å line, formed at typical flaring plasma temperatures ($`T10^7\mathrm{K}`$);
* O v 1371.3 Å line, formed at TR temperatures ($`T\mathrm{2.2\; 10}^5\mathrm{K}`$).

Both lines are partially blended with nearby lines (Feldman et al. (1977)). The Fe xxi 1354.1 Å line partially blends with the chromospheric C i 1355.844 Å line; anyway this C i line is very narrow ($`0.12`$ Å), and, moreover, Cheng et al. (1979) showed that, during the flare maximum and decay phase, the intensity of the C i 1355.844 Å line was $`20`$% of the Fe xxi 1354.1 Å line. The O v 1371.3 Å line instead appeared blended with a very narrow line at 1371.37 Å (not yet identified) during many flares observed by Skylab, which was not present in the quiescent phase (Feldman et al. (1977)).

The UVSP observed the rising phase in both lines. The flux in the O v 1371.3 Å line, already high in the pre-flare phase, peaked at 17:02, i.e. at the same time as the peak observed in the hard X-rays. Then the emission in this line gradually decreased while the emission in the Fe xxi 1354.1 Å line was still increasing (CP88). The light curve in the O v 1371.3 Å line was different from the other ones observed simultaneously, because it peaked twice in the pre-flare phase (at 16:58UT and at 16:59UT) and, moreover, the flux was higher where a filament was observed in the H$`\alpha `$ images. MacNeice et al. (1985) wrote that material expulsions appeared in this filament, at the velocity of $`60\mathrm{k}\mathrm{m}\mathrm{s}^1`$ before the rising phase of the flare. This filament disappeared after a short time and its disruption might be correlated to the increased emission in the O v 1371.3 Å line.

The light curves in the EUV lines recorded during this flare have been published in CP88. Cheng and Pallavicini distinguished three different zones in the flaring region, named as kernels F1, F2 and L1. The two kernels F1 and F2 covered the two foot-points of the loop while kernel L1 corresponded to the region between them, covering the top of the loop. The light curves in both lines were analyzed separately for each kernel as well as for the whole raster containing the entire flaring region, and are shown in Figs. 2-5.

From the model results we calculate the flux in a particular line at a distance $`R`$ from the Sun as

$$F=\frac{2A}{4\pi R^2}_{s_1}^{s_2}nn_eG(T)𝑑s,$$
(1)
where $`R`$ is set equal to 1AU in our calculations, $`A`$ is the loop cross-section (assumed constant), $`G(T)`$ is the emission function tabulated by several authors for most observed lines, $`n`$ is the hydrogen number density, $`n_e`$ the electron number density and $`s_1`$ and $`s_2`$ are the extreme loop points considered in the spatial integration; we multiply the flux times 2 because the loop is supposed to be symmetric and therefore the integral is evaluated on half a loop length.

As a first step the integral  is calculated only in the loop volume corresponding to region L1 (two pixels). From Fig. 10 in CP88 we can guess that the loop was along the diagonal of kernel L1; assuming a semicircular geometry for the flaring coronal loop, and considering projection effects, the flux  is evaluated from $`s_1=11\mathrm{Mm}`$ to $`s_2=20\mathrm{Mm}`$ along half a loop, i.e. over a distance $`9\mathrm{Mm}`$ from the loop top.

Results for he Fe xxi 1354.1 Å are shown in Figs. 2 and 3 and are obtained using the tables for the emission function $`G(T)`$ calculated by Monsignori Fossi (1994, private communication). The observed light curve appears similar to those obtained for the X-ray lines with the FCS. This fact is not surprising as the FCS lines and the Fe xxi 1354.1 Å line originate in the same part of the atmosphere.

The curve computed with simulation B (base heating) is closer to the observed one during the flare onset, and the shape of the light curve is well simulated for the first 400s. However the flux decreases too rapidly during the flare decay. On the other hand, with the heating at the top (simulation A), the curve is too low during the early phase, but it is high even well after the heating is switched off. The modeled light curve peaks later than the observed one, but follows the flare decay emission better, even though also model A predicts a more rapid decrease of the intensity than observed, implying that further heating might be released during the flare decay in the EUV emitting plasma.

In Fig. 3 the emission integrated over the whole loop is compared with the flux in the Fe xxi 1354.1 Å line coming from the whole raster for both the simulations. The modeled curves are now very different from the observed one, as the total measured intensity is much higher than the calculated one in both cases.

The observed emission in the O v 1371.3 Å line was brighter in both kernels F1 and F2, corresponding to the two foot-points of the loop, than elsewhere in the raster region. A chromospheric filament was probably responsible of the initially increased emission in kernel F2 during the pre-flare phase (see above). The observed flux in region F2 is higher than in F1 and the two light curves are different (see CP88, Fig. 10), suggesting the presence of other emitting chromospheric structures in region F2. For this reason we have compared our calculations only with the data of kernel F1 and not with those of F2. In kernel F1 there is high pre-flare emission, which could be related to the presence of other closed structures emitting in the O v 1371.3 Å line or in the blended unidentified line mentioned above.

From our hydrodynamic calculations we simulate the light curve in this line using two different formulations for the emissivity $`G(T)`$:

1. the spectral emission function tabulated by Landini & Monsignori Fossi (1990) and following upgrades (thereafter LMF);
2. the emissivity computed with Raymond’s spectral code (Raymond & Smith (1977), and following upgrades, henceforth RS).

The two modeled light curves have the same profile but they differ by almost one order of magnitude. Discrepancies in the results obtained with different spectral models have already pointed out by Pallavicini (1994) and constitute an important difficulty in comparing real data with the hydrodynamic calculations or any other modeling results. Anyway, the discrepancy among spectral models does not alter significantly the shape of the light curve, but mostly the intensity.

We have first compared the flux integrated over half a loop with the emission from kernel F1; as a matter of fact, according to our model, only the TR contributes to the emission in the O v 1371.3 Å line, and therefore, only the foot-points of the loop are bright in this wavelength. In Fig. 4 and in Fig. 5 we compare our numerical results (both simulations A and B) with the observed flux in kernel F1 (top panel). We also plot the light curves predicted by our hydrodynamic calculations and the measured flux coming from the whole raster (bottom panel). The raster flux is larger than that predicted with a single loop model, either if we assume the LMF spectral model or the RS model. This fact is not surprising because many other structures present in the raster might contribute to the emission, as for the Fe xxi 1354.1 Å line. Results obtained with the RS spectral model are in better agreement with the observations in kernel F1.

The O v 1371.3 Å line peaks earlier than the Fe xxi 1354.1 Å line in our simulations as well as in the real observation but the O v 1371.3 Å light curves of our models are qualitatively different from the data plotted in CP88, at least for the first 5 minutes. The model with the heating at the loop top and the RS spectral model approximate the decay light curve quite well. This could be said also for the bottom heated model for $`t<700\mathrm{s}`$. Then a thermal instability occurs (see long-dashed lines in Fig. 4 and in Fig. 5). The rapid cooling of the atmosphere, mostly due to the increase of radiative losses as the temperature decreases below $`10^6\mathrm{K}`$, determines a significant peak of the emission which makes model B unlikely to describe this flare.

## 5 Discussion and conclusions

The X-ray emission of this flaring loop has been accurately modeled by Peres et al. (1987) using the hydrodynamic results of the PH code: in that work they obtained theoretical light curves very close to the observed ones. In this paper we compare the results of our numerical calculations with both typical TR emission and coronal ones, simultaneously.

From the analysis of all the modeled light curves in both the X-rays and EUV bands and the data registered during the event, we note that the top heated loop model gives results in better agreement with the coronal emission than the bottom heated loop model, during the entire flare evolution, in agreement with Peres et al. (1987). On the basis of our new calculations we can add that this model also accounts for the observed Fe xxi 1354.1 Å line during a large fraction of the November 12, 1980 flare. We note that the computed light curves in the Fe xxi 1354.1 Å line have a shape similar to those of the X-ray lines formed in the same temperature range, and therefore originating from the same part of the atmosphere.

Both our models predict Fe xxi line flux close to the observed one at the time of the flare X-ray line peak, which occurred during the decay of the flare light curve in the observed O v 1371.3 Å line. Also the top-heated model yields an already decaying OV light curve at the time of coronal lines flare maximum. However during the early flare the lower TR emission cannot be fitted with the same model which consistently yields lower emission than observed. This suggests that more plasma than modeled might have contributed to the O v 1371.3 Å line emission.

In summary, the analysis of the hot coronal EUV emission (Fe xxi 1354.1 Å line) confirms the scenario derived with the previous study (Peres et al. (1987)) based on X-ray lines. The study of the O v 1371.3 Å line, instead, shows a rather different evolution and the relevant light curve is poorly fitted by the hydrodynamic loop model which instead works well for the hot coronal emission. We therefore confirm that the single loop model (albeit a schematic approximation of reality) works well for the corona of this flare, and therefore that a single loop - or a bundle of loops evolving coherently - dominated the coronal emission, as MacNeice et al. (1985) and Peres et al. (1987) suggested. The colder plasma emission, instead, appears dominated by other structures, probably some already present at an earlier phase, others evolving and reaching their maximum emission before the Fe xxi 1354.1 Å line peak. Also Feldman (1983), Widing & Cook (1987), Doschek (1997), Mason (1998) observed that there is a mismatch between TR and coronal flare emission.

It appears that a single loop model is not adequate to fit the lower TR lines simultaneously to the coronal lines (which are well fitted), at least for this flare. To this end more complex models may be required, such as multi-structure models.

###### Acknowledgements.

This work has been done with partial support of the Italian Ministero dell’Università e della ricerca Scientifica e Tecnologica and of the Agenzia Spaziale Italiana.