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# Polyelectrolyte Multilayering on a Charged Sphere

## I Introduction

Polyelectrolyte multilayer thin films are made of alternating layers of polycations (PCs) and polyanions (PAs). The so-called layer by layer method, first introduced in planar geometry by Decher, consists in a successive adsorption of the polyions onto a charged surface and has proved to be extremely efficientDecher\_1992 ; Decher\_1997 . Due to the many potential technological applications such as biosensing Caruso\_Langmuir\_1997 , catalysis Onda\_1999 , optical devices Wu\_JACS\_1999  etc., this process is nowadays widely used. Various techniques are employed to control the polymer multilayer buildup such as optical Dijt\_1994 ; Kovacevic\_2002  and neutron Schmitt\_1993 ; Loesche\_Macromol\_1998  reflectometry, AFM McAloney\_2001 , UV spectroscopy Schoeler\_2002 , NMR techniques mccormick02a\_pre , and others. Some experiments (see e.g., Ref. Helm\_Macromolecules\_1998 ) were devoted to the basic mechanisms governing polyelectrolyte multilayering on planar mica-surfaces where especially, the role of surface charge overcompensation was pointed out.

Another very interesting application is provided by the polyelectrolyte coating of spherical metallic nanoparticles Caruso\_Science\_1998 ; Caruso\_JPCB\_2001 . This process can modify in a well controlled way the physico-chemical surface properties of the colloidal particle. Despite of the huge amount of experimental works, the detailed understanding of the multilayering process is still rather unclear, especially for a charged colloidal sphere. Hence the study of polyelectrolyte multilayering is motivated by both experimental and theoretical interests.

On the theoretical side, the literature on this subject is rather poor. Based on Debye-Hückel approximations for the electrostatic interactions and including lateral correlations by considering different typical semiflexible polyelectrolyte-layer structures, Netz and JoannyNetz\_Macromol\_1999b  found a remarkable stability of the periodic structure of the multilayers in planar geometry. For weakly charged flexible polyelectrolytes at high ionic strength qualitative agreements between theory Castelnovo\_2000 , based on scaling laws, and experimental observations Loesche\_Macromol\_1998 ; Fahrat\_1999  have been provided. The driving force of all these multilayering processes is of electrostatic origin and it is based on an overcharging mechanism, where the first layer overcharges the macroion and the subsequent layers overcharge the layers underneath. However, the role of non-electrostatic interactions though pointed out in Ref. Castelnovo\_2000 ; Joanny\_EPJB\_1999  is not clear. In particular, it is still open whether the layer build up is an equilibrium- or out of equilibrium process, which resembles more a succession of dynamically trapped states. Therefore we do not know whether or not the complex polyelectrolyte is in thermodynamical equilibrium. This point has also been emphasized in a recent experimental work on planar multilayers Kovacevic\_2002  where considerable kinetic effects were reported. So far, there are nor analytical results neither simulation data for multilayering formation onto charged spheres.

The goal of this paper is to study the underlying physics involved in the polyelectrolyte multilayering onto a charged colloidal sphere by means of MC simulations. The paper is organized as follows: Sec. II is devoted to the description of our MC simulation method. The relevant target quantities are specified in Sec. III. The single chain adsorption is studied in Sec. IV, and the polyelectrolyte bilayering in Sec. V. Then the multilayering process is investigated in Sec. VI. The case of short polyelectrolyte chains is considered in Sec. VII. Finally, Sec. VIII contains some brief concluding remarks.

## II Simulation method

The setup of the system under consideration is very similar to those recently investigated by means of molecular dynamics simulations Messina\_PRE\_2002 ; Messina\_JCP\_2002 . Within the framework of the primitive model we consider one charged colloidal sphere characterized by a radius $`a`$ ($`=4.5\sigma `$) and a bare charge $`Q_M=Z_Me`$ (where $`e`$ is the elementary charge and $`Z_M=40`$) surrounded by $`Z_M`$ neutralizing monovalent ($`Z_c=1`$) counterions and an implicit solvent (water) of relative dielectric permittivity $`ϵ_r80`$. In the remaining of the paper, we will refer to the term macroion as the charged colloidal sphere. Polyelectrolyte chains ($`N_+`$ PCs and $`N_{}`$ PAs) are made up of $`N_m`$ monovalent monomers ($`Z_m=1`$) of diameter $`\sigma `$. For the sake of simplicity, we only consider here symmetrical complexes where PC and PA chains have the same length and carry the same charge in absolute value. To each charged PC or PA we also add $`N_m`$ small monovalent ($`Z_c=1`$) counterions (anions and cations countering the charge of the polyelectrolytes) of diameter $`\sigma `$, hence always a charge neutral entity was added. Thereby all the microions have the same valence $`Z=Z_c=Z_m=1`$ as well as the same diameter $`\sigma `$. Added salt of course would even weaken the effects observed and would be especially important for the case of an adsorption interaction between macroion and polyelectrolyte.

All these particles making up the system are confined in an impermeable spherical cell of radius $`R=60\sigma `$. The spherical macroion is held fixed and located at the center of the cell. To avoid the appearance of image charges Messina\_image\_2002 , we assume that the macroion has the same dielectric constant as the solvent.

Standard canonical MC simulations following the Metropolis scheme were used Metropolis\_JCP\_1953 ; Allen\_book\_1987 . The total energy of interaction of the system can be written as

$$U_{tot}=\underset{i,i<j}{}U_{hs}+U_{coul}+U_{FENE}+U_{LJ}+U_{vdw},$$
(1)
where all the contributions of the pair potentials in Eq. (1) are described in detail below.

Excluded volume interactions are modeled via a hard sphere potential $`U_{hs}`$ note\_HS  defined as follows

$$U_{hs}(r)=\{\begin{array}{cc}\mathrm{},\hfill & \mathrm{for}r<r_{cut}\hfill \\ 0,\hfill & \mathrm{for}rr_{cut}\hfill \end{array}$$
(2)
where $`r_{cut}=\sigma `$ for the microion-microion excluded volume interaction, and $`r_{cut}=a+\sigma /2`$ for the macroion-microion excluded volume interaction. Hence the center-center distance of closest approach between the macroion and a microion is $`r_0=a+\sigma /2=5\sigma `$.

The pair electrostatic interaction between two ions $`i`$ and $`j`$ (where $`i`$ and $`j`$ can be either a microion or the macroion) reads

$$U_{coul}(r_{ij})=\pm k_BTl_B\frac{Z_iZ_j}{r_{ij}},$$
(3)
where +(-) applies to charges of the same (opposite) sign and $`l_B=e^2/4\pi ϵ_0ϵ_rk_BT`$ is the Bjerrum length corresponding to the distance at which two elementary charges interact with $`k_BT`$. To link our simulation parameters to experimental units and room temperature ($`T=298`$K) we choose $`\sigma =4.25`$ Å leading to the Bjerrum length of water $`l_B=1.68\sigma =7.14`$ Å and to a macroion surface charge density of $`0.14\mathrm{Cm}^2`$.

The polyelectrolyte chain connectivity is modeled by using a standard FENE potential in good solvent (see, e.g., Kremer\_FENE\_1993 ), which reads

$$U_{FENE}(r)=\{\begin{array}{cc}\frac{1}{2}\kappa R_0^2\mathrm{ln}\left[1\frac{r^2}{R_0^2}\right],\hfill & \text{for}r<R_0\hfill \\ & \\ \mathrm{},\hfill & \text{for}rR_0\hfill \end{array}$$
(4)
where we chose $`\kappa =27k_BT/\sigma ^2`$ and $`R_0=1.5\sigma `$. The excluded volume interaction between chain monomers is taken into account via a purely repulsive Lennard-Jones (LJ) potential given by

$$U_{LJ}(r)=\{\begin{array}{cc}4ϵ\left[\left(\frac{\sigma }{r}\right)^{12}\left(\frac{\sigma }{r}\right)^6\right]+ϵ,\hfill & \text{for}r2^{1/6}\sigma \hfill \\ & \\ 0,\hfill & \text{for}r>2^{1/6}\sigma \hfill \end{array}$$
(5)
where $`ϵ=k_BT`$. These parameters lead to an equilibrium bond length $`l=0.98\sigma `$.

An important interaction in the multilayering process addressed in this study is the non-electrostatic short ranged attraction, $`U_{vdw}`$, between the macroion and the PC chain. To account for this kind of interaction, we choose without loss of generality a van der Waals (VDW) potential of interaction between the macroion and a PC monomer that is given by

$$U_{vdw}(r)=ϵ\chi _{vdw}\left(\frac{\sigma }{rr_0+\sigma }\right)^6\text{for}rr_0,$$
(6)
where $`\chi _{vdw}`$ is a positive dimensionless parameter describing the strength of the attraction. Thereby, at contact (i.e., $`r=r_0`$), the magnitude of the attraction is $`\chi _{vdw}ϵ=\chi _{vdw}k_BT`$, and for $`\chi _{vdw}=1`$, one recovers the standard attractive component of the LJ-potential \[see Eq. (5)\]. Since it is not straightforward to link this strength of adsorption directly to experimental values, we therefore investigated different possible strengths of attraction, which are known to be realistic for soft matter systems.

All the simulation parameters are gathered in Table 1. The set of simulated systems can be found in Table 2. Single-particle moves were considered with an acceptance ratio of $`2030\%`$ for the monomers and $`50\%`$ for the counterions. At equilibrium, the (average) length of the trial moves $`\mathrm{\Delta }r`$ are about $`30\sigma `$ for the counterions and $`0.1\sigma `$ for the monomers. About $`10^5`$ to $`10^6`$ MC steps per particle were required for equilibration, and about $`2\times 10^6`$ subsequent MC steps were used to perform measurements.

## III Target quantities

Before presenting the results, we briefly describe the different observables that are going to be measured. Of first importance, we compute the radial density of monomers $`n_\pm (r)`$ around the spherical macroion normalized as follows

$$_{r_0}^R4\pi r^2n_\pm (r)𝑑r=N_\pm N_m$$
(7)
where $`(+)`$ applies to PCs (PAs). This quantity is of special interest to characterize the degree of ordering in the vicinity of the macroion surface.

The total number of accumulated monomers $`\overline{N}_\pm (r)`$ within a distance $`r`$ from the macroion center is then given by

$$\overline{N}_\pm (r)=_{r_0}^r4\pi r^2n_\pm (r^{})𝑑r^{}$$
(8)
where $`(+)`$ applies to PCs (PAs). This observable will be used for the study of the adsorption of (i) a single PC chain (Sec. IV) and (ii) two oppositely charged polyelectrolytes (Sec. V).

Another quantity of special interest is the global net fluid charge $`Q(r)`$ which is defined as follows

$$Q(r)=_{r_0}^r4\pi r^2Z\left[\stackrel{~}{n}_+(r^{})\stackrel{~}{n}_{}(r^{})\right]𝑑r^{},$$
(9)
where $`\stackrel{~}{n}_+`$ ($`\stackrel{~}{n}_{}`$) include the density of all the positive (negative) microions. Thus, $`Q(r)`$ corresponds to the total fluid charge (omitting the macroion bare charge $`Z_M`$) within a distance $`r`$ from the macroion center, and at the cell wall $`Q(r=R)=Z_M`$. Up to a factor proportional to $`1/r^2`$, $`\left[Q(r)Z_M\right]`$ gives (by simple application of the Gauss theorem) the mean electric field at $`r`$. Therefore $`Q(r)`$ can measure the strength of the macroion charge screening by the charged species present in its surrounding solution.

## IV Single chain adsorption

In this part, we study the adsorption of a single long PC chain (system $`A`$) for different couplings $`\chi _{vdw}`$. Experimentally this would correspond to the process of the first polyelectrolyte layer formation.

The monomer density $`n_+(r)`$ and fraction $`\overline{N}_+(r)/N_m`$ are depicted in Fig. 1(a) and Fig. 1(b), respectively. The density $`n_+(r)`$ near contact ($`rr_0`$) increases considerably with $`\chi _{vdw}`$ as expected. At a radial distance of $`1.5\sigma `$ from the macroion surface (i.e., $`r=r_0+\sigma `$), more than 97% of the monomers are adsorbed for sufficiently large $`\chi _{vdw}`$ (here $`\chi _{vdw}>3`$) against only 78% for $`\chi _{vdw}=0`$.

The net fluid charge $`Q(r)`$ is reported in Fig. 2. In all cases we observe a macroion charge reversal (i.e., $`Q(r)/Z_M>1`$), as expected from previous studies Wallin\_Langmuir\_1996\_I ; Wallin\_JPhysChem\_1996\_II  addressing only $`\chi _{vdw}=0`$. The position $`r=r^{}`$ at which $`Q(r^{})`$ gets its maximal value decreases with $`\chi _{vdw}`$, due to the $`\chi _{vdw}`$-enhanced adsorption of the chain. This overcharging increases with $`\chi _{vdw}`$, since the gain in energy by macroion-monomer VDW interactions can better overcome (the higher $`\chi _{vdw}`$) the cost of the self-energy stemming from the adsorbed excess charge. Note that the maximal value of charge reversal of $`100\%`$ allowed by the total PC charge (i.e., $`Q(r^{})/Z_M=2`$) can not be reached due to a slight accumulation of microanions.

Typical equilibrium configurations can be found in Fig. 3. For all $`\chi _{vdw}`$ values, there is a wrapping of the chain around the macroion. In parallel, one can clearly see that the formation of chain loops is gradually inhibited by increasing $`\chi _{vdw}`$.

Although all the obtained results are intuitively easy to understand, they will turn out to be helpful in order to have a quantitative analysis of the effect of an extra short-range attraction already on the level of a single chain adsorption.

## V Adsorption of two oppositely charged polyelectrolytes

We now consider the case where we have additionally a PA chain (system $`B`$), so that we have a neutral polyelectrolyte complex (i.e., one PC and one PA). Experimentally this would correspond to the process of the second polyelectrolyte layer formation (with system $`A`$ as the initial state). We stress the fact that this process is fully reversible for the parameters investigated in our present study. In particular, we checked that the same final equilibrium configuration is obtained either by (i) starting from system $`A`$ and then adding a PA or (ii) starting with no chains and then adding the two oppositely charged polyelectrolytes, together with their counterions, simultaneously.

The monomer density $`n_\pm (r)`$ and fraction $`\overline{N}_\pm (r)/N_m`$ are depicted in Fig. 4(a) and Fig. 4(b), respectively. The corresponding microstructures are sketched in Fig. 5. The density of PC monomers $`n_+(r)`$ near contact ($`rr_0`$) increases considerably with $`\chi _{vdw}`$ as expected. However, a comparison with system $`A`$ (see Fig. 1) indicates that the adsorption of PC monomers (at given $`\chi _{vdw}`$) is weaker when an additional PA is present. This is consistent with the idea that the PC chain tends to build up a globular state by getting complexed to the PA chain. This feature is well illustrated in Fig. 5. More precisely, for sufficiently small $`\chi _{vdw}1`$, the polyelectrolyte globular state is highly favorable compared to the ”flat” bilayer state (see also Fig. 5). Nevertheless, at sufficiently large $`\chi _{vdw}2`$, the first layer made up of PC monomers is sufficiently stable to produce a second layer made up of PA monomers. Thereby, the two chains wrap around the macroion. As far as the PA monomer adsorption is concerned, Fig. 4 shows that $`n_{}(r)`$ always increases with $`\chi _{vdw}`$. For $`\chi _{vdw}=0`$, the polyelectrolyte complex is very close to the globular polyelectrolyte bulk state (i.e., in the absence of the macroion). This a non-trivial result, since naively one would expect a ”true” multilayering for any $`\chi _{vdw}`$. It is only for large $`\chi _{vdw}3`$ that one gets a true bilayer formation, where there is a pronounced peak in $`n_{}(r)`$ around $`rr_0\sigma `$.

It is useful to introduce the following dimensionless interaction parameters $`\mathrm{\Gamma }_M=Z_MZ\frac{l_B}{r_0}`$, which measures the strength of the macroion-PC electrostatic attraction, and $`\mathrm{\Gamma }_m=Z^2\frac{l_B}{\sigma }`$ which controls the PC-PA complex interaction. For large values of $`\mathrm{\Gamma }_m`$ the bulk complex will always be in a globular state, since then the Coulomb interaction will give rise to a chain collapse, similar to those seen in polyelectrolyte systems. Thus, for a sufficiently large value of $`\mathrm{\Gamma }_m/\mathrm{\Gamma }_M`$ at given $`\chi _{vdw}`$, the globular state will always be favorable and no bilayering can occurs. In this case unwrapping occurs, similarly to the microstructures depicted in Fig. 5(a) and Fig. 5(b). On the other hand, we find at fixed parameters $`\mathrm{\Gamma }_m`$ and $`\mathrm{\Gamma }_M`$, that one needs a s sufficiently large value $`\chi _{vdw}^{}`$, in order to achieve bilayering.

One can summarize these important results as follows:

* The equilibrium bilayering process on a spherical charged colloid with long polyelectrolyte chains requires a sufficiently strong extra short-ranged macroion-PC attraction.

A closer look on Fig. 4(b) reveals a further non-trivial behavior in the profiles of $`\overline{N}_\pm (r)`$ at high $`\chi _{vdw}`$. Very close to the macroion surface we always have a monotonic behavior of the fraction of adsorbed PC \[$`\overline{N}_+(r;\chi _{vdw})`$\] and PA monomers \[$`\overline{N}_{}(r;\chi _{vdw})`$\] with respect to $`\chi _{vdw}`$ as it should be. However, for a certain distance away from the surface we observe an unexpected behavior where $`\overline{N}_+(r;\chi _{vdw}=3)>\overline{N}_+(r;\chi _{vdw}=5)`$ as well as $`\overline{N}_{}(r;\chi _{vdw}=3)>\overline{N}_{}(r;\chi _{vdw}=5)`$. One can qualitatively explain this effect by the onset of the formation of one (or several) polyelectrolyte microglobule(s), i.e., small cluster(s) of oppositely charged monomers \[see Figs. 5 (d) and (e)\]. This is indeed possible because at high $`\chi _{vdw}`$ in principle more PC ( and consequently also PA) monomers want to get close to the macroion surface. Already for neutral chains a two dimensional flat adsorbed chain needs a high (surface) binding energy. Compared to bulk conformations the chain entropy is roughly reduced by $`k_BTN\mathrm{ln}(q_{d=2}/q_{d=3})`$. Here $`q`$ is the effective number of conformational degrees of freedom of a bond, giving that $`\mathrm{ln}(q_{d=2}/q_{d=3})=O(1)`$. Thus local microglobules that induce a small local desorption, are entropically much more favorable. Also, on the level of the energy, an increase of $`q`$ concomitantly favors the PC-PA microglobule.

The net fluid charge $`Q(r)`$ is reported in Fig.6. For $`\chi _{vdw}2`$ the macroion gets even overcharged and undercharged as one gets away from its surface, whereas for low $`\chi _{vdw}`$ no local overcharging occurs. Again, at high $`\chi _{vdw}`$ the strength of the charge oscillation is not a monotonic function of $`\chi _{vdw}`$ where we observe a higher local overcharging (and undercharging) with $`\chi _{vdw}=3`$ than with $`\chi _{vdw}=5`$. This latter feature is fully consistent with the profiles of $`\overline{N}_\pm (r)`$ \[see Fig. 4(b)\] previously discussed note\_counterions\_OC . However this onset of local (surface) microglobules (for $`\chi _{vdw}=5`$) is not strong enough to produce a non-monotonic behavior of $`r^{}`$ with respect to $`\chi _{vdw}`$.

## VI Multilayering

We now turn to the case where there are many polyelectrolytes (with $`N_{PE}3`$) in the system. We recall that when $`\chi _{vdw}0`$, the VDW interaction concern monomers of all PCs lying within the range of interaction. To keep the number of plots manageable, we will present our results obtained for $`\chi _{vdw}=0`$ and $`\chi _{vdw}=3`$. The case $`\chi _{vdw}=0`$ is (conceptually) important since it corresponds to the situation where only purely electrostatic interactions are present. The other case $`\chi _{vdw}=3`$ seems to be a reasonable choice, since we found a ”true” bilayering for that value. Moreover, such a strength should be easily accessible experimentally.

### VI.1 Adsorption with $`\chi _{vdw}=0`$

The density profiles of $`n_\pm (r)`$ for the systems $`AG`$ (with $`\chi _{vdw}=0`$) are reported in Fig. 7 and the corresponding microstructures are sketched in Fig. 8.

Figure 7 shows that when the total polyelectrolyte charge,

$$Q_{PE}(N_+N_{})N_me,$$
(10)
is zero, the density of PC monomers $`n_+(r)`$ near contact is lower than when charge $`Q_{PE}=N_me`$ (recalling that our systems are such that $`Q_{PE}=0`$ or $`N_me`$). This tendency \[lower $`n_+(r)`$ near contact with $`Q_{PE}=0`$\] gradually decreases as the total number $`N_{PE}`$ of polyelectrolytes is increased. In particular for the system $`G`$ where $`N_{PE}=12`$ and $`Q_{PE}=0`$, the density $`n_+(r)`$ near contact is nearly identical to that of systems $`A`$, $`C`$ and $`E`$ where $`Q_{PE}=N_me`$. On the other hand, when $`Q_{PE}=N_me`$ then $`n_+(r)`$ near contact is nearly independent of $`N_{PE}`$. The height of the peak in the PA monomer density $`n_{}(r)`$ increases monotonically with $`N_{PE}`$. Concomitantly, a third layer made of PC monomers builds up for high enough $`N_{PE}`$. This multilayering is especially remarkable for $`N_{PE}=12`$ (system $`G`$).

All these features concerning the first layer structure can be rationalized with simple ideas. When $`Q_{PE}=0`$, then the resulting global attraction between the macroion and the polyelectrolyte complex is much weaker than when $`Q_{PE}=N_me`$. In this latter situation where $`Q_{PE}=N_me`$, this excess charge carried by a PC chain leads to a relatively strong PC adsorption near the surface. The equilibrium configurations sketched in Fig. 8 suggest a wrapping from the PC monomers when $`Q_{PE}=N_me`$ \[see Fig. 8(a) and (c)\] and a (partial) unwrapping when $`Q_{PE}=0`$ \[see Fig. 8(b), (d)\]. Even for high $`N_{PE}=12`$ \[see Fig. 8(e)\], we can see this tendency of unwrapping leading to a polyelectrolyte-complex globular state. However, for symmetry reasons, when the total number of monomers is large enough as it is the case with $`N_{PE}=12`$, the distribution of the polyelectrolyte complex gets more isotropic leading to a weaker unwrapping at $`Q_{PE}=0`$.

The collapse into a globular polyelectrolyte complex becomes even more spectacular when $`\sigma `$ is reduced (i.e., larger $`\mathrm{\Gamma }_m`$) MD\_layering . In that case (not reported here), we found a wrapping (for $`Q_{PE}=N_me`$) similar to that depicted in Fig. 8(a) and (c), and a strong unwrapping (for $`Q_{PE}=0`$) where the compact neutral polyelectrolyte complex is adsorbed onto a small area of the colloid.

The net fluid charge $`Q(r)`$ is reported in Fig. 9. As expected one detects an overcharging and undercharging for $`Q_{PE}=N_me`$ and $`Q_{PE}=0`$, respectively. For $`Q_{PE}=0`$, the macroion is also locally overcharged very close to the macroion surface and its strength increases with $`N_{PE}`$. On the other hand, the strength of the undercharging (occurring at the largest radial position $`r^{}`$ of the extrema) at $`Q_{PE}=0`$ is nearly independent of $`N_{PE}`$. In parallel, the strength of the overcharging (occurring at the largest radial position $`r^{}`$ of the extrema) measured at $`Q_{PE}=N_me`$ is also nearly independent of $`N_{PE}`$ (systems $`C`$ and $`E`$). Moreover, our simulations show that for $`N_{PE}2`$ the strength of the overcharging (with $`Q_{PE}=N_me`$) and undercharging (with $`Q_{PE}=0`$) have nearly the same amplitude, in qualitative agreement with experimental data.

### VI.2 Adsorption with $`\chi _{vdw}0`$

In this part, we consider the additional attractive VDW macroion-PC monomer interaction with $`\chi _{vdw}=3`$. The same investigation as with $`\chi _{vdw}=0`$ is carried out here.

The density profiles of $`n_\pm (r)`$ for the systems $`AG`$ (with $`\chi _{vdw}=3`$) are reported in Fig. 10 and the corresponding microstructures are sketched in Fig. 11.

Figure 10 shows that the density $`n_+(r)`$ near contact (for a given system) is about six times larger than that obtained at $`\chi _{vdw}=0`$ (compare Fig. 7). When $`Q_{PE}=N_me`$, the density $`n_+(r)`$ at contact (slightly) increases monotonically with $`N_{PE}`$ in contrast to what happened at $`\chi _{vdw}=0`$ where it was nearly independent of $`N_{PE}`$. When $`Q_{PE}=0`$, we remark that the density $`n_+(r)`$ near contact is nearly independent of $`N_{PE}`$ (for $`N_{PE}2`$) in contrast to what happened at $`\chi _{vdw}=0`$.

As far as the PA density $`n_{}(r)`$ is concerned, the height of the first peak (for a given system) is about twice larger than that obtained at $`\chi _{vdw}=0`$. This height is a monotonic function of $`N_{PE}`$ within a given regime of $`Q_{PE}`$ (here, either $`0`$ or $`N_me`$). Nevertheless, in general this height exhibits a non-trivial dependence on $`N_{PE}`$, in contrast to our results with $`\chi _{vdw}=0`$. For the systems $`B`$ and $`C`$ both containing a single PA chain ($`N_{}=1`$), the height of the first peak in $`n_{}(r)`$ is smaller with $`N_+=2`$ (system $`C`$) than with $`N_+=1`$ (system $`B`$). This is again due to the formation of clusters of oppositely charged monomers that takes place above the first layer. This effect is more pronounced when the amount of PC monomers (at given $`N_{}`$) is larger (system $`C`$), leading to a local desorption of PA monomer. Those features are remarkable by a comparison of the snapshots of the systems $`B`$ and $`C`$ depicted in Fig. 5(d) and Fig. 11(a), respectively. Similar arguments can be used for the systems $`D`$ and $`E`$, where the same effect is found. At large $`N_{PE}`$, the height of the first peak in $`n_{}(r)`$ saturates as expected.

For $`3N_{PE}6`$, our simulation shows that the formation of the third layer \[i.e., the second peak in $`n_+(r)`$ at $`rr_02.6\sigma `$\] is enhanced when $`Q_{PE}=N_me`$ at fixed $`N_+`$. This effect can again be explained in terms of polyelectrolyte (micro)globules formation. Indeed, above the second layer, the formation of clusters made up of oppositely charged monomers is enhanced when the polyelectrolyte complex (seen by the underneath bilayer) is uncharged which corresponds to a state of charge $`Q_{PE}=0`$.

It is interesting to see that with $`N_{PE}=12`$ one even gets a second peak (and not a shoulder) in $`n_{}(r)`$, which is the signature of a fourth layer. This qualitatively contrasts with our findings at $`\chi _{vdw}=0`$. Therefore, we conclude that the effect of an extra short-ranged macroion-PC attraction is crucial for the multilayering process.

On a more qualitative level, it is very insightful to compare the microstructures obtained with purely electrostatic interactions ($`\chi _{vdw}=0`$) sketched in Fig. 8 with those obtained with a short-ranged VDW macroion-PC interaction ($`\chi _{vdw}=3`$) sketched in Fig. 11. From such a visual inspection, it is clear that in all cases the adsorbed polyelectrolyte complex is flatter at $`\chi _{vdw}=3`$ than at $`\chi _{vdw}=0`$. An other important qualitative difference, is that the unwrapping occurring at $`\chi _{vdw}=0`$ with $`Q_{PE}=0`$ \[see Fig. 8(b) and (d)\] is no longer effective when $`\chi _{vdw}=3`$ \[see Fig. 11(b) and (d)\]. In the same spirit, for a large number of chains ($`N_{PE}=12`$), the macroion surface is only partially covered by the PC monomers where some (large) holes appear \[see Fig. 8(e)\], in contrast to what occurs at $`\chi _{vdw}=3`$, where all the macroion surface is covered \[see Fig. 11(e)\].

The net fluid charge $`Q(r)`$ is reported in Fig. 12. As expected one finds an overcharging and undercharging for $`Q_{PE}=N_me`$ and $`Q_{PE}=0`$, respectively. Now one can get a local overcharging larger than 100% (i.e., $`Q(r)/Z_M>2`$) due to the VDW attraction that can lead to a first layer with many PC chains. For systems $`C`$ and $`E`$ we see that the overcharging at the third layer is around 50% and nearly independent of $`N_{PE}`$.

On the other hand, the strength of the undercharging (occurring at the largest radial position $`r^{}`$ of the extrema) at $`Q_{PE}=0`$ decreases with increasing $`N_{PE}`$, providing a gradually weaker driving force for the subsequent adsorption of the PC chain. On the basis of our results with $`\chi _{vdw}=0`$, we expect that the strength of the undercharging at $`\chi _{vdw}=3`$ (for larger $`N_{PE}`$) should stabilize around 50%. So it appears that the oscillation of under- and overcharging are not 100%, but rather close to 50%. This is probably sensitive to the specific model parameters chosen. What can be stated from our data is, that there is no reason to find a generally applicable overcharging fraction. Especially for the case of relatively small colloids, the results will strongly depend on the specific system parameters, which are both of electrostatic as well as non-electrostatic nature.

## VII Case of short chains

We now investigate the effect of chain length dependence. In this case the adsorption of a single chain does not necessarily produce an overcharging since the chain length ($`N_m=10`$ \- system $`H`$) is too short. The density profiles of $`n_\pm (r)`$ are reported in Fig. 13 for various $`\chi _{vdw}`$, and the corresponding microstructures are sketched in Fig. 14.

In the purely electrostatic regime ($`\chi _{vdw}=0`$), the polyelectrolyte adsorption is weak and it significantly increases with $`\chi _{vdw}`$. However, for all reported cases, we only observe a bilayering in contrast with previous long chain systems (compare Fig. 13 with Fig. 7 and Fig. 10) where thereby a true multilayering was reported.

In addition we observe several globally neutral polyelectrolyte complexes in the bulk, whose number decreases with $`\chi _{vdw}`$ (see Fig. 14). This feature was inhibited for long chains due to the strong PC-PA binding energy that keeps all the chains near the macroion surface. At sufficiently strong $`\chi _{vdw}`$ \[see Fig. 14(c) with $`\chi _{vdw}=5`$\], the macroion area gets largely (and uniformly) covered by the PC chains, leading to a strong bilayering. Nevertheless, due to the weak PC-PA binding energy, the formation of additional layer seems to be prohibited in contrasts to what was observed at $`\chi _{vdw}=3`$ with systems $`D`$ and $`E`$ that contain a similar number of monomers. Those observations lead us to the relevant conclusion that multilayering with short chains (if experimentally observed on a charged colloidal sphere) must involve additional non-trivial driving forces like specific PC monomer-PA monomer interactions that are not captured by our model. This again seems to be in agreement with the arguments presented in Ref.Kovacevic\_2002  which argue against a stable thermodynamic equilibrium complex when there is excess polyelectrolytes present.

The net fluid charge plotted in Fig. 15 indicates that only one charge oscillation (around the isoelectric point) is obtained in contrast to what can happen with longer chains. Again, here the driving force for the bilayer formation is the overcharging that increases with $`\chi _{vdw}`$.

## VIII Concluding remarks

We have carried out MC simulations to study the basic mechanisms involved in forming equilibrium polyelectrolyte complexes on a charged colloidal sphere. This work emphasizes the role of the short-range Van der Waals-like attraction (characterized here by $`\chi _{vdw}`$) between the spherical macroion surface and the oppositely charged adsorbed chain(s).

It was demonstrated that, for the bilayering process involving two long oppositely charged chains at fixed $`\mathrm{\Gamma }_m`$ and $`\mathrm{\Gamma }_M`$, it is necessary to have a sufficiently high $`\chi _{vdw}`$. In particular, below a certain value of $`\chi _{vdw}=\chi _{vdw}^{}`$, a dense adsorbed polyelectrolyte globule is obtained, whereas above $`\chi _{vdw}^{}`$ a flat bilayer builds up.

The same qualitatively applies to the case of many (more than two) long polyelectrolytes. In a purely electrostatic regime (i.e., $`\chi _{vdw}=0`$) one can never obtain a true (uniform) multilayering. However, by increasing $`\chi _{vdw}`$, one gradually increases the polyelectrolyte (polycation and polyanion) chain adsorption ultimately leading to a true multilayering where the macroion is uniformly covered. Nonetheless, at given $`\chi _{vdw}`$ and especially for small $`\chi _{vdw}`$, the polyelectrolyte globular state is always favored when its net charge is zero.

As far as the short chain case is concerned, it was shown that even bilayering can not be reached within the pure electrostatic regime. Only at higher $`\chi _{vdw}`$ (higher than those coming into play with long chains), one recovers a bilayer formation. However, multilayering (beyond bilayering) with very short chains seems to be very unlikely within our model. The large complex would not be thermodynamically stable and dissolve into smaller charge neutral polyelectrolyte complexes, consistent with the ideas presented in Ref.Kovacevic\_2002 .

As an overall conclusion, our results clearly demonstrated that besides an overcharging driving force \[i.e., successive macroion (effective) charge reversal by successive polymer layering), the stability of the polyelectrolyte multilayer is strongly influenced by the specific macroion-polyelectrolyte short range attraction. This statement should at least hold for the investigated cases of equilibrium structures.

A future study should systematically study other important effects, such as chain flexibility, specific interchain monomer-monomer interaction, microions valency etc… Nevertheless, our present findings hopefully will generate some further systematic studies to explore the effects of non-electrostatic effects for the layer-by-layer deposition technique.

###### Acknowledgements.

R. M. thanks F. Caruso and S. K. Mayya for helpful and stimulating discussions. This work was supported by Laboratoires Européens Associés (LEA) and the SFB 625.


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# Nonthermal Particles and Radiation Produced by Cluster Merger Shocks

## 1 Introduction

In the hierarchical merging cluster scenario, clusters grow in mass by accreting nearby clusters. Approximately 30–40% of galaxy clusters show evidence of substructure in both the optical Beers, Geller & Huchra (1982) and X-ray wavelengths Forman et al. (1981). Velocity differences between the observed structures is $`1000`$$`2000`$$`\mathrm{km}\mathrm{s}^1`$. With gravitational forces driving the interaction between the two systems, cluster mergers are consistent with highly-parabolic orbits. Typical sound speeds within the intracluster medium (ICM) are $`1000`$$`\mathrm{km}\mathrm{s}^1`$, so shocks will form at the interaction boundary of the two systems.

Shock fronts that form in the ICM as a result of a cluster merger event are thought to be associated with the cluster radio relics, which are diffuse emission found on the cluster periphery with no known optical counterpart. The shock compression will orient any existing cluster magnetic field into the plane of the shock. Radio relics are characterized by highly organized magnetic fields with field strengths in the $`1`$$`\mu `$G range with linearly polarized field lines in the vicinity of the shock Enßlin (1998). The shock front will accelerate a fraction of the thermal particles within the ICM by first-order Fermi acceleration.

It has been proposed that cluster mergers are the dominant contributor to the diffuse $`\gamma `$-ray background Loeb & Waxman (2000). Some unidentified EGRET sources are claimed to be associated with $`\gamma `$-ray emission from galaxy clusters Totani & Kitayama (2000). Excess EUV emission from Coma can be explained by nonthermal electrons accelerated at merger shocks Atoyan & Völk (2000). Variations in radio surface brightness will result from superposition of cluster emissions Waxman & Loeb (2000).

## 2 Models

We present the results of a computer code designed to calculate the time-dependent particle distribution functions evolving through adiabatic and radiative losses for electrons and protons accelerated by the first-order Fermi process at the cluster merger shock Berrington & Dermer (2002). The model calculates the shock speed from the shock formed in a cluster merger event by the interaction speeds expected from two point masses interacting under their mutual gravity. The point masses are assumed to be on elliptical orbits whose onset is initiated by the collapse and merger of primordial density fluctuations. The collision is a result of the two bodies “falling out” of the Hubble flow and onto a nearby cluster. Expected total orbital energies are $`E_{\mathrm{tot}}10^{63}`$$`10^{64}\mathrm{ergs}`$. Expected collision velocities between a $`10^{15}\mathrm{M}_{}`$ and a $`10^{14}\mathrm{M}_{}`$ mass cluster range from $`1800`$$`3500\mathrm{km}\mathrm{s}^1`$. The electron and proton distribution functions originate from a momentum power-law injection spectrum. In terms of particle kinetic energy $`E_{e,p}=(\gamma _{e,p}1)m_{e,p}c^2`$, the injection function is

$$Q_{e,p}(E_{e,p},t)=Q_{e,p}^0c^{s(t)1}\left[E_{e,p}\left(E_{e,p}+2m_{e,p}c^2\right)\right]^{\frac{s(t)+1}{2}}\left(E_{e,p}+m_{e,p}c^2\right)e^{\frac{E_{e,p}}{E_{\mathrm{max}}(t)}},$$
(1)
where an exponential cutoff $`E_{\mathrm{max}}`$ has been applied and is determined by the maximum energy associated with the available time since the beginning of the merger event, by a comparison of the Larmor radius with the size scale of the system, and by a comparison of the energy-gain rate through first-order Fermi acceleration with the energy-loss rate due to adiabatic, synchrotron and Compton processes. The injected particle function is normalized through the normalization constant $`Q_{e,p}^0`$ which is determined by

$$_{E_{\mathrm{min}}}^{E_{\mathrm{max}}}𝑑EE_{e,p}Q_{e,p}(E,t)=\frac{\eta _{e,p}}{2}A_s\eta _{\mathrm{He}}^enm_pv_s^3.$$
(2)
where $`\eta _{e,p}`$ is an efficiency factor, $`v_s`$ is the shock speed $`A_s`$ is the area of the shock front; $`E_{\mathrm{max}}`$ and $`E_{\mathrm{min}}`$ are the maximum and minimum particle energies; $`\eta _{\mathrm{He}}^e`$ is an enhancement factor to account for the presence of ions heavier than Hydrogen. We assume an efficiency factor $`\eta _{e,p}=5\%`$ for both protons and electrons. With this method the total energy deposited into nonthermal particle production is $`\eta _{e,p}E_{\mathrm{tot}}`$. The particle density $`n`$ is calculated according the $`\beta `$ model, and averaged over the shock front.

The time evolving particle spectrum is determined by solving the Fokker-Planck equation in energy space for a spatially homogeneous ICM, given by

$$\frac{N(E,t)}{t}=\frac{1}{2}\frac{^2}{E^2}[D(E,t)N(E,t)]\frac{}{E}[\dot{E}_{\mathrm{tot}}(E,t)N(E,t)]+Q(E,t)\underset{i=\pi ,p\gamma ,d}{}\frac{N(E,t)}{\tau _i(E,t)}.$$
(3)
The quantity $`\dot{E}_{\mathrm{tot}}(E,t)`$ represents the total synchrotron, Compton, Coulomb, and adiabatic energy-loss rate for electrons, and the sum of the Coulomb and adiabatic energy-loss rates for protons. Both protons and electrons are subject to diffusion in energy space by Coulomb interactions. The protons experience catastrophic losses due to proton-proton collisions on the timescale $`\tau _\pi `$, proton-$`\gamma `$ collisions on the timescale $`\tau _{p\gamma }`$, and spatial diffusion from the cluster on timescale $`\tau _d`$. Spectra of secondary electrons and positrons are calculated from pion-decay products, and are subject to the same physical processes as the primary electrons. $`Q(E,t)`$ is the particle injection function.

The synchrotron, Compton, bremsstrahlung, and pion-decay $`\gamma `$-ray spectral components are calculated from the particle spectra following the methods described by Berrington & Dermer (2002). We use a standard parameter set with a mean ICM number density $`n_0=10^3\mathrm{cm}^3`$ and a uniform cluster magnetic field of $`B=1.0\mu \text{G}`$. Thus, $`V(t)=A(t)v_st`$.

## 3 Results

Fig. 1 shows the light curves at various energies for a cluster merger shock between a $`10^{14}\mathrm{M}_{}`$ and $`10^{15}\mathrm{M}_{}`$ with radii of 1.5 Mpc and 0.75 Mpc, respectively, with a central gas number density of $`n_0`$=$`10^3`$, and a magnetic field of B=1$`\mu `$G is assumed. The assumed core radius for the dominant cluster profile is 250 kpc, and $`\beta `$=0.75. We assume a cosmology defined by $`\mathrm{H}_0`$ = 70$`\mathrm{km}\mathrm{s}^1\mathrm{Mpc}^1`$, and ($`\mathrm{\Omega }_0`$,$`\mathrm{\Omega }_R`$,$`\mathrm{\Omega }_\mathrm{\Lambda }`$)=(0.3,0.0,0.7). We assume the shock forms at a redshift of $`z_i`$=0.3. The light curves exhibit a similar characteristic independent of frequency with the peak luminosity occurring when the centers of mass of the two clusters pass. The emission slowly decay and approach a plateau at times $`t>t_{\mathrm{acc}}`$ when particle injection has stopped. The rate of decay slows with decreasing energy with the lowest energies exhibiting the slowest decay rates. The late time plateaus are from $`\pi ^0`$ $`\gamma `$-rays for photons with E$`>`$1 GeV, and secondary electrons for the radio energies. With these expected fluxes, it is unlikely that the more than a few of the isotropic unidentified EGRET sources can be attributed to the radiation of nonthermal particles produced in cluster merger shocks.

The diffuse extragalactic $`\gamma `$-ray background is a featureless power law with photon index of 2.10($`\pm `$0.03). Fig. 2 shows the hardest particle injection spectral index, $`s_{\mathrm{min}}`$, for a cluster merger shock as function of the mass of the dominant cluster with varying values of core radii, $`r_c`$, and $`\beta `$’s. The particle spectral indices expected from the average values of $`r_c`$ and $`\beta `$ obtained from ROSAT observations of 45 Abell clusters Wu & Xue (2000) are 2.2-2.4. Only the dark matter profiles with strong central peaks produce particle indices $`<`$2.1. This discrepancy in the particle indices suggests that nonthermal radiation from cluster merger shocks can make only a minor contribution to the diffuse extragalactic $`\gamma `$-ray background unless dark matter halos contain strong central peaks.


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# Structure and mass distribution of spiral galaxies at intermediate redshifts

## 1 Introduction

The study of dark matter halo properties and central densities allows to constrain possible galaxy formation models and large scale stucture formation scenarios (Primack primack (2002); Khairul Alam et al. khai (2002)). It is interesting to analyse the corresponding data at different redshifts. For this kind of analysis it is needed to know both the distribution of visible and dark matter. Unfortunately, the structure and mass distribution of stellar populations, and therefore, the discrimination between visible and dark matter in very distant galaxies is still largely unknown.

General morphological evolution of galaxies at intermediate and high redshifts has been studied, for example by Smail et al. (smai (1997)), Andreon et al. (andr (1997)), Lubin et al. (lubi (1998)), Fabricant et al. (fabr (2000)), van den Bergh et al. (berg (2000)), van Dokkum et al. (2001a ), La Barbera et al. (barb (2002)), Im et al. (im (2002)). Several statistical correlations and color gradients in clusters at redshifts $`z=0.31`$ have been studied by Stanford et al. (stan (1998)), Ziegler et al. (zieg1 (1999)), van Dokkum et al. (dokk2 (2000)), Saglia et al. (sagl (2000)), Tamura & Ohta (ta:oh (2000)). More sophisticated correlation parameters for elliptical galaxies, the Fundamental Plane parameters involving dynamical information, have been determined by Kelson et al. (kels1 (1997)), van Dokkum et al. (dokk1 (1998), 2001b ), Kelson et al. (kels2 (2000)), Treu et al. (treu (2001)).

These studies indicate that most of the stellar content of early-type galaxies has formed at redshifts $`z>23`$, and has passed normal chemical evolution and there is no significant age difference between field and cluster galaxies. Within the standard $`\mathrm{\Lambda }`$CDM model, field ellipticals must be younger than cluster ellipticals. On the other hand, the fraction of early-type galaxies in clusters is smaller and the fraction of E+A (post-starburst) galaxies is higher at intermediate redshifts, indicating some morphological transformations from $`z1`$ to the present time. Theoretical models indicate that truncation of star formation rate can successfully explain this kind of morphological changes (van Dokkum & Franx, do:fr2 (2001); Bicker et al. bick (2002)).

Less is known about the structure of spiral galaxies at intermediate redshifts. For analysing the emission line profiles of disk galaxies, it is needed to distinguish the rotation and dispersion components. Spectrograph slit width is usually only slightly smaller than galactic dimensions which makes derived rotation curves uncertain and often only maximum values of rotation velocities can be estimated.

By now the maximum values of rotation velocities have been measured for distant galaxies up to redshift $`z=1.34`$ (Colless et al. coll (1994); Forbes et al. forb (1996); Rix et al. rix (1997); Simard & Pritchet si:pr (1998), Schade et al. scha (1999); Mallen-Ornelas et al. mall (1999); Briggs et al. brig (2001); van Dokkum & Stanford do:st (2001)). When plotted to the Tully-Fisher diagram, these measurements allow to compare the measured galaxies with the local ones. Rotation curves of very distant galaxies have been measured only by Vogt et al. (vogt1 (1996), vogt2 (1997)), Ziegler et al. (zieg2 (2002)) and Steidel et al. (stei (2002)). These data allow more detailed modeling of the structure of corresponding galaxies, especially if the curve extends beyond the solid-body rotation part.

To construct a self-consistent photometrical and dynamical model of a galaxy, both surface photometry and rotation curve data are needed. In the case of galaxies at intermediate redshifts the typical scale is $`510`$ kpc per arcsec and in order to determine the parameters of galactic components, it is recommendable to use also high-resolution HST photometry in addition to other photometrical data.

For our modeling, the galaxies had to match the following criteria. Their velocity profiles had to be undisturbed, symmetric with respect to the galactic centre and with sufficient extent. Galaxies seen almost face-on were not suitable due to uncertainties of the inclination angle of the galactic plane. We also could not use galaxies being seen edge-on, because for these galaxies the surface brightness distribution is largely influenced by galactic absorption. For detailed modeling, we selected three galaxies with rotation curves measured by Vogt et al. (vogt1 (1996)): 074-2237, 064-4412, 094-2210. For deriving the surface brightness distribution of these galaxies, we used images from the HST archive. General properties of these galaxies are given in Table 1. In the present work we take $`H_0=65`$ km/s/Mpc and $`q_0=0.5.`$

## 2 Photometrical structure

The images of all three galaxies were retrieved from the archive of the Hubble Space Telescope (WFPC2, observational programs 5090 and 5109, filters F814W and F606W). For processing we used pipeline-reduced on-the-flight calibrated images. 12 exposures in both colors were available for the galaxy 074-2237 and 4 exposures for the other two. Details about image processing and derivation of surface brihtness profiles are described in Tamm & Tenjes (ta:te (2001)). Here we summarize only basic steps, bringing out especially these aspects which differ from the previous processing. Processing was done with IRAF/STSDAS packages.

In order to elliminate cosmic rays, exposures were combined using the STSDAS task combine (option crrej). Before estimating the background, combined images were filtered to smooth down noises (task adaptive). We found no evidence of galaxy distortion caused by adaptive filtering. As the investigated galaxies were rather small in CCD frames, it was sufficient to subtract in all cases a constant background value from the images. Background values were determined by interpolating the values of the surrounding regions of the galaxies. This stage differs from the one we have used earlier. New on-the-flight calibration of the HST archive data has improved the quality of the original images, especially in the case of the galaxy 064-4412. The background levels were (in WFPC2 intensity counts) 11.7 (I)and 19.8 (V) for the galaxy 074-2262; 6.40 (I) and 7.25 (V) for the galaxy 064-4412; 6.25 (I) and 7.25 (V) for the galaxy 094-2210. Images of the three galaxies after background subtraction are given in Fig. 1.

The resulting images were deconvolved using the Lucy-Richardson algorithm for modeling PSF with the help of TinyTim 6.0. V-band images of 064-4412 and 094-2210 were not deconvolved, because due to a low signal-to-noise ratio deconvolution process gave unrealistic results. In order to calculate isophotes, task ellipse was used. The fitting process was carried out several times for each of the galaxies in order to estimate and reduce uncertainties. The scatter of the dots in Fig. 2 illustrates uncertainties of isophote fitting.

Before final calibration, we estimated the corrections of the luminosity flux for the geometric distortion and the charge transfer efficiency effect of the WFPC2 (Holtzman et al. 1995a ). We added 2% to the signal to compensate for the geometric distortion of 064-4412 and 094-2210 and 1.5% in the case of 074-2237. To transfer the luminosity counts into standard Johnson magnitudes, the calibration described by Holtzman et al. (1995b ) (H95) was used. For the filter F814W, we used the flight photometric system Eq. (8) and the coefficients from Table 7 in H95:

$$I=2.5\mathrm{log}(DN/t)0.062(VI)+0.025(VI)^2+$$

$$20.839+2.5\mathrm{log}(GR)+0.1+0.05.$$

For F606W filter, we used the synthetic calibration Eq. (9) and coefficients from Table 10 in H95:

$$V=2.5\mathrm{log}(DN/t)+0.254(VI)+0.012(VI)^2+$$

$$22.093+2.5\mathrm{log}(GR)+0.1+0.05.$$

Here GR is gain ratio as defined in H95, the term 0.1 corrects the formula for infinite aperture and 0.05 is the correction due to long exposures. $`VI`$ was calculated iteratively. Luminosity flux was corrected for the cosmological distortion by a factor $`(1+z)^4.`$

Luminosities have been corrected for absorption in our Galaxy according to Schlegel et al. (schl (1998)).

We estimated the k-correction in two ways. First, the observed colors were transformed to such standard colors for which the k-correction would be minimal. For this we used the method described in van Dokkum & Franx (do:fr1 (1996)) and Kelson et al. (kels2 (2000)). At redshift $`z=0.15`$ a suitable transformation would be from V to B and for redshifts 0.9 and 0.99 from I to B. For all three galaxies we used synthetic spectra of a Sbc–Scd galaxy derived by Coleman et al. (cole (1980)). Zero points relating AB magnitudes and Johnson magnitudes were taken from Frei & Gunn (fr:gu (1994)). Second, the k-corrections were estimated by using the chemical evolution models by Schulz et al. (schu (2002)). Again, at $`z=0.15`$ V color was transformed to B color, assuming the rest-frame $`(\mathrm{B}\mathrm{V})=0.63`$, at redshifts 0.90 and 0.99 I color was transformed to B color, assuming the rest-frame $`(\mathrm{B}\mathrm{I})=1.76`$. For the nearest galaxy, we took solar metallicity, for the two others $`Z=0.008`$. The results obtained by two methods nearly coincide in the case of the nearest galaxy, for more distant galaxies the agreement is within $`\pm 0.15^\mathrm{m}`$. Averaging the results of the two methods yields the following relations:

$$\begin{array}{cc}B(z=0.15)\hfill & =V+0.32,\hfill \\ B(z=0.90)\hfill & =I+0.90,\hfill \\ B(z=0.99)\hfill & =I+1.02.\hfill \end{array}$$

Here $`V`$, $`I`$ and $`(VI)`$ are observed Johnson magnitudes and $`B`$ is the Johnson magnitude in galactic rest-frame. The final galactic surface brightness profiles are presented in Fig. 3 by open circles. Error bars characterize uncertainties of both background determination and isophote construction.

## 3 Galactic models

Although several stellar populations can be discriminated in spiral galaxies, in the case of modeling very distant galaxies it is reasonable to limit the main stellar components to two – the bulge and the disk. Parameters of any other stellar component (central nucleus, metal poor halo, thick disk) could not be determined at present from available photometric observations. To construct a dynamical model, a dark matter component – the dark halo must be added to visible components. Of course, the photometrical and dynamical models must be mutually consistent.

When handling only surface photometry data, it is convenient to describe the galactic structure with the help of some simple parametric formulae for the surface density. Most common formulae are the de Vaucouleurs formula, the exponential law or the more general Sérsic formula. Most flexible is the Sérsic formula with an additional parameter, allowing to control the steepness of the surface density decrease (Sérsic sersic (1968)). Density distribution parameters must be determined e.g. by the least squares method. Using also kinematic data and constructing a dynamical model consistent with the photometry, the same density distribution law must be used for rotation curve modeling (and for velocity dispersion curve, if possible). In the case of the Sérsic formula, it can be done for spherical systems with an integer Sérsic index $`m`$ (Mazure & Capelato ma:ca (2002)). For a noninteger index and ellipsoidal surface density distribution a consistent solution for rotation curve calculations is not known.

In the present paper, the density distribution parameters are determined by the least squares method and they can have any value. Thus, it is not reasonable to use the Sérsic law for surface density distribution. It is more physical to start from the spatial density law. An analytical expression for spatial densities, reproducing well the Sérsic formula, was derived by Trujillo et al. (truj2 (2002)). Although this formula is useful, we decided to use for the bulge and for the disk an analyticaly simpler form (1), allowing to use more easily least-square fitting simultaneously for light distribution and rotation curve.

In our model the visible part of a galaxy is given as a superposition of the bulge and the disk. The spatial density distribution of every visible component (the bulge and the disk) is approximated by an inhomogeneous ellipsoid of rotational symmetry with constant axial ratio $`q`$ and the density distribution law (Einasto einasto (1969))

$$\rho (a)=\rho (0)\mathrm{exp}[(a/(ka_0))^{1/N}],$$
(1)
where $`\rho (0)=hM/(4\pi qa_0^3)`$ is the central density, $`M`$ is the component mass. Next, $`a=\sqrt{R^2+z^2/q^2}`$, where $`R`$ and $`z`$ are two cylindrical coordinates. $`a_0`$ is the harmonic mean radius

$$a_0^1=_0^{\mathrm{}}a^1𝑑M,$$
(2)
where $`dM=4\pi qa^2\rho (a)da`$ is the mass of the ellipsoidal shell of thickness $`da`$. Coefficients $`h`$ and $`k`$ are normalizing parameters, depending on $`N`$, which allows to vary the density behavior with $`a`$. The harmonic mean radius characterizes rather well the real extent of a component, independently of the parameter $`N`$. The definition of normalizing parameters $`h`$ and $`k`$ and their calculation is described in Tenjes et al. (tenj1 (1994)), Appendix B. Eq. 1 allows sufficiently precise numerical integration and has a minimum number of free parameters.

The dark matter (DM) distribution is represented by a spherical isothermal law

$$\rho (a)=\{\begin{array}{cc}\rho (0)([1+(\frac{a}{a_c})^2]^1[1+(\frac{a^0}{a_c})^2]^1)\hfill & aa^0\hfill \\ 0\hfill & a>a^0\text{.}\hfill \end{array}$$
(3)
Here $`a^0`$ is the outer cutoff radius of the isothermal sphere.

The density distributions for the bulge and the disk were projected along the line of sight, divided by their mass-to-luminosity ratios $`f`$ and their sum gives us the surface brightness distribution of the model

$$L(A)=2\underset{i=1}{\overset{2}{}}\frac{q_i}{Q_if_i}_A^{\mathrm{}}\frac{\rho _i(a)ada}{(a^2A^2)^{1/2}},$$
(4)
where $`A`$ is the major semiaxis of the equidensity ellipse of the projected light distribution, $`Q_i`$ are their apparent axial ratios $`Q^2=\mathrm{cos}^2\gamma +q^2\mathrm{sin}^2\gamma `$. The angle between the plane of a galaxy and the plane of the sky is denoted by $`\gamma `$. Summation index $`i`$ designates two visible components, the bulge and the disk.

The masses of the components we determined from the rotation law

$$v_i^2(R)=4\pi q_iG_0^R\frac{\rho _i(a)a^2da}{(R^2e_i^2a^2)^{1/2}},$$
(5)
$$V^2(R)=\underset{i=1}{\overset{3}{}}v_i^2(R),$$
(6)
where $`G`$ is the gravitational constant, $`e=\sqrt{1q^2}`$ is eccentricity, and $`R`$ is the distance in the equatorial plane of the galaxy. Summation is over all three components now.

Model parameters $`a_0`$, $`q`$, $`L_B`$, $`M`$ and $`N`$ for the bulge and the disk were determined by a subsequent least-squares approximation process. As the first step, we made a crude estimation of the population parameters. The purpose of this step is only to avoid obviously unphysical parameters – relations (4) and (5) are nonlinear and fitting the model to the observations is not a straightforward procedure. Next a mathematically correct solution for each galaxy was found. Details of the least squares approximation and the general modeling procedure were described by Einasto & Haud (ei:ha (1989)), Tenjes et al. (tenj1 (1994), tenj2 (1998)).

The rotation curves of the galaxies 074-2237, 064-4412, 094-2210 have a rather small extent (see Figs. 46). We do not have any additional information about the dynamics of these galaxies at large galactocentric radii. For this reason, the outer cutoff radius of the DM component remains undetermined at present. We fixed $`a^0=5a_0`$ on the basis of the structure of nearby galaxies. This value influences the rotation curve behavior only in extreme outer regions of galaxies and does not influence our results. Then we assumed by analogy with nearby galaxies that the rotation curve of these galaxies remains flat at least up to 30 kpc (Sofue & Rubin so:ru (2001)).

As we have no information about velocity dispersions in the central regions of our galaxies we can calculate only the circular velocities (Eqs. 56). If the value of velocity dispersions is comparable to the value of rotational velocity at a particular distance, the latter does not correspond to the value of circular velocity. The difference is known in galactic dynamics as the asymmetric drift. Typical emission-line dispersions in galaxies at intermediate redshifts are 30–100 km/s (Koo et al. koo (1997); Guzman et al. guzm (1997); Im et al. im1 (2001)). Thus, within central $`0.5\mathrm{}0.7\mathrm{}`$ model velocities must be higher than the observed rotational velocities.

## 4 Results and discussion

Calculated from our photometry, the total apparent Johnson V luminosity of the galaxy 074-2237 is $`V=19.28\pm 0.05`$, which coincides well with the $`\mathrm{V}_{606}`$ luminosity estimates by Vogt et al. (vogt1 (1996)) 18.70 and Simard et al. (sima (2002)) 18.78. The mean apparent color index is $`(\mathrm{V}\mathrm{I})=1.5\pm 0.2`$. The difference between the Johnson V and $`\mathrm{V}_{606}`$ is $`0.49^m`$, if $`(\mathrm{V}\mathrm{I})=`$1.5.

The calculated total apparent Johnson I luminosity of the galaxy 064-4412 is $`I=22.43`$, which also coincides well with the $`I_{814}`$ luminosity estimates by Vogt et al. (vogt1 (1996)) 22.38 and by Simard et al. (sima (2002)) 22.33. The mean apparent color index is $`(\mathrm{V}\mathrm{I})=2.2`$. The difference between the Johnson I and $`\mathrm{I}_{814}`$ is $`0.12^m`$ if $`(\mathrm{V}\mathrm{I})=`$2.3.

The total apparent Johnson I luminosity of the galaxy 094-2210 from our photometry is $`I=21.47`$. The $`I_{814}`$ luminosity estimate by Vogt et al. (vogt1 (1996)) is 21.41 and by Simard et al. (sima (2002)) it is 21.21. The mean apparent color index is $`(\mathrm{V}\mathrm{I})=2.4`$.

The final two-component models fit the photometric B-profiles with a mean relative error of 0.2–0.5 per cent. For the fitting of the rotation curves, we constructed two models for each galaxy. One kinematical model corresponds to the mathematically best fit at all distances, even in the central regions. However, due to the arguments given in the last paragraph of the previous section, this model is unphysical, because it underestimates the bulge mass. Therefore, a second model was constructed with the bulge mass fixed at higher values. At present we have no independent basis to estimate the bulge mass. We hope that two different models allow the reader to understand how the bulge mass variation influences the overall behaviour of rotation curves in all three concrete cases. Real bulge masses and thus also mass-to-light ratios may be higher than the values resulting from Table 2. To derive real bulge mass-to-light ratios, additional observations (central stellar velocity dispersions) are needed.

The parameters of the final models (the axis ratio $`q`$, the harmonic mean radius $`a_0`$, the total mass of the population $`M`$, the structural parameter $`N`$, the dimensionless normalizing constants $`h`$ and $`k`$, B-luminosities and corresponding mass-to-light ratios) are given in Table 2. Bulge and DM masses are given in parentheses to indicate that on the basis of present observational data it is not possible to determine these values uniquely. The last column in Table 2 gives the masses for low bulge mass models. The final models are denoted by thick solid lines in Figs. 36. Models of individual visible components are represented by dashed lines, the model of the dark matter component by a thin solid line. In Table 3, calculated from the models, integrated parameters are given: apparent I-band magnitude, total mass of the visible matter, total intrinsic luminosity and mass-to-light ratio of the visible matter.

It is interesting to compare the central surface brightnesses of galactic disks with the results obtained for local galaxies. For the galaxies modeled here, the central brightnesses of disks are $`\mu _B(0)=`$ 21.4, 21.3, 21.1. The mean value for two galaxies at redshifts $`z=0.91`$ is $`\mu _B(0)=21.2`$. For local galaxies the original value by Freeman (freeman (1970)) was 21.65. However, this value probably depends on the galactic morphological type and luminosity, and thus has considerable scatter (Graham & de Blok gr:bl (2001)). For galaxies at redshifts $`z=0.51`$ Schade et al. (scha2 (1996)) derived $`\mu _B(0)=20.0`$, when transformed to conventional broadband magnitudes, but also with a rather significant scatter. Our values are clearly higher. However, it must be taken into account that central brightnesses of disks have been determined by Schade et al. (scha2 (1996)) within the assumption of exponential disks and $`r^{1/4}`$ bulge. When fitting the disks of our two higher redshift galaxies with parameters $`N=1`$, the resulting disk central brightnesses are brighter by 0.6 mag, i.e. the mean value is $`\mu _B(0)=20.6`$. Disk central brightness is sensitive also to bulge parameters. Our bulge profile is quite different from the $`r^{1/4}`$ law. And finally, when taking into account also the uncertainties in k-correction, our values for the disk central brightnesses are not peculiar.

Figure 3 shows that the light distribution in outer parts of the galaxies studied in the present paper is rather steep (the parameter $`N`$ is small). In all cases, the disk density distribution in outer parts is steeper than for a simple exponential disk. Central concentration parameters (Trujillo et al. truj1 (2001)) for these galaxies are rather small, about 0.15. Steep decrease of the surface brightness in outer parts of galaxies may be the result of the outer truncation of the disk. According to Pohlen et al. (pohl (2000)), the truncation occurs at distances of about 3 disk scale lengths. In the case of galaxies studied here, the surface photometry does not extend to so large distances.

The central density of the dark matter $`\rho (0)=hM/(4\pi a_0^3),`$ characterizing the rotation velocity gradient at the center caused by the dark halo, is rather well determined from observations and nearly independent of the choice of the dark halo outer cutoff radius. Calculated from our models, the central densities of DM components are $`\rho (0)=`$ 0.0092, 0.028, and 0.015 in units $`\mathrm{M}_{\mathrm{}}/\mathrm{pc}^3`$. It is important to stress that these values are calculated for maximum disk models and are thus the lower limits. This must be taken into account especially in the case of the first value (the galaxy 074-2237) where models with lower disk mass and higher DM density give equally good fit for the rotation curve. The visible and DM masses become equal for this galaxy at $`R=17`$ kpc in our maximum disk model. A mass distribution model of the galaxy 074-2237 was conctructed also by Fuchs et al. (fuch (1996)) who used for mass determination a model of spiral arm formation via swing-amplification. They concluded that in order to create a two-armed spiral structure, higher DM densities are needed when compared with the maximum disk models. According to their model, the central DM density of 074-2237 is 0.025.

It is possible to construct mass distribution models for galaxies without assuming the existence of a DM component. Corresponding models are given in Figs 79. It is seen that the calculated rotation curves start to decrease after the last observed point of the rotation curves. Thus, within the available at present observations, the models without any dark halo fit well with observations.

As mentioned earlier, due to the limitied extent of rotational curves it is not possible to determine any parameters of the DM distribution. Figures 79 show that rotation curves can be well fitted without DM. However, we think that there are enough independent arguments in support of the existence of DM and thus, realistic models must include a DM component. For this reason, on the basis of nearby galaxies weumed that rotation curves remain flat up to the distances of about 30 kpc (see Sofue & Rubin so:ru (2001)). This assumption still does not enable to determine the total DM mass and its characteristic radius. Only the central density of the DM component can be found. Therefore, the mass and the radius of the DM component given in Table 2 are simply fixed. It is possible to fix, e. g. the DM mass two times smaller, decreasing correspondingly the DM radius in a way that the central density remain unchanged. The central density of DM can be dermined from models within the assumption of the flatness of rotation curves. The central density of DM is not sensitive to the uncertainties of bulge mass.

The central density of the dark matter distribution is a parameter allowing to constrain possible cosmological models and corresponding parameters at early periods of structure formation (see eg. Navarro & Steinmetz na:st (2000), Shapiro & Iliev sh:il (2002), Khairul Alam et al. khai (2002), Zentner & Bullock ze:bu (2002)). We think it is reasonable to derive also the central DM densities at different redshifts. In the present paper we have used only one density distribution model for DM (Equation 3). In subsequent papers we intend to enlarge the sample of modeled galaxies and study the dependence of model parameters on different DM distribution models (e.g. models by Navarro et al. nava (1997), Burkert burkert (1995)).

###### Acknowledgements.

We would like to thank the anonymous referee for useful comments and suggestions. We thank Dr. U. Haud for making available his programs for light distribution model calculations. Surface photometry data used in the present study are from STScI Archive and we thank the members of observational proposals 5109 (PI J. Westphal) and 5090 (PI E. Groth) for their work. We acknowledge the financial support from the Estonian Science Foundation (grant 4702) and DAAD (grant A0209036). Part of the paper was written at Goettingen University Observatory and we thank the staff for hospitality. We also thank Dr. N. Vogt for communicating his data in numerical form as electronic files.


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# Effect of double-polarization data in fits to single-pion photoproduction

## Abstract

We investigate the influence of new Jefferson Lab polarization-transfer, $`C_x^{}`$ and $`C_z^{}`$, and recoil polarization, $`P_y`$, measurements in multipole fits to the single-pion photoproduction database. Results are compared to those found with the addition of a double-polarization quantity associated with the Gerasimov$``$Drell-Hearn sum rule.

The single-pion photoproduction process has been studied extensively, both experimentally and theoretically, for several decades. Over the resonance region, there now exists a database of approximately twenty thousand angular and total cross section measurements. This set consists mainly of unpolarized cross sections, many of these having been obtained without the benefit of tagged photons.

Experimental programs now underway have been adding very precise cross sections, many involving tagged photons, polarization, and a wide angular acceptance. Coverage is not yet complete. As a result, our knowledge of the underlying resonance contributions is based on a mix of data, old and new, some of which are certainly flawed. Fits to the full data set tend to favor the newer measurements GW\_pi . However, experience has shown that sensitive quantities can be biased by older results, particularly if they cover a gap in the newer measurements, and are presented with comparable uncertainties bonn\_e2 .

Polarization quantities have been particularly influential in constraining multipole analyses. For this process, there are 8 independent quantities, each providing a new constraint on the 4 helicity amplitudes. In the $`\mathrm{\Delta }(1232)`$ region, a single resonance is dominant, and in this case (only) each new quantity can be translated into a constraint on a single ($`M_{1+}^{3/2}`$) multipole and its interference with other smaller multipoles. Here, and also at higher energies, the beam-polarization ($`\mathrm{\Sigma }`$) has been useful in revealing problems graal  with the existing SAID GW\_pi  and MAID maid  fits.

Until recently, very few double-polarization measurements existed, and the available data had large uncertainties, weakening their influence in unweighted fits. As a by-product of the ongoing GDH measurements, angular distributions of the difference of helicity 1/2 and 3/2 cross sections, related to the beam-target polarization quantity ($`E`$bds , have been measured and fitted GDH . While SAID and MAID gave qualitatively correct predictions for this quantity, deviations starting at 700 MeV were linked to the $`N(1520)`$ photo-decay amplitudes GDH .

A double-polarization experiment gilman , giving the new beam-recoil quantities $`C_x^{}`$ and $`C_z^{}`$, has been completed by the Hall A Collaboration at Jefferson Lab. These measurements, which extend from 0.83 GeV to 4.03 GeV, are given with high precision, and cover a region dominated by older data. While SAID and MAID predict the lowest energy results, at energies of 1 GeV and beyond even qualitative agreement is lost sabit . In addition, just beyond the energy range of SAID, the recoil polarization ($`P_y`$), also measured in Ref. gilman , appears to have a rapid angular variation not seen below 2 GeV.

We have attempted to fit these new values of $`P_y`$, $`C_x^{}`$, and $`C_z^{}`$ in order to determine their effect on our multipole solution. In Figs. 1 and 2, we compare our results (SM02) prior to the measurement of Ref. gilman , (SG02) including the new $`P_y`$, $`C_x^{}`$, and $`C_z^{}`$ points, and (SC02) a forced fit. At 815 MeV and 1215 MeV, comparisons with MAID are also presented. The forced fit has weighted the data of Ref.gilman  by a factor of 4. By weighting data, we magnify changes in the multipole amplitudes, and more clearly see where data conflicts occur. In the case of the E2/M1 ratio, for example, an early forced fit forced  to $`\mathrm{\Sigma }`$ data resulted in a value of $`2.9\%`$, when the predominant value was $`1.5\%`$.

In Figs. 1 and 2, it is clear that both SAID and MAID, at the lower energies where they can be compared, have a shape consistent with the $`C_{x^{},z^{}}`$ data. The deviations at 1620 MeV and 1900 MeV are much larger. However, except for a few points, the fit including data from Ref. gilman  is not appreciably different from the “forced” fit, and appears to adequately describe these new results. In Fig. 3, we show that forcing a fit to this new set has not degraded our fit to the GDH measurements. Other double-polarization observables deviate considerably, according to the weighting of these polarization-transfer data. These revised fits have been carried out using the parametrization described in Ref. GW\_pi . No increase in the angular momentum limit for parametrized waves was found to be necessary.

In Fig. 4, we display the above fits for $`P_y`$. As more weight is given to the measurements of Ref. gilman , an interesting feature emerges in the angular distribution at 1900 MeV. A sharp structure at about 60 is seen in the forced fit. This is correlated with the improved fit seen in Fig. 2(d), for $`C_z^{}`$, and Fig. 3(b), for the target-polarization quantity $`T`$. This feature of the single-spin asymmetries is not new, however, and was present in the old analysis of Barbour, Crawford, and Parsons barbour .

The changes displayed in Figs. 1 through 4 cannot be attributed to a single resonance or partial wave, as was argued for the GDH observable in Ref. GDH . A number of multipoles show moderate changes changes , and only some qualitative observations are possible. For example, a change in the $`E_{0+}^{3/2}`$ multipole can effect the overall shift seen in Fig. 1(d), and changes in either the $`M_{1+}^{1/2}`$ or $`M_{1+}^{3/2}`$ multipoles produce a peaking structure such as is seen in Figs. 3(b) and 4(d). However, a more complicated change in several amplitudes has given the full result. Some of the most prominent changes are displayed in Fig. 5.

In summary, we have found it possible to fit recent double-polarization measurements which initially showed significant deviations from both SAID and MAID. Adding these precise new data has actually improved our fit to some other quantities, most obviously the target-polarization asymmetry, and has been accomplished without a substantial degradation of our fit to other observables. The resulting shifts in our multipoles indicate that the region above 1 GeV is still underconstrained. Further shifts should be expected as the present generation of photon facilities contributes data to this region. In this regard, the proposed polarized-target/beam program for Hall B of JLab would be extremely useful loi .

###### Acknowledgements.

We thank R. Gilman for helpful discussions. This work was supported in part by the U. S. Department of Energy Grant DE–FG02–99ER41110. The authors gratefully acknowledge a contract from Jefferson Lab under which this work was done. Jefferson Lab is operated by the Southeastern Universities Research Association under the U. S. Department of Energy Contract DE–AC05–84ER40150.


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# Prediction of |𝑉₁₃| and the Dirac phase in the Neutrino Mixing Matrix⋆

## Abstract

We considered a model where $`|V_{13}|=0`$ so that $`\delta =0`$ at $`M_R`$ and analyzed mixing angles and CP violation angles at the low energy scale by using the renormalization group in the MSSM model. In this model, parameters at $`M_R`$ scale are two mixing angles ($`\theta _{12}`$ and $`\theta _{23}`$), three neutrino masses, and two Majorana phases. We found that (1) $`\mathrm{sin}^22\theta _{12}`$ at the low energy scale must be less than that at $`M_R`$ scale, (2) the induced $`|V_{13}|`$ can be as large as 0.05 if masses of neutrinos are around 0.05 eV.

thanks: a talk given at PANIC02, Osaka, September, 2002

The recent experimental data by SuperKamiokande and SNO show that the solar neutrino mixing angle is $`\mathrm{tan}^2\theta _{}0.34`$ and the atmospheric neutrino mixing angle is $`\mathrm{sin}^22\theta _{\mathrm{atm}}1`$, while $`|\mathrm{sin}\theta _{13}|`$=$`|V_{13}|<0.16`$. These data show a particular pattern, that is, mixing angles $`\theta _{12}=\theta _{}`$ and $`\theta _{23}=\theta _{\mathrm{atm}}`$ are large, while $`\theta _{13}`$ is quite small.
There must be some reason why $`\theta _{13}`$ is so small in comparison with the other. By taking this fact seriously, we assume that $`\theta _{13}=0`$ so that the Dirac phase, $`\delta `$ is zero at $`M_R`$ where neutrino mass matrix is generated. The neutrino mixing matrix at $`M_R`$ is described by two mixing angles, three neutrino masses and two Majorana phases. In this scenario, the angle $`\mathrm{sin}\theta _{13}=|V_{13}|`$ and $`\delta `$ are induced by the renormalization group. We construct a model along this scenario and observe what is the role of Majorana phases for the renormalization group, in what situation the experimentally measurable size of $`|V_{13}|`$ is induced and what is the prediction for $`\delta `$ following the recent work by Miura, Shindou and Takasugi .
The mass matrix at $`M_R`$: The mass matrix which gives $`V_{13}=0`$ is generally expressed by $`m_\nu (M_R)=O\mathrm{diag}(M_1,M_2e^{i\alpha _0},M_3e^{i\beta _0})O^T`$, where $`\alpha _0`$ and $`\beta _0`$ are Majorana phases. $`O`$ is the mixing matrix at $`M_R`$ scale and is given by $`O=O_{23}(\theta _{23})O_{12}(\theta _{12})`$
The neutrino mass matrix at $`m_Z`$: The mass matrix is given by $`m_\nu (m_Z)=\mathrm{diag}(1,1,\alpha )OD_\nu O^T\mathrm{diag}(1,1,\alpha )`$, where $`\alpha `$ is defined by $`\alpha 1ϵ=1/\sqrt{I_\tau }=(\frac{m_Z}{M_R})^{\frac{1}{8\pi ^2}(1+\mathrm{tan}^2\beta )(m_\tau /v)^2}<1`$. Here, $`v^2=v_u^2+v_d^2`$ and $`\mathrm{tan}\beta =v_u/v_d`$ with $`v_i=H_i(i=u,d)`$ for the MSSM model. By taking $`M_\mathrm{R}=10^{13}(\mathrm{GeV})`$ and $`2<\mathrm{tan}\beta <50`$, we find $`8\times 10^4<ϵ<5\times 10^2`$.
The followings are known: (a) The mixing angles are stable for the case of the hierarchical or the anti-hierarchical neutrino mass scheme, $`m_1m_2m_3`$ or $`m_3m_1m_2`$. (b) The instability occurs for $`m_1m_2`$. (c) The Majorana phases in neutrino masses may play important role.
We focus on the unstable case, $`M_1M_2,\mathrm{\hspace{0.33em}0}<\mathrm{\Delta }_{21}|\mathrm{\Delta }_{31}|`$, $`0<\mathrm{\Delta }_{21}M_1^2,ϵM_1^2ϵM_2^2|\mathrm{\Delta }_{31}|`$, where $`\mathrm{\Delta }_{21}=M_2^2M_1^2`$, $`\mathrm{\Delta }_{31}=M_3^2M_1^2`$. The diagonalization of the neutrino mass matrix is made analytically.
We parameterize the mixing matrix at $`m_Z`$ scale as

$`V=\left(\begin{array}{ccc}c_{}& s_{}& |V_{13}|e^{i\delta }\\ s_{}c_{\mathrm{atm}}& c_{}c_{\mathrm{atm}}& s_{\mathrm{atm}}\\ s_{}s_{\mathrm{atm}}& c_{}s_{\mathrm{atm}}& c_{\mathrm{atm}}\end{array}\right)\left(\begin{array}{ccc}1& & \\ & e^{i\alpha _M}& \\ & & e^{i\beta _M}\end{array}\right),`$ (1)
and masses as $`m_i`$. Among them, stable quantities are $`m_i`$ and $`\mathrm{\Delta }m_{\mathrm{atm}}^2=m_3^2m_2^2`$ and $`\theta _{\mathrm{atm}}`$, that is, $`m_iM_i`$, $`\mathrm{\Delta }m_{\mathrm{atm}}^2M_3^2M_1^2`$ and $`\theta _{\mathrm{atm}}\theta _{23}`$. The unstable ones are $`\theta _{}`$ and $`\mathrm{\Delta }m_{}^2=m_2^2m_1^2`$. The angle $`\theta _{13}|V_{13}|`$ and a Dirac phase $`\delta `$ are induced by the renormalization group.
As for $`\mathrm{\Delta }m_{}^2`$, we have $`\mathrm{\Delta }m_{}^2=(\mathrm{\Delta }_{21}4ϵm_1^2s_{\mathrm{atm}}^2\mathrm{cos}2\theta _{12})/\mathrm{cos}2\theta `$, where $`\mathrm{tan}2\theta =4ϵm_1^2s_{\mathrm{atm}}^2\mathrm{sin}2\theta _{12}\mathrm{cos}\frac{\alpha _0}{2}/(\mathrm{\Delta }_{21}4ϵm_1^2s_{\mathrm{atm}}^2\mathrm{cos}2\theta _{12})`$ In the following, we take the convention, $`\mathrm{\Delta }_{21}>0`$ and $`\mathrm{\Delta }m_{}^2>0`$ in accordance with $`\mathrm{tan}^2\theta _{}=0.34<1`$.
As for the solar mixing angle, we have $`s_{}=|s_{12}c+c_{12}se^{i\alpha _0/2}|`$, $`c_{}=|c_{12}cs_{12}se^{i\alpha _0/2}|`$. The angle $`s_{13}=\mathrm{sin}\theta _{13}`$ is given by $`|V_{13}|=ϵm_1m_3\mathrm{sin}2\theta _{12}\times \mathrm{sin}2\theta _{\mathrm{atm}}\mathrm{sin}\frac{\alpha _0}{2}/\mathrm{\Delta }m_{\mathrm{atm}}^2`$. The Dirac phase, $`\delta `$ and two Majorana phases, $`\alpha _M`$ and $`\beta _M`$ are given explicitly.
(1) $`\mathrm{tan}^2\theta _{}`$: The solar mixing angle $`\theta _{}`$ at $`m_Z`$ and $`\theta _{12}`$ at $`M_R`$ are related as

$`1+\mathrm{cos}\alpha _0={\displaystyle \frac{|\mathrm{cos}2\theta _{}|h\mathrm{cos}^22\theta _{12}+\mathrm{cos}2\theta _{12}\sqrt{h^2\mathrm{cos}^22\theta _{12}+2|\mathrm{cos}2\theta _{}|h+1}}{h\mathrm{sin}^22\theta _{12}}},`$
where $`h=2ϵm_1^2s_{\mathrm{atm}}^2/\mathrm{\Delta }m_{}^2`$. From this formula, we see that the solar mixing angle, $`\theta _{}`$ is given by $`m_1`$ (the mass at $`m_z`$), $`\theta _{12}`$ (the angle at $`M_R`$), and $`\alpha _0`$ (Majorana phase), if we use $`\theta _{\mathrm{atm}}`$, $`\mathrm{\Delta }m_{}^2`$ and $`ϵ`$. We computed the relation among $`m_1`$, $`\theta _{12}`$ and $`\alpha _0`$ by taking $`\mathrm{tan}^2\theta _{}=0.37`$, $`\mathrm{\Delta }m_{}^2=5\times 10^5\mathrm{eV}^2`$ and $`\mathrm{sin}^22\theta _{\mathrm{atm}}=1`$ for $`\mathrm{tan}\beta =50`$. The result is shown in Fig.1, where we observe that the wide range of $`\theta _{12}`$ (the solar angle at $`M_R`$) can reproduce the experimental solar angle $`\theta _{}`$ when for $`m_10.05`$ eV and $`\pi /2<\alpha _0<\pi `$. By requiring $`01+\mathrm{cos}\alpha 2`$,

$`{\displaystyle \frac{\mathrm{sin}^22\theta _{}}{\mathrm{sin}^22\theta _{}+(|\mathrm{cos}2\theta _{}|+4ϵs_{\mathrm{atm}}^2(m_1^2/\mathrm{\Delta }m_{}^2))^2}}\mathrm{sin}^22\theta _{12}\mathrm{sin}^22\theta _{}.`$ (3)
(2) $`|V_{13}|`$: This quantity is proportional to $`ϵm_1m_3/\mathrm{\Delta }m_{\mathrm{atm}}^2`$ so that it is small. In Fig.2, we plot the predicted value of $`|V_{13}|(m_1/m_3)`$ in the $`\mathrm{sin}^2\theta _{}`$ and $`m_1`$ plane for $`\mathrm{tan}\beta =50`$. We observe that $`|V_{13}|0.05`$ may be expected when $`m_10.05`$eV.
(3) $`\delta `$: We parametrize it as $`\delta =\delta _1\beta _0`$. Then, we can predict $`\delta _1`$ as a function of $`m_1`$, $`\theta _{12}`$ and $`\alpha _0`$. In Fig.3, we show the expected value of $`\mathrm{sin}\delta _1`$ ($`\delta _1=\delta \beta _0`$).
(4) $`m_\nu `$: The effective mass for the neutrinoless double beta decay in this mode is given by

$`m_\nu \left|{\displaystyle \underset{j}{}}m_jV_{ej}^2\right|m_1\sqrt{1\mathrm{sin}^22\theta _{12}\mathrm{sin}^2{\displaystyle \frac{\alpha _0}{2}}}m_1,`$ (4)
where we used $`m_1m_2`$. If $`m_10.05`$eV, we expect $`m_\nu `$ to be the same order as seen in Fig.3.
Summary: The assumption that $`|V_{13}|=0`$ at $`M_R`$ scale is attractive because this it enables to predict the value of $`|V_{13}|`$ and the Dirac phase is induced by the renormalization group, through two Majorana phases. Since at high energy there are only Majorana phases, which may be related to Majorana phases which contribute to Leptogenesis.

Acknowledgment: This work is supported in part by the Japanese Grant-in-Aid for Scientific Research of Ministry of Education, Culture, Sports, Science and Technology (No.12047218).