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# Conformation of a Polyelectrolyte Complexed to a Like-Charged Colloid

## Abstract

We report results from a molecular dynamics (MD) simulation on the conformations of a long flexible polyelectrolyte complexed to a charged sphere, both negatively charged, in the presence of neutralizing counterions in the strong Coulomb coupling regime. The structure of this complex is very sensitive to the charge density of the polyelectrolyte. For a fully charged polyelectrolyte the polymer forms a dense two-dimensional ”disk”, whereas for a partially charged polyelectrolyte the monomers are spread over the colloidal surface. A mechanism involving the overcharging of the polyelectrolyte by counterions is proposed to explain the observed conformations.

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Polyelectrolytes in polar solvents are polymers carrying dissociated ionic groups. When a polyelectrolyte is in the vicinity of a charged colloidal particle, both may coagulate leading to charge complexation. Studying this process is motivated by many sources. The presence of polyelectrolytes has important effects on the stabilization of colloidal suspensions Evans\_book\_1999 . Besides that, for polyelectrolytes such as DNA the interaction with the interface of charged membranes or charged particles (histones) is crucial for many biophysical properties Holde\_chromatin\_1989 . Finally long range Coulomb interactions represent a theoretical challenge, especially for the understanding of effective attractions between like charged bodiesha97a ; shklovskii99a ; levin99a ; lau00a .

The adsorption of polyelectrolytes onto an oppositely charged spherical particle has recently been experimentally extensively studied Holde\_chromatin\_1989 ; McQuigg\_JPhysChem\_1992 ; Grunstein\_Nature\_1997 ; Caruso\_Science\_1998 . Various authors have also investigated this phenomenon theoretically Muthukumar\_JCP\_1994 ; Marky\_JMolBiol\_1995 ; Sens\_PRL\_1999 ; Mateescu\_EPL\_1999 ; Netz\_Macromol\_1999 ; Schiessel\_EPL\_2000 ; Nguyen\_EPL\_2000  and by numerical simulations Wallin\_Langmuir\_1996\_I ; Kong\_JCP\_1998 ; kunze00a . However, much less is known concerning the complexation of a charged sphere with a like-charged polyelectrolyte. To our knowledge there has been no study in this direction until now.

In this Letter, we report the rather unexpected complexation between a charged sphere and a long flexible polyelectrolyte, both like (here negatively) charged. This article constitutes a first attempt to elucidate this striking phenomenon. We present results of MD simulation of the two macroions taking into account the counterions explicitly, but add for simplicity no salt. We propose a mechanism stemming from the polyelectrolyte overcharging to explain the complexation structure as well as the observed polyelectrolyte conformations.

The MD method employed here is based on the Langevin equation and is the same as the one employed in previous studies Messina\_PRL\_2000 . Consider within the framework of the primitive model one spherical macroion characterized by a radius $`r_0`$ and a bare charge $`Q=Z_Me`$ (where $`e`$ is the elementary charge and $`Z_M>0`$) surrounded by an implicit solvent of relative dielectric permittivity $`ϵ_r`$. The polymer chain is made up of $`N_m`$ monomers of diameter $`l`$. Both ends of the chain are always charged. The monomer charge fraction is $`f`$ (i.e. every $`1/f`$ monomer is charged) so that the chain contains $`N_{cm}=(N_m1)f+1`$ charged monomers. The monomer charge is $`q_m=Z_me`$ (with $`Z_m>0`$). To ensure global electroneutrality we added $`N_c`$ small counterions of diameter $`\sigma `$ and charge $`+Z_ce`$ (with $`Z_c>0`$). The whole system is confined in an impermeable spherical cell of radius $`R`$, and the spherical macroion is held fixed at the center of the cell. The dielectric permittivity is the same everywhere, in and outside the cell.

Except for the spherical macroion all particles are mobile. Excluded volume interactions are introduced via a pure short-range repulsive Lennard-Jones potential given by

$$U_{LJ}(r)=4ϵ_{LJ}\left[\left(\frac{\sigma }{rr_0}\right)^{12}\left(\frac{\sigma }{rr_0}\right)^6\right]+ϵ_{LJ}$$
(1)
for $`rr_0<2^{1/6}\sigma `$, and $`0`$ otherwise. We have set $`r_0=7\sigma `$ for the macroion-counterion interaction, and $`r_0=0`$ otherwise. The length and energy simulation units are defined by $`\sigma `$ (counterion diameter) and $`ϵ_{LJ}`$, respectively. The closest center-center distance of the ions to the spherical macroion is $`a=r_0+\sigma =8\sigma `$. The macroion volume fraction is defined as $`f_M=(a/R)^3`$ and was fixed with $`R=40\sigma `$ to $`8\times 10^3`$.

The electrostatic interaction between any pair $`ij`$, where $`i`$ and $`j`$ denote either a macroion or a charged microion (counterion or charged monomer), reads

$$\frac{U_{coul}(r)}{k_BT}=l_B\frac{Z_iZ_j}{r},$$
(2)
where $`l_B=e^2/4\pi ϵ_0ϵ_rk_BT`$ is the Bjerrum length. To link this to experimental units and room temperature we denote $`ϵ_{LJ}=k_BT`$ ($`T=298`$ K). Being interested in the strong Coulomb coupling regime we choose the relative permittivity $`ϵ_r=16`$, corresponding to $`l_B=10\sigma `$ (with $`\sigma =3.57`$ Å), divalent microions ($`Z_m=Z_c=2`$) and $`Z_M=180`$.

The polyelectrolyte chain connectivity is modeled by using a standard anharmonic finitely extensible nonlinear elastic (FENE) potential in good solvent (see for example Ref. KG\_JCP\_1990 ), which reads $`U_{FENE}(r)=\frac{1}{2}\kappa R_0^2\mathrm{ln}\left[1\frac{r^2}{R_0^2}\right]`$, where $`\kappa `$ is the spring constant chosen as $`1000k_BT/\sigma ^2`$ and $`R_0=1.5\sigma `$. These values lead to an equilibrium bond length $`l=0.8\sigma `$.

Four different parameter combinations, denoted by run A, B, C and D, were investigated and are summarized in Table 1. Going from run A to D we decreased the charge fraction $`f`$ from 1 to 0.2, and thereby decreased the linear charge density $`\lambda _{PE}`$ of the polyelectrolyte. The contour length of the chain is much larger than the colloidal particle diameter ($`N_ml/(2r_0)14`$ times), so that in principle the chain can wrap around the colloidal particle several times.

Figure 1 shows typical equilibrium configurations of the colloid-polyelectrolyte complex. Note that in all reported cases complexation occurs and the polyelectrolyte is completely adsorbed on the colloidal surface. However, the structure of the resulting complexes depends strongly on $`f`$. For the fully charged polyelectrolyte case \[see Fig. 1(a) with $`f=1`$\] the chain monomers are closely packed together with their counterions forming a two-dimensional dense aggregate. This conformation consists of alternating lines made of monomers and counterions, respectively. When the linear charge density is reduced \[see Fig. 1(b) and Fig. 1(c)\], the complex structures are qualitatively different. In these cases the chain monomers are no longer densely packed. For run B \[Fig. 1(b)\], the monomers spread more over the colloidal surface and the polymer chain partially wraps around the sphere suggesting almost a surface pearl necklace structure. For run C \[Fig. 1(c)\], the chain wraps entirely over the colloidal surface, leading to a quasi isotropic distribution of the monomers around the spherical macroion.

The physical reason of the complex formation is due to the strong counterion mediated attractions. Basically, the charged species is trying to crystallize in a way which is compatible with the topological constraints (here mainly the chain connectivity and the macroion surface).

To quantify the adsorption of the chain monomers and counterions on the macroion surface, we look at the observable $`P(r)`$, being defined as the amount of monomers (counterions) reduced to the total number of monomers $`N_m`$ (the total number of counterions $`N_c`$) within a distance $`r`$ from the spherical macroion center. Results are depicted in Fig. 2, where we observe for all runs that the particles are condensed within a distance of about $`10\sigma `$ from the colloid center and more than 80% of the monomers and counterions are within a distance of $`9.3\sigma `$ from the colloid center, corresponding roughly to two particle layers. Due to strong electrostatic attraction between the sphere and the counterions and strong electrostatic repulsion between the sphere and the charged monomers, the first layer ($`ra=8\sigma `$) is exclusively made up of counterions. Note that the monomer depletion in this first layer also concerns neutral monomers (runs B-D) and this effect is attributed to the chain

connectivity. The charged monomers in the second layer repel each other strongly, and keep for high values of $`f`$ the chain under tension and thus the neutral monomers almost out of the first layer. The second layer consists of both, chain monomers and counterions.

Next, we investigate the radius of gyration $`R_g`$ (in three dimensions) of the chain in order to gain insight of the spreading of the monomers over the sphere. Results are reported in Fig. 3. It clearly indicates that $`R_g`$ increases with increasing $`f`$, which demonstrates that the spreading of the monomers over the macroion surface is enhanced by decreasing the polyelectrolyte charge density. The jump in $`R_g`$ is particularly large between the results for $`f=1`$ and $`f<1`$. This is in agreement with the visual inspections of the polymer conformations presented in Fig. 1.

Moreover, the isotropic case (monomers fully spread over the particle) corresponding to $`R_ga+l=8.8\sigma `$ is already reached for $`f=1/2`$ (run $`B`$).

In the following we are going to argue that the polyelectrolyte overcharging is a fundamental key to explain the observed complex structure. Let $`N_{cd}`$ be the number of condensed counterions on the polyelectrolyte where counterions are assumed to be condensed onto the polyelectrolyte when they lie within a distance $`r_c=1.2\sigma `$ to the nearest chain monomer. Then the overcharging ratio $`\chi _{PE}`$ is defined as

$$\chi _{PE}=\frac{N_{cd}}{N_{cm}},$$
(3)
which is merely the ratio between the amount of the total condensed counterion charge (on the chain) and the polyelectrolyte bare charge.

This overcharging can also be analytically predicted by the simple assumption that the uncondensed counterions, i.e. those who are not ”attached” to the chain, have the same surface pair distribution as in the case where the polyelectrolyte and its condensed counterions are absent, i. e., where we just have the macroion and its condensed counterions presentNOTE\_gr . This allows us to consider the polyelectrolyte chain as a neutral object, namely the bare charged chain plus its own neutralizing counterions which then in turn gets overcharged by intercepting all counterions of the macroion which are thought of being uniformly distributed over the macroion surface. We consider counterions as belonging to the chain if their center lies within a ribbon of width $`2r_c`$ and area $`A_{rib}=2r_cN_ml`$. If $`c`$ is the counterion (of the macroion) concentration then the theoretical overcharge $`\chi _{th}`$ is merely given by

$$\chi _{th}=1+\frac{A_{rib}c}{N_{cm}}=1+\frac{2r_cN_mlZ_M}{N_{cm}Z_c4\pi a^2},$$
(4)
and for $`N_m1`$ we have

$$\chi _{th}1+C/f,$$
(5)
where $`C=\frac{2r_clZ_M}{Z_c4\pi a^2}`$.

Results are presented in Fig. 4. It indicates that in all cases overcharging is present (i.e., $`\chi _{PE}>1`$), and that $`\chi _{PE}`$ increases with decreasing polyelectrolyte charge density. We have excellent agreement (less than 10% difference) between the simulational results and our toy model \[Eq. (4)\]. In turn it explains why $`\chi _{PE}`$ varies quasi linearly with $`1/f`$.

The f-dependency of the complexation structure can be explained with this overcharging. Indeed, in terms of many-body physics the overcharged polyelectrolyte can be seen as a dressed (or renormalized) particle \[bare particle + clothing\] with a new effective (or renormalized) linear charge density $`\lambda _{PE}^{}=(\chi _{PE}1)\lambda _{PE}`$ which has an opposite sign to the bare linear charge density $`\lambda _{PE}`$ NOTE\_Many\_Body . In this respect, one can also define a renormalized charged monomer of effective charge

$$q_m^{}=(\chi _{PE}1)q_m.$$
(6)
Using Eq. (6) and the results of Fig. 4 this shows that the absolute value of $`q_m^{}`$ increases with increasing $`1/f`$, and therefore the renormalized polyelectrolyte self-interaction leads to a stronger effective monomer- effective monomer repulsion, which in turn explains why the chain expands with increasing $`1/f`$ (see Fig. 1 and Fig. 3 for the corresponding structures) NOTE\_Many\_Body\_b .

In summary, we have shown that in the strong Coulomb coupling regime, a charged spherical macroion and a long polyelectrolyte can make a complex even if both carry many like charges. The resulting structure of the charge complex depends strongly on the linear charge density of the chain. For a fully charged polyelectrolyte, its chain monomers and condensed counterions are densely packed and the polymer wraps only partially the sphere. By decreasing the linear charge density, the wrapping becomes complete. The resulting polyelectrolyte conformations can be explained by the degree of overcharging of the polyelectrolyte which in turn depends on its linear charge density.

A future study will include many other important effects, such as chain length and flexibility, enlarged permittivity constant (weaker Coulomb coupling), added salts, and microions valence to name just the most important parameters. Nevertheless, our observations should trigger new theoretical and experimental works.

This work has been supported by Laboratoires Européens Associés (LEA).


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# 1 Introduction

## 1 Introduction

We have recently suggested that a light, stable, strongly self-coupled scalar field coupled with the Higgs field would be an interesting candidate for solving the problems of the Cold Dark Matter (CDM) model at galactic scales . In here we discuss some early Universe history of this particle . Our proposal involves a particle physics-motivated model, where the DM particles are allowed to self-interact so as to have a large scattering cross section and negligible annihilation or dissipation. The self-interaction results in a characteristic length scale given by the mean free path of the particle in the halo. This idea was originally proposed to suppress small scale power in the standard CDM model  and has been recently revived, in a general context, in order to address CDM difficulties at galactic scale . Our model  is a concrete realization of this idea and involves an extra gauge singlet as the self-interacting, non-dissipative cold dark matter particle. Following Ref. , we call this scalar particle phion, $`\varphi `$, and assume that it couples to the Standard Model (SM) Higgs boson, $`h`$, with a Lagrangian density given by:

$$=\frac{1}{2}(_\mu \varphi )^2\frac{1}{2}m_\varphi ^2\varphi ^2\frac{g}{4!}\varphi ^4+g^{}v\varphi ^2h,$$
(1)
where $`g`$ is the phion self-coupling constant, $`m_\varphi `$ its mass, $`v=246\text{GeV}`$ is the Higgs vacuum expectation value and $`g^{}`$ is the coupling between $`\varphi `$ and $`h`$. A model along these lines have been previously discussed . Clearly the interaction term between the phion and the Higgs boson arises from a quartic interaction $`\frac{g^{}}{2}\varphi ^2H^2`$, where $`H`$ is the electroweak Higgs doublet. As shown in , the $`\varphi `$ mass does not arise from spontaneous symmetry breaking since this would yield a tiny scalar self-coupling constant. The phion mass in (1) should be regarded as as a phenomenological parameter arising from a more encompassing theory.

As is well known, scalar particles have been repeatedly invoked as DM candidates ; however, our proposal has the salient feature that it brings about a connection with the SM Higgs boson which could arise in extensions of the SM. For instance, the hidden sector of heterotic string theories does give rise to astrophysically interesting self-interacting scalars . For reasonable values of $`g^{}`$, the new scalar would introduce a novel invisible decay mode for the Higgs boson. This could, in principle, provide an explanation for the failure in finding the Higgs boson at accelerators sofar.

On the astrophysical front, recent observational data on large scale structure, Cosmic Microwave Background anisotropies and type Ia Supernovae suggest that $`\mathrm{\Omega }_{tot}1`$, of which $`\mathrm{\Omega }_{baryons}0.05`$ and $`\mathrm{\Omega }_\mathrm{\Lambda }0.65`$ ; the remaining contribution, $`\mathrm{\Omega }_{DM}0.3`$ (apart from neutrinos that may contribute a small fraction), comes from dark matter (DM), which determines the hierarchy of the structure formation in the Universe. The most prominent theories of structure formation are now $`\mathrm{\Lambda }`$CDM and QCDM, which consist, respectively, of the standard Cold Dark Matter (CDM) model supplemented by a cosmological constant or a dark energy, i.e. a negative pressure component.

In the CDM model, initial Gaussian density fluctuations, mostly in non-relativistic collisionless particles, the so-called cold dark matter, grow during the inflationary period of the Universe and evolve, via gravitational instability, into the structures one observes at present. However, it has been found that the CDM model cannot sucessfully accomodate the data observed on all scales. For instance, N-body simulations predict a number of halos which is about an order of magnitude grater than the observed number at the level of Local Group . Furthermore, astrophysical systems that are DM dominated, e.g. dwarf galaxies  show shallow matter–density profiles with finite central densities. This contradicts high resolution N-body simulations , which have singular cores, with $`\rho r^\gamma `$ and $`\gamma `$ in the range between 1 and 2. This can be interpreted as an indication of the fact that since cold collisionless DM particles do not have any characteristic length scale they lead, due to hierarchical gravitational collapse, to very dense dark matter halos that present negligible core radius.

On the other hand, recent numerical simulations  indicate that the self-interaction of DM particles does bring noticeable improvements on the properties of the CDM model on small scales.

At present, $`\varphi `$ particles are non-relativistic, with typical velocities $`v200`$ km s<sup>-1</sup>, and, therefore, it is impossible to dissipate energy creating more particles in reactions like $`\varphi \varphi \varphi \varphi \varphi \varphi `$. Thus, as only the elastic channel is kinematically accessible, near threshold, the cross section is given by:

$$\sigma (\varphi \varphi \varphi \varphi )\sigma _{\varphi \varphi }=\frac{g^2}{16\pi s}\frac{g^2}{64\pi m_\varphi ^2}.$$
(2)
A limit on $`m_\varphi `$ and $`g`$ can be obtained by demanding that the mean free path of the particle $`\varphi `$, $`\lambda _\varphi `$, is in the interval $`1\text{kpc}<\lambda _\varphi <1`$Mpc . Hence, we have:

$$\lambda _\varphi =\frac{1}{\sigma _{\varphi \varphi }n_\varphi }=\frac{m_\varphi }{\sigma _{\varphi \varphi }\rho _\varphi ^h},$$
(3)
where $`n_\varphi `$ and $`\rho _\varphi ^h`$ are, respectively, the number and mass density of $`\varphi `$ particles in the halo. Eqs. (2) and (3) imply that

$`\sigma _{\varphi \varphi }`$ $`=`$ $`2.1\times 10^3\left({\displaystyle \frac{m_\varphi }{\text{GeV}}}\right)\left({\displaystyle \frac{\lambda _\varphi }{\text{Mpc}}}\right)^1`$ (4)
$`\times `$ $`\left({\displaystyle \frac{\rho _\varphi ^h}{0.4\text{GeV}\text{cm}^3}}\right)^1\text{GeV}^2,`$
which, in turn, leads to:

$$m_\varphi =13g^{2/3}\left(\frac{\lambda _\varphi }{\text{Mpc}}\right)^{1/3}\left(\frac{\rho _\varphi ^h}{0.4\text{GeV}\text{cm}^3}\right)^{1/3}\text{MeV}.$$
(5)
We shall next analyse how the requirement that $`\mathrm{\Omega }_\varphi h^20.3`$, i.e. that the phion is a suitable DM candidate, and that the phion is able to explain small scale structure, leads to bounds on the couplings $`g`$ and $`g^{}`$.

## 2 Phion density estimate

If the coupling constant $`g^{}`$ is sufficiently small, phions decouple early in the thermal history of the Universe and are diluted by subsequent entropy production. In Ref. , it was considered out-of-equilibrium phion production via inflaton decay in the context of $`N=1`$ Supergravity inflationary models (see. e.g.  and references therein) and found that $`\mathrm{\Omega }_\varphi h^20.3`$ can be naturally achieved.

On the other hand, for certain values of the coupling $`g^{}`$, it is possible that $`\varphi `$ particles are in thermal equilibrium with ordinary matter. In order to determine whether this is the case, we will make the usual comparison between the thermalization rate $`\mathrm{\Gamma }_{th}`$ and the expansion rate of the Universe $`H`$.

The thermalization rate is given by

$$\mathrm{\Gamma }_{th}=n<\sigma _{ann}v_{rel}>,$$
(6)
where $`n=1.2\times T^3/\pi ^2`$ is the density of relativistic phions and $`<\sigma _{ann}v_{rel}>`$ is the annihilation cross section averaged over relative velocities. On the other hand, the expansion rate is given by:

$$H=\left(\frac{4\pi ^3g_{}}{45}\right)^{1/2}\frac{T^2}{M_P}=1.66\times g_{}^{1/2}\frac{T^2}{M_P}.$$
(7)
At temperatures above the electroweak phase transition, $`T_{EW}300\text{GeV}`$, a typical value in many extensions of the SM where one hopes to find the required features to achieve successful baryogenesis, the order parameter (the vacuum expectation value of the Higgs field) vanishes, and hence the $`\varphi \varphi h`$ coupling is non-operative. However, this interaction term has its origin in the 4-point coupling, $`\varphi \varphi hh`$, which can keep, at high temperatures, the phion-Higgs system into thermal equilibrium. Using the temperature as the center-of-mass energy, the cross section is given by:

$$\sigma _{ann}v_{rel}\frac{g^2}{32\pi T^2},$$
(8)
which implies that phions are in thermal equilibrium for temperatures smaller than

$$T_{eq}\frac{g^2M_P}{32\pi ^3g_{}^{1/2}}.$$
(9)
Therefore, phions cannot be in thermal equilibrium before the electroweak phase transition if $`g^{}\text{ }<10^7`$.

Thermal equilibrium can be achieved just below $`T_{EW}`$, when the trilinear coupling is operative, if $`g^{}`$ is such that the thermalization rate, $`\mathrm{\Gamma }_{th}`$, exceeds the Hubble expansion rate. Let us quantify the conditions on $`g^{}`$ to satisfy this condition.

The phion annihilation cross section ($`T\text{ }>m_h`$) is given by the relativistic Breit-Wigner resonance formula:

$$\sigma _{ann}v_{rel}=\frac{4\pi (s/m_h^2)\mathrm{\Gamma }(h\varphi \varphi )\mathrm{\Gamma }_h}{(sm_h^2)^2+m_h^2\mathrm{\Gamma }_h^2},$$
(10)
where $`\mathrm{\Gamma }_h`$ is the total Higgs decay rate. At the resonance peak ($`s=m_h^2`$) it simplifies to

$$\sigma _{ann}v_{rel}=\frac{4\pi }{m_h^2}BR(h\varphi \varphi ).$$
(11)
From the Higgs decay width into phions

$$\mathrm{\Gamma }(h\varphi \varphi )=\frac{g{}_{}{}^{}{}_{}{}^{2}v_{}^{2}(m_h^24m_\varphi ^2)^{1/2}}{32\pi m_h^2},$$
(12)
we get the decoupling temperature in the limit $`m_hm_\varphi `$:

$$T_D150\frac{\mathrm{\Gamma }_hm_h^3}{g^2M_Pv^2}.$$
(13)
Thus, in order to have a decoupling temperature of the order of the Higgs mass, the coupling constant should be fairly small:

$$g^{}10^{10},$$
(14)
where we have introduced the SM value of $`\mathrm{\Gamma }_h=3.2\text{MeV}`$, obtained from the code HDECAY , for a $`m_h=115\text{GeV}`$ Higgs boson.

Hence, if $`g^{}10^{10}`$, the phions will be kept into thermal equilibrium after the electroweak phase transition. In this situation, there are two possible scenarios depending whether they decouple while relativistic or otherwise.

In order to study these scenarios, we have to establish the decoupling temperature at $`Tm_\varphi T_{EW}`$, in which case the phion annihilation cross section involves virtual Higgs exchange ($`h^{}`$), as in Figure 1, and is given by :

$$\sigma _{ann}v_{rel}=\frac{8g_{}^{}{}_{}{}^{2}v^2}{(4m_\varphi ^2m_h^2)^2+m_h^2\mathrm{\Gamma }_h^2}F_X,$$
(15)
where

$$F_X=\underset{m_h^{}2m_\varphi }{lim}\left(\frac{\mathrm{\Gamma }_{h^{}X}}{m_h^{}}\right),$$
(16)
and $`\mathrm{\Gamma }_{h^{}X}`$ refers to the width for the decay $`h^{}X`$ ($`X\varphi \varphi `$, since we are dealing with inelastic scattering only), for $`m_h^{}=2m_\varphi `$. For the mass range of interest to us, $`m_\varphi 10100\text{MeV}`$, one finds $`F_X10^{13}`$ .

Under these conditions, the relationship between the coupling constant $`g^{}`$ and the decoupling temperature $`T_D`$ is given by

$$g^2=5.5\frac{(m_h/100\text{GeV})^4}{(T_D/\text{MeV})}.$$
(17)
If $`g^{}0.1`$, the phions decouple while relativistic and are as abundant as photons. Since we are interested in stable light phions, it is a major concern avoiding phion overproduction if it decouples while relativistic. Actually, we find that there is an analogue of Lee-Weinberg limit for neutrinos (see e.g. ):

$$\mathrm{\Omega }_\varphi h^20.08\frac{m_\varphi }{1\text{eV}},$$
(18)
yielding a very stringent bound, $`m_\varphi \text{ }<4\text{eV}`$, and therefore, $`g\text{ }<2.5\times 10^{10}`$, for the phion self-coupling constant so to solve the small scale structure problem of the collisionless CDM.

In order to ensure that the phions decouple non-relativistically and that their abundance reduces to acceptable levels without fine-tuning the self-coupling constant, $`g^{}>0.1`$ is required. It follows from standard methods that the phion relic abundance , is given by

$$\mathrm{\Omega }_\varphi h^2=\frac{1.07\times 10^9x_F}{g_{}^{1/2}M_P\sigma _{ann}v_{rel}},$$
(19)
where $`g_{}`$ denotes the number of degrees of freedom in equilibrium at annihilation and $`x_Fm_\varphi /T_F`$ is the inverse of the freeze-out temperature in units of the phion mass. The relevant cross section is the phion annihilation cross section involving virtual Higgs exchange, Eq. (15), with $`F_X10^{13}`$ . The freeze-out temperature is set by the solution of the Boltzmann equation

$$x_F\mathrm{ln}[0.038(g_{}x_F)^{1/2}M_Pm_\varphi \sigma _{ann}v_{rel}].$$
(20)
For obtaining $`x_F1`$ and to apply Eq. (19), it is required that $`g^{}\text{ }>1.2`$, for $`m_\varphi =50\text{MeV}`$ and $`m_h=115\text{GeV}`$. However, due to the smallness of the cross section, the relic abundance of the phion is several orders of magnitude larger than the observed value. Therefore, one can conclude that a phion particle with a mass in this range is excluded.

The smallness of the phion annihilation cross section for $`m_\varphi 50\text{MeV}`$ has its origin in the small factor $`F_X10^{13}`$. However, this factor increases significantly with larger phion masses. For $`m_\varphi 1\text{GeV}`$, $`F_X10^7`$. We find that the requirement $`\mathrm{\Omega }_\varphi h^20.3`$ implies that $`m_\varphi \text{ }>500\text{MeV}`$ and $`g^{}\text{ }>2`$ (which is at the edge of validity of perturbation theory), a solution which holds only for $`m_h\text{ }<130\text{GeV}`$. Heavier phion and Higgs particles tend to make $`\mathrm{\Omega }_\varphi h^2>0.3`$. Our results are depicted in Figure 2.

For these large values of the coupling constant, the decay width of the Higgs into phions is given by:

$$\mathrm{\Gamma }(h\varphi \varphi )=5.23\left(\frac{m_h}{115\text{GeV}}\right)^1g{}_{}{}^{}{}_{}{}^{2}\text{GeV}.$$
(21)
Thus, the Higgs width is totally dominated by the invisible decay mode and this model can be easily tested at future colliders.

## 3 Conclusions

In this contribution, we have derived, bounds on $`g^{}`$, the coupling constant of the Higgs boson to a stable scalar particle, which contribute to Higgs decay via invisible channels. This particle, the phion, is suitable self-interacting dark matter candidate and allows for a solution of the difficulties of the CDM model on small scales.

We find that, for $`g^{}\text{ }<10^{10}`$, the phions never reach thermal equilibrium and are only produced by out-of-equilibrium decay of the inflaton field . In this scenario, the phion does not contribute to the invisible Higgs boson decay channel. For $`g^{}\text{ }>10^{10}`$, we have found that, if $`g^{}\text{ }<0.1`$, the phion decouples while still relativistic and a limit for its mass, $`m_\varphi \text{ }<4\text{eV}`$ can be derived, which, in turn, implies in a strong bound on the phion self-coupling constant, $`g\text{ }<10^9`$. On the other hand, if $`g^{}\text{ }>1`$, the phion decouples while non-relativistic; but, its abundance is not cosmologically acceptable for phion masses in the range of $`50100\text{MeV}`$ due to the small annihilation cross section. For masses in the range of $`0.52\text{GeV}`$, we find that abundances of $`\mathrm{\Omega }_\varphi h^20.3`$ require large values of the coupling $`g^{}2.5`$ and $`m_h\text{ }<130\text{GeV}`$. In this scenario, the Higgs width is dominated by the invisible $`h\varphi \varphi `$ mode and can be tested at future colliders.

ACKNOWLEDGEMENTS

M.C.B. and O.B. would like to acknowledge the partial support of FCT (Portugal) under the grant POCTI/1999/FIS/36285. R.R. is partially supported by a PRONEX (CNPq - Brazil) grant.


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# 1 Introduction

## 1 Introduction

The holographic duality which connects $`d+1`$-dimensional gravity in Anti-de Sitter (AdS) background with $`d`$-dimensional conformal field theory (CFT) has been discussed vigorously for some years. The one of the evidences for the existence of the AdS/CFT correspondence is that the isometry of $`d+1`$-dimensional AdS space $`SO(d,2)`$ is identical with the conformal symmetry of $`d`$-dimensional Minkowski space. Recently much attention has been paid for the duality between de Sitter (dS) gravity and CFT by the analogy of the AdS/CFT correspondence, because the isometry of $`d+1`$-dimensional de Sitter space, $`SO(d+1,1)`$, exactly agrees with the conformal symmetry of $`d`$-dimensional Euclidean space. Thus it might be natural to expect the correspondence between $`d+1`$-dimensional gravity in de Sitter space and $`d`$-dimensional Euclidean CFT (the dS/CFT correspondence). Moreover the holographic principle between the radiation dominated Friedmann-Robertson-Walker (FRW) universe in $`d`$-dimensions and same dimensional CFT with a dual $`d+1`$-dimensional AdS description was studied in ref.. Especially, we can see the correspondence between black hole entropy and the entropy of the CFT which is derived by making the appropriate identifications for FRW equation with the generalized Cardy formula111 The Cardy formula is originally the entropy formula of the CFT only for 2-dimensions.. The generalized Cardy formula expresses the entropy formula of the CFT in any dimensions. From the point of brane-world physics, the CFT/FRW relation sheds further light on the study of the brane CFT in the background of AdS Schwarzschild black hole. There was much activity on the studies of related questions.

The purpose of this letter is the further study of the CFT in de Sitter (dS) Schwarzschild background guided by the analogy of AdS Schwarzschild background. The investigation of dS brane in dS Schwarzschild background in terms of FRW equations has been initiated in ref.. The important difference between AdS space and dS space is the sign of cosmological constant. In case of the brane with time-like (Minkowski) metric on AdS Schwarzschild background, the cosmological constant does not appear because we can choose brane tension to cancel it. But it is impossible for dS Schwarzschild background with the positive cosmological constant. We will see that the cosmological constant always appears in FRW equations deduced from time-like brane trajectory in dS Schwarzschild background 222The work deriving brane cosmological equation in a systematic way for a brane embedded in a bulk with a cosmological constant has been first examined in ref... It is interesting to note that the brane with space-like (Euclidean) metric in dS Schwarzschild background, the cosmological constant of the brane does not appear for the same reason in case of AdS Schwarzschild background. From the point of view of the dS/CFT correspondence, the investigation of space-like brane is more interesting than that of time-like brane.

Furthermore we argue the entropy of the brane CFT which is derived by using generalized Cardy formula for both time-like and space-like branes. We will see that when the brane crosses the horizon of dS Schwarzschild black hole, both for time-like and space-like branes, the entropy of the CFT is identical with the black hole entropy of 5-dimensional dS background as it happens in the AdS/CFT correspondence.

## 2 FRW equations in the background of de Sitter
Schwarzschild black hole

We first consider a 4-dimensional time-like brane in 5-dimensional dS Schwarzschild background. From the analogy of the AdS/CFT correspondence, we can regard that 4-dimensional CFT exists on the brane which is the boundary of the 5-dimensional dS Schwarzschild background. The dynamics of the brane is described by the boundary action:

$`_b={\displaystyle \frac{1}{8\pi G_5}}{\displaystyle _{}}\sqrt{g}𝒦+{\displaystyle \frac{\kappa }{8\pi G_5}}{\displaystyle _{}}\sqrt{g},𝒦=𝒦_i^i`$ (1)
Here $`G_5`$ is 5-dimensional bulk Newton constant, $``$ denotes the surface of the brane, $`g`$ is the determinant of the induced metric on $``$, $`𝒦_{ij}`$ is the extrinsic curvature, $`\kappa `$ is a parameter related to tension of the brane.

From this Lagrangian, we can get the equation of motion of the brane as follows:

$`𝒦_{ij}={\displaystyle \frac{\kappa }{2}}g_{ij},`$ (2)
which implies that $``$ is a brane of constant extrinsic curvature. The bulk action is given by 5-dimensional Einstein action with cosmological constant. The dS Schwarzschild space is one of the exact solutions of bulk equations of motion and can be written in the following form,

$`ds_5^2`$ $`=`$ $`\widehat{G}_{\mu \nu }dx^\mu dx^\nu `$
$`=`$ $`\mathrm{e}^{2\rho }dt^2+\mathrm{e}^{2\rho }dr^2+r^2d\mathrm{\Omega }_3^2,`$
$`\mathrm{e}^{2\rho }`$ $`=`$ $`{\displaystyle \frac{1}{r^2}}\left(\mu +r^2{\displaystyle \frac{r^4}{l^2}}\right).`$ (3)
Here $`l`$ is the curvature radius of dS and $`\mu `$ is the black hole mass. In case of AdS Schwarzschild gravity, there is a holographic relation between FRW brane universe which is reduction from AdS Schwarzschild background and boundary CFT which lives on the brane. We assume that there are some holographic relations between FRW universe which is reduction from dS Schwarzschild background and boundary CFT 333The investigation of dS brane in dS Schwarzschild background in terms of FRW equations has been initiated in ref... To investigate it, we rewrite dS Schwarzschild metric (2) in the form of FRW metric by using a new time parameter $`\tau `$ 444The method discussed here is based on the work.. And the parameter $`t`$ and $`r`$ in (2) are the function of $`\tau `$, namely $`r=r(\tau ),t=t(\tau )`$. For the purpose of getting the 4-dimensional FRW metric, we impose the following condition,

$`e^{2\rho }\left({\displaystyle \frac{t}{\tau }}\right)^2+e^{2\rho }\left({\displaystyle \frac{r}{\tau }}\right)^2=1.`$ (4)
Thus we obtain FRW metric:

$`ds_4^2=g_{ij}dx^idx^j=d\tau ^2+r^2d\mathrm{\Omega }_3^2.`$ (5)
The extrinsic curvature, $`𝒦_{ij}`$, of the brane can be calculated and expressed in term of the function $`r(\tau )`$ and $`t(\tau )`$. Thus one rewrites the equations of motion (2) as

$`{\displaystyle \frac{dt}{d\tau }}={\displaystyle \frac{\kappa r}{2}}e^{2\rho }.`$ (6)
Using (4) and (6), we can derive FRW equation for a radiation dominated universe, Hubble parameter $`H`$ which is defined by $`H=\frac{1}{r}\frac{dr}{d\tau }`$ is given by

$`H^2={\displaystyle \frac{1}{l^2}}{\displaystyle \frac{1}{r^2}}+{\displaystyle \frac{\mu }{r^4}}+{\displaystyle \frac{\kappa ^2}{4}}.`$ (7)
Following AdS Schwarzschild gravity case, we choose $`\kappa =2/l`$ from now on 555 From the point of view of brane-world physics, the tension of brane should be determined without ambiguity. In fact, we can calculate it to cancel the leading divergence of bulk AdS Schwarzschild.. This equation can be rewritten by using 4-dimensional energy $`E_4`$ and volume $`V`$ in the form of the standard FRW equation with the positive cosmological constant $`\mathrm{\Lambda }`$:

$`H^2`$ $`=`$ $`{\displaystyle \frac{1}{r^2}}+{\displaystyle \frac{8\pi G_4}{3}}{\displaystyle \frac{E_4}{V}}+{\displaystyle \frac{\mathrm{\Lambda }}{3}},`$
$`E_4`$ $`=`$ $`{\displaystyle \frac{3\mu V}{8\pi G_4r^4}},\mathrm{\Lambda }={\displaystyle \frac{6}{l^2}}.`$ (8)
Here $`G_4`$ is the 4-dimensional gravitational coupling, which is defined by

$`G_4={\displaystyle \frac{2G_5}{l}}.`$ (9)
$`E_4`$ can be regarded as 4-dimensional energy on the brane in dS Schwarzschild background which is identical with AdS Schwarzschild case. The cosmological constant $`\mathrm{\Lambda }`$ does not appear in AdS Schwarzschild background because we can choose brane tension $`\kappa `$ to cancel the cosmological constant of AdS Schwarzschild background. But it is impossible for dS Schwarzschild case because if we choose brane tension to cancel the cosmological constant of dS Schwarzschild background, the brane tension should be imaginary.

By differentiating eq.(2) with respect to $`\tau `$, we obtain the second FRW equation:

$`\dot{H}`$ $`=`$ $`4\pi G_4\left({\displaystyle \frac{E_4}{V}}+p\right)+{\displaystyle \frac{1}{r^2}},`$
$`p`$ $`=`$ $`{\displaystyle \frac{\mu }{8\pi G_4r^4}}.`$ (10)
Here $`p`$ is 4-dimensional pressure of the matter on the boundary. From eqs.(2) and (2), we find that the energy-momentum tensor is traceless:666 The stress-energy tensor of CFT was caldulated in some asymptotically dS space in a sense of dS/CFT correspondence.

$$T_{}^{\mathrm{matter}\mu }{}_{\mu }{}^{}=\frac{E_4}{V}+3p=0.$$
(11)
Therefore the matter on the brane can be regarded as the radiation, which is consistent with ref.. This means the field theory on the brane should be CFT as in case of AdS Schwarzschild background.

Next, we consider space-like brane in 5-dimensional dS Schwarzschild background. Similarly, we impose the following condition to obtain space-like brane metric instead of eq.(4):

$`e^{2\rho }\left({\displaystyle \frac{t}{\tau }}\right)^2+e^{2\rho }\left({\displaystyle \frac{r}{\tau }}\right)^2=1.`$ (12)
Thus we get following FRW-like metric: 777This metric is also derived by Wick-rotation $`\tau i\tau `$ in eq.(5).

$`ds_4^2=g_{ij}dx^idx^j=d\tau ^2+r^2d\mathrm{\Omega }_3^2.`$ (13)
We again calculate the equations of motion and the extrinsic curvature of space-like brane instead of (2) and (6). These equations lead FRW like equation as follows: 888In ref., the similar equations to eqs.(7), (14) were obtained in terms of Ricci scalar of the induced metric of the brane.

$`H^2={\displaystyle \frac{1}{l^2}}+{\displaystyle \frac{1}{r^2}}{\displaystyle \frac{\mu }{r^4}}+{\displaystyle \frac{\kappa ^2}{4}}.`$ (14)
To cancel the cosmological constant, we take $`\kappa =2/l`$ in the same way of AdS Schwarzschild gravity. We assume this equation can be rewritten by using 4-dimensional energy $`E_4`$ and volume $`V`$ by the analogous form of the standard FRW equations: 999The reason why the sign of FRW equations is different from the standard FRW equations (2) results from the condition (12), namely $`\tau i\tau `$ in eq.(5).

$`H^2`$ $`=`$ $`{\displaystyle \frac{1}{r^2}}{\displaystyle \frac{8\pi G_4}{3}}{\displaystyle \frac{E_4}{V}},E_4={\displaystyle \frac{3\mu V}{8\pi G_4r^4}}.`$ (15)
$`\dot{H}`$ $`=`$ $`4\pi G_4\left({\displaystyle \frac{E_4}{V}}+p\right){\displaystyle \frac{1}{r^2}},p={\displaystyle \frac{\mu }{8\pi G_4r^4}}.`$ (16)
Therefore we find the energy-momentum tensor is traceless from eqs.(15) and (16) again.

We stress again that we can take cosmological constant to zero for FRW-like equation in space-like brane in dS Schwarzschild background as the same way in the AdS/CFT correspondence. This will imply that the dS/CFT correspondence can be valid for space-like brane in dS Schwarzschild background.

## 3 The Cardy-Verlinde formula for the dS/CFT
correspondence

In ref., E. Verlinde showed that the $`d`$-dimensional FRW equation can be regarded as an analogue of the Cardy formula of 2-dimensional CFT.

$$S_4=2\pi \sqrt{\frac{c}{6}\left(L_0\frac{c}{24}\right)}.$$
(17)
For time-like brane of 5-dimensional dS Schwarzschild background, identifying

$`{\displaystyle \frac{2\pi }{3}}\left(E_4r+{\displaystyle \frac{\mathrm{\Lambda }Vr}{8\pi G_4}}\right)`$ $``$ $`2\pi L_0,`$
$`{\displaystyle \frac{V}{8\pi G_4r}}`$ $``$ $`{\displaystyle \frac{c}{24}},`$
$`{\displaystyle \frac{HV}{2G_4}}`$ $``$ $`S_4,`$ (18)
FRW equation (2) has the form (17). The effect of the cosmological constant appears in Cardy formula. We included contribution of the cosmological constant in $`L_0`$ because it shifts the vacuum energy. This means the cosmological entropy bound which is discussed in ref.  should be changed. The Bekenstein bound in 4-dimensions is

$`SS_B,S_B{\displaystyle \frac{2\pi }{3}}Er.`$ (19)
Using eq.(3), the Bekenstein entropy bound should be changed as follows:

$`SS_B,S_B{\displaystyle \frac{2\pi }{3}}\left(Er+{\displaystyle \frac{\mathrm{\Lambda }Vr}{8\pi G_4}}\right).`$ (20)
Then we find out that the effect of the cosmological constant appears in the change of the Bekenstein entropy bound.

For the case of space-like brane, identifying

$`{\displaystyle \frac{2\pi }{3}}E_4r`$ $``$ $`2\pi L_0,`$
$`{\displaystyle \frac{V}{8\pi G_4r}}`$ $``$ $`{\displaystyle \frac{c}{24}},`$
$`{\displaystyle \frac{HV}{2G_4}}`$ $``$ $`S_4,`$ (21)
which is identical with AdS Schwarzschild case exactly.

For both cases, the moments when the brane crosses the horizon101010The time-like brane can only cross the black hole horizon, but the space-like brane can cross the black hole and cosmological horizons. $`r=r_H`$ which is derived from $`e^{2\rho (r_H)}=0`$, the Hubble parameter in (7) becomes

$`H=\pm {\displaystyle \frac{1}{l}}.`$ (22)
Here the plus sign corresponds to the expanding brane universe and the minus one to the contracting universe. We choose the expanding case. Note that eq.(22) is the same form as the case of AdS Schwarzschild black hole. Using eqs.(9),(3), we obtain 4-dimensional entropy $`S_4`$ as follows:

$`S_4={\displaystyle \frac{V}{2lG_4}}={\displaystyle \frac{V}{4G_5}}.`$ (23)
This entropy is nothing but the Bekenstein-Hawking entropy of 5-dimensional dS black hole similar to AdS/CFT correspondence 111111The black hole entropy of AdS background agrees with that of dS background..

We now understand that discovered relation between FRW equations and entropy formulas in ref. can be also applied to dS Schwarzschild background. If we take time-like brane which is the boundary of dS Schwarzschild background, the cosmological constant of the brane appears in FRW equations. Therefore the effect of cosmological constant contributes to raising the the Bekenstein entropy bound. But if we take space-like brane in dS Schwarzschild background, we obtain the approximately same result of AdS Schwarzschild black hole. The difference between space-like brane in dS Schwarzschild background and time-like brane in AdS Schwarzschild background is the sign of FRW equations. When the brane crosses the horizon of dS Schwarzschild black hole, both for time-like and space-like brane, the entropy formula of the CFT exactly agrees with the black hole entropy of 5-dimensional dS background as it happens in the AdS/CFT correspondence. This implies that the holographic principle holds true for dS Schwarzschild background.

## Acknowledgements

The author would like to thank S. Nojiri and S.D. Odintsov for reading the manuscript and useful discussions. The author wishes to thank Y. Hyakutake, A. Ishibashi for helpful discussions and advices. This work was supported in part by the Japan Society for the Promotion of Science under the Postdoctoral Research Programs.