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# Like-Charge Colloid-Polyelectrolyte Complexation

## I Introduction

The adsorption of polyelectrolytes onto an oppositely charged spherical particle has been experimentally extensively studied recently Holde\_chromatin\_1989 ; McQuigg\_JPhysChem\_1992 ; Grunstein\_Nature\_1997 ; Caruso\_Science\_1998 . Various authors have investigated this phenomenon theoretically Muthukumar\_JCP\_1994 ; Marky\_JMolBiol\_1995 ; Sens\_PRL\_1999 ; Mateescu\_EPL\_1999 ; Park\_EPL\_1999 ; Netz\_Macromol\_1999 ; Schiessel\_EPL\_2000 ; Kunze\_PRL\_2000 ; Nguyen\_Physica\_2001  and by Monte Carlo simulations Wallin\_Langmuir\_1996\_I ; Wallin\_JPhysChem\_1996\_II ; Wallin\_JPhysChemB\_1997\_III ; Kong\_JCP\_1998 ; Jonsson\_JCP\_2001 . Nonetheless, much less is known concerning the complexation of a charged sphere with a like-charged polyelectrolyte. It is only very recently that we reported in a short communication such a phenomenon in the strong Coulomb coupling regime Messina\_PRL\_2001 . From a theoretical point of view, the long range Coulomb interactions of these systems represents a formidable challenge, and especially the understanding of effective attraction of like charged bodies has attracted recent attention

In this paper, we elaborate on the complexation between a sphere and a long flexible polyelectrolyte both negatively charged. While complexation in the strong coupling limit it is expected, we report new and rather unexpected chain conformations. We present MD simulation results without added salt but taking into account the counterions explicitly. Various Coulomb couplings as well as different polyelectrolyte linear charge densities are investigated. A detailed study of the ions (monomer and counterion) distribution is reported and mechanisms accounting for the different encountered complex structures are proposed.

The paper is organized as follows. Section II contains details of our MD simulation model. Section III is devoted to the strong Coulomb coupling regime. Section IV is devoted to the intermediate Coulomb coupling regime. In Sec. V, we consider the like-charge complexation in the weak Coulomb coupling regime corresponding to water solvent.

## II Simulation method

The MD method employed here is based on the Langevin equation and is similar to that employed in previous studies KG\_JCP\_1990 . Consider within the framework of the primitive model one spherical macroion characterized by a diameter $`d`$ and a bare charge $`Q_M=Z_Me`$ (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 $`\sigma `$. Both ends of the chain are always charged and each $`1/f`$ 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 $`Z_m>0`$). The small counterions, assumed all identical, ensure global electroneutrality and have a diameter $`\sigma `$ and charge $`+Z_ce`$ (with $`Z_c>0`$). All these particles making up the system are confined in an impermeable spherical cell of radius $`R`$, and the spherical macroion is held fixed at the center of the cell.

The equation of motion of any mobile particle (counterion or monomer) $`i`$ reads

$$m\frac{d^2𝐫_i}{dt^2}=_iU(𝐫_i)m\gamma \frac{d𝐫_i}{dt}+𝐖_i(t),$$
(1)
where m is the mass particle (supposed identical for all mobile species), U is the total potential force and $`\gamma `$ is the friction coefficient. Friction and stochastic force are linked by the dissipation-fluctuation theorem $`<𝐖_i(t)𝐖_j(t^{})>=6m\gamma k_BT\delta _{ij}\delta (tt^{^{}})`$.

Excluded volume interactions are introduced via a pure short range repulsive Lennard-Jones (LJ) potential given by

$$U_{LJ}(r)=\{\begin{array}{c}4ϵ\left[\left(\frac{\sigma }{rr_0}\right)^{12}\left(\frac{\sigma }{rr_0}\right)^6\right]+ϵ,\hfill \\ 0,\hfill \end{array}\begin{array}{c}\text{for}rr_0<r_{cut},\hfill \\ \text{for}rr_0r_{cut},\hfill \end{array}$$
(2)
where $`r_0=0`$ for the microion-microion interaction, $`r_0=7\sigma `$ for the macroion-microion interaction and $`r_{cut}`$ = $`2^{1/6}\sigma `$ is the cutoff radius. This leads to $`d=2r_0+\sigma =15\sigma `$, whereas the closest center-center distance of the microions to the spherical macroion is $`a=r_0+\sigma =8\sigma `$. The macroion volume fraction is defined as $`f_M=(a/R)^3`$ and is fixed to $`8\times 10^3`$ with $`R=40\sigma `$.

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

$$\frac{U_{coul}(r)}{k_BT}=l_B\frac{Z_iZ_j}{r},$$
(3)
where $`l_B=e^2/4\pi ϵ_0ϵ_rk_BT`$ is the Bjerrum length. Energies are measured in units of $`ϵ=k_BT`$ with $`T=298`$ K. Choosing $`\sigma =3.57`$ Å rrequires that the Bjerrum length of water at room temperature equals $`2\sigma `$ (7.14 Å). In this work the macroion charge is fixed at $`Z_M=180`$.

The polyelectrolyte chain connectivity is modeled by using a standard finitely extensible nonlinear elastic (FENE) potential in good solvent (see for example Ref. KG\_JCP\_1990 ), which reads

$$U_{FENE}(r)=\{\begin{array}{c}\frac{1}{2}\kappa R_0^2\mathrm{ln}\left[1\frac{r^2}{R_0^2}\right],\hfill \\ \mathrm{},\hfill \end{array}\begin{array}{c}\text{for}r<R_0,\hfill \\ \text{for}rR_0,\hfill \end{array}$$
(4)
where $`\kappa `$ is the spring constant-like chosen as $`1000k_BT/\sigma ^2`$and $`R_0=1.5\sigma `$. These values lead to an equilibrium bond length $`l=0.8\sigma `$.

Typical simulation parameters are summarized in Table 1. The simulation runs are reported in Table 2. Each simulation run requires about $`10^7`$ MD steps, and equilibrium is typically reached after $`5\times 10^5`$ up to $`3\times 10^6`$ steps. We normally performed between $`5\times 10^6`$ and $`10^7`$ MD steps to take measurements. We cover the whole range of strength of Coulomb electrostatic interaction from the strong coupling limit, which is more theoretical interest, to the weak coupling limit, which corresponds to an aqueous solvent.

## III Strong Coulomb coupling

First we look at the like-charge complexation in the strong Coulomb coupling regime. We choose the relative permittivity $`ϵ_r=16`$, corresponding to $`l_B=10\sigma `$, and divalent microions ($`Z_m=Z_c=2`$). Such a set of parameters is of special theoretical interest to study the influence of strong electrostatic correlations.

### III.1 Single charged object

In this section we first study separately (i) the spherical macroion and (ii) the flexible polyelectrolyte in the presence of their surrounding neutralizing divalent counterions separately . This provides the reference states for the more complicated situation, where both of these two objects interact.

#### III.1.1 Spherical macroion

Consider an isolated macroion with its surrounding divalent counterions. A pertinent parameter to describe the Coulomb coupling for such highly asymmetric electrolyte solution (macroion and counterions) is the so-called “plasma” parameter $`\mathrm{\Gamma }=Z_c^2l_B/a_{cc}`$, where $`a_{cc}`$ (which will be determined below) is the average distance (triangular lattice parameter in the ground state) between counterions lying on the macroion surface Rouzina\_JCP\_1996 . For the strong Coulomb coupling considered we find $`\mathrm{\Gamma }13`$ (with $`Z_M=180`$), and for finite macroion volume fraction (here $`f_M=8\times 10^3`$), all counterions lie in the vicinity of the macroion surface Messina\_PRL\_2000 ; Messina\_PRE\_2001 ; Messina\_EPL\_2000 ; Messina\_EPJE\_2001 .

To characterize the counterion layer structure, we compute the counterion correlation function $`g(s)`$ on the surface of the sphere Messina\_PRE\_2001 ; Messina\_EPJE\_2001 , defined as:

$$c^2g(s)=\underset{ij}{}\delta (s^{}s_i)\delta (s^{\prime \prime }s_j),$$
(5)
where $`c=N_c/4\pi a^2`$ is the surface counterion concentration ($`N_c=Z_M/Z_c`$ being the number of counterions), and $`s=|s^{}s^{\prime \prime }|`$ corresponds to the arc length on the sphere of radius $`a`$ (center-distance of closest approach of macroion and counterion). Each counterion (located in the vicinity of the surface) is radially projected on the (”contact”) shell around the macroion center of radius $`a=8\sigma `$. Correlation functions are computed by averaging $`g(s)`$ over 1000 independent equilibrium configurations which are statistically uncorrelated. The pair distribution $`g(s)`$ is normalized as follows

$$c_0^{\pi a}2\pi sg(s)𝑑s=(N_c1).$$
(6)
Because of the finite size and the topology of the sphere, $`g(s)`$ has a cut-off at $`\pi a`$ (=25.1 $`\sigma `$) and a zero value there. Therefore, at large values of $`s`$, $`g(s)`$ cannot directly be compared to the correlation function in an infinite plane.

Results are depicted in Fig. 1 for $`Z_M=180`$. The first peak111It is this value $`a_{cc}3\sigma `$ which gives $`\mathrm{\Gamma }13`$. appears at about $`s=a_{cc}3\sigma `$ whereas the second peak about $`s6\sigma `$ and finally the third small peak around $`s9\sigma `$. This structure, which is highly correlated, is referred to as a strongly correlated liquid (SCL) Messina\_PRE\_2001 ; Shklowskii\_PRE\_1999b , but not yet a Wigner crystal. A typical equilibrium configuration is depicted in Fig. 2 where one can see the local arrangement close to a triangular lattice.

#### III.1.2 Polyelectrolyte chain

Now we investigate an isolated polyelectrolyte chain together with its surrounding divalent counterions in bulk confined to the same spherical cell of radius $`R=40\sigma `$. We consider four monomer charge fractions (i. e. four linear charge densities) $`f=1`$, 1/2, 1/3 and 1/5. The chain is made up of $`N_m=256`$ monomers ($`N_m=257`$ for $`f=1/2`$). while $`Z_m=Z_c=2`$, The polymer chain parameters are identical to those of the complexation case (see Table 2). The chain extension is characterized by its radius of gyration $`R_g`$ given by

$$R_g^2=\frac{1}{N_m}\underset{i=1}{\overset{N_m}{}}(𝐫_i𝐫_{CM})^2,$$
(7)
where $`𝐫_{CM}`$ is the center of mass position of the chain.

The corresponding values of $`R_g`$ can be found in Table 2 (see $`R_g^{(bulk)}`$ for runs A-D). The chain extension varies little with $`f`$ and is roughly given by $`R_g4\sigma `$. For this strong Coulomb coupling, all counterions are “condensed” into the polyelectrolyte globule for all three linear charge densities considered. The strong counterion condensation induces a collapse of the chain, which is by now well understood Stevens\_PRL\_1993 ; Stevens\_JCP\_1995 ; Winkler\_PRL\_1997 ; Brilliantov\_PRL\_1998 ; Golestanian\_PRL\_1999 . A typical equilibrium chain conformation is shown in Fig. 3 for $`f=1`$. As expected the structure is very compact and highly ordered. Very similar structures are obtained for $`f=1/2`$, 1/3 and 1/5.

### III.2 Complexation

We now investigate the complexation of a highly charged colloid with a long flexible polyelectrolyte, both negatively charged. Four different parameter combinations, denoted by run A, B, C and D, were investigated which are summarized in Table 2. Going from run A to D the polyelectrolyte charge fraction $`f`$ decreases from 1 to 1/5. The contour length of the chain is much larger ($`N_ml/d14`$ times) than the colloidal particle diameter.

#### III.2.1 Observation of the complexation

Figure 4 shows typical equilibrium configurations of the colloid-polyelectrolyte complex. We notice that in all reported cases complexation occurs and the polyelectrolyte is completely adsorbed onto the colloidal surface, that is, in presence of a highly charged colloid, the polyelectrolyte conformation becomes quasi two-dimensional in contrast to the bulk case (compare Fig. 4 with Fig. 3). However the structure of these resulting complexes depends strongly on the value of $`f`$. For the fully charged polyelectrolyte case \[run $`A`$ with $`f=1`$ \- see Fig. 4(a)\] the monomers are closely packed forming a two-dimensional compact Hamiltonian-walk with the condensed counterions on the polyelectrolyte. This structure consists of closed packed lines made from either counterions or monomers. When the linear change density is reduced \[see Fig. 4(b-d)\], the complex structures are qualitatively different. In these cases the monomers are no longer closely packed. For run B \[$`f=1/2`$, Fig. 4(b)\], the monomers spread more over the particle surface and the polymer partially wraps around the sphere exhibiting a quasi two-dimensional surface pearl-necklace structure. For run $`C`$ \[$`f=1/3`$, Fig. 4(c)\] and run $`D`$ \[$`f=1/5`$, Fig. 4(d)\], the monomers spread entirely over the particle surface, and the chain wraps the colloidal particle leading to an almost isotropic distribution of the monomers around the spherical macroion.

The like-charge complex formation is due to the strong counterion mediated correlations which are known to induce attractions in the strong Coulomb coupling regime. Basically, the charged species will try to order locally in a way which is compatible with the chain connectivity and the macroion surface constraints. We now quantify those observations and propose a simple mechanism to explain the observed conformations.

#### III.2.2 Adsorption profile

To quantify the adsorption of the monomers and counterions on the macroion particle surface, we analyze three quantities: (i) the ion radial distribution function $`n_i(r)`$, (ii) the ion fraction $`P_i(r)`$ and (iii) the net fluid charge $`Q_i(r)`$ (omitting the macroion bare charge $`Z_M`$), where $`r`$ is the distance from the spherical macroion center. The radial ion distribution function $`n_i(r)`$ is normalized as follows

$$_{r_0}^Rn_i(r)4\pi r^2𝑑r=N_i\mathrm{with}i=c,m;$$
(8)
where $`N_i`$ is the total number of ions, and the subscripts $`c`$ and $`m`$ stand for counterion and monomer respectively. The reduced integrated ion radial density $`P_i(r)`$ is linked to $`n_i(r)`$ via

$$P_i(r)=\frac{_{r_0}^rn_i(r^{^{}})4\pi r^2𝑑r^{^{}}}{N_i}\mathrm{with}i=c,m.$$
(9)
Note that for $`f<1`$, neutral and charged monomers are all included in the quantities $`n_m(r)`$ and $`P_m(r)`$. The net fluid charge $`Q(r)`$ is given by

$$Q(r)=_{r_0}^r\left[Z_cn_c(r^{^{}})Z_mn_m(r^{^{}})\right]4\pi r^2𝑑r^{^{}},$$
(10)
where we choose $`e=1`$.

Integrated distribution $`P(r)`$, radial distribution $`n(r)`$ and fluid net charge $`Q(r)`$ profiles are depicted in Figs. 5(a-c) respectively. Fig. 5(a) shows that all atoms for all runs 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 atomic layers \[see also the radial distribution in Fig 5(b)\]. 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 \[see Figs 5(a-b)\]. Note that the monomer depletion in this first counterion layer also concerns neutral monomers (runs B-D) and this effect is attributed to the chain connectivity. This means that the repulsion stemming from the charged monomers impose the polymer structure as long as $`f`$ and the Coulomb coupling are sufficiently high, which is the case in the present study. The height of the first peak in the counterion $`n_c(r)`$ profile is almost independent on $`f`$. The second ion layer is mixed of monomers and counterions, however with a majority of monomers \[see Figs 5(a-b)\]. Indeed the first monomer peak in the $`n_m(r)`$ profile (located at $`r8.7\sigma `$) and the second counterion peak in the $`n_c(r)`$ profile (located at $`r9.2\sigma `$) are only separated by roughly $`\mathrm{\Delta }r0.5\sigma `$ \[see Fig 5(b)\]. This leads to a medium position located at $`r9\sigma `$ corresponding to a bilayer thickness. The height of the second peak in the counterion $`n_c(r)`$ profile increases with increasing $`f`$ \[see Fig 5(b)\].

For $`f=1`$ (run $`A`$), we observe a massive macroion charge inversion of more than 100% \[i.e. $`Q(r)/Z_M>2`$\] in the first layer as well as a strong charge oscillation \[see Fig. 5(c)\]. Upon reducing $`f`$ (runs $`BD`$) the macroion charge overcompensation decreases as well as the charge oscillation amplitude \[see Fig. 5(c)\]. This is due to the fact that upon reducing $`f`$ less counterions are present and their correlations change.

#### III.2.3 Polyelectrolyte chain radius of gyration

Next, we investigate the radius of gyration $`R_g`$ of the chain, i.e. Eq. (7), in order to gain insight of the spreading of the monomers over the sphere. The results reported in Fig. 6 (for $`l_B=10\sigma `$) show that $`R_g`$ increases with decreasing decreasing $`f`$ 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 $`f=1`$ and $`f<1`$. This is in agreement with the visual inspection of the chain conformations presented in Fig. 4. Moreover, the isotropic case (monomers fully spread over the particle) corresponding to $`R_g8.7\sigma `$ (222This value corresponds to the the first monomer peak position in the $`n_m(r)`$ profile \[see Fig.5 (b)\]. ) is already reached for $`f=1/2`$ (run B).

#### III.2.4 Surface counterion correlation function

In this section we are interested in determining the structure of the “free” counterions which are not condensed onto the polyelectrolyte chain. Counterions are called “condensed” on the polyelectrolyte chain when they lie within a distance $`r_c=1.2\sigma `$ perpendicular to the chain (Fig. 7). All other counterions are called “free”, although they are still adsorbed onto the colloidal surface. To characterize the structure of the free counterions we proceed in the same way as in Sec. III.1.1. The surface free counterion correlation function $`g_{free}(s)`$ is now given by

$$c_{free}^2g_{free}(s)=\underset{ij}{}\delta (s^{}s_i)\delta (s^{\prime \prime }s_j),$$
(11)
where the sum in Eq. (11) is restricted to the free counterions, and $`c_{free}=N_{free}/4\pi a^2`$ is the surface free counterion concentration, with $`N_{free}`$ being the average number of free counterions. The normalization is obtained as follows

$$c_{free}_0^{\pi a}2\pi sg_{free}(s)𝑑s=(N_{free}1).$$
(12)
Results are depicted in Fig. 8 for runs A-D. The important result is that the first peak of $`g_{free}(r)`$ is located at the same position ($`s3\sigma `$) as in the “unperturbed” case of an isolated macroion (without polyelectrolyte) studied in Sec. III.1.1 (see Fig. 1). Although the second peak of $`g_{free}(s)`$ is less pronounced than in the “unperturbed” case (compare Fig. 8 with Fig. 1), the local order of the free counterion structure is still high as can be visually inspected on the snapshots sketched in Fig. 4. Thus the adsorbed chain only affects the counterion distribution significantly in its immediate neighborhood.

#### III.2.5 Polyelectrolyte overcharging

We now show that the concept of polyelectrolyte overcharging can be used to explain the observed complex structures. Let $`N_{cd}`$ be the number of counterions we consider as condensed onto the polyelectrolyte. Then the overcharging ratio $`\chi _{PE}`$ is defined as

$$\chi _{PE}=\frac{N_{cd}}{N_{cm}},$$
(13)
which is merely the ratio between the amount of the total condensed counterion charge and the polyelectrolyte bare charge.

This “overcharging” can also be analytically predicted by the simple assumption that the presence of the polyelectrolyte (with its counterions) does not affect the free counterion distribution333This mainly holds for the first correlational peak which is the most important for the present discussion, as we showed in the previous Sec. III.2.4. . Let us consider the bare charged chain plus its own neutralizing counterions as an uncharged object that gets overcharged by intercepting all counterions (of the macroion) whose center lie within a ribbon of width $`2r_c`$ and area $`A_{rib}=2r_cN_ml`$ (Fig. 7). If $`c`$ is the counterion (of the macroion) concentration then the theoretical overcharging ratio $`\chi _{th}`$ is merely given by

$$\chi _{th}=1+\frac{A_{rib}c}{N_{cm}}=1+\frac{2r_cN_mlZ_M}{N_{cm}Z_c4\pi a^2},$$
(14)
and since the number of charged monomers $`N_{cm}`$ is given by $`N_{cm}=(N_m1)f+1`$, Eq. (14) reduces for $`N_m1`$ to

$$\chi _{th}1+C/f,$$
(15)
with $`C=\frac{2r_clZ_M}{Z_c4\pi a^2}`$.

Results are presented in Fig. 9 and the corresponding values can be found in Table 3. It indicates that in all cases overcharging occurs (i.e., $`\chi _{PE}>1`$), and that it increases with decreasing polyelectrolyte charge density. We have excellent agreement (less than 10% difference) between simulation results and our toy model \[Eq. (14)\]. In turn it explains why $`\chi _{PE}`$ varies almost linearly with $`1/f`$ in our simulations.

The f-dependency of the complexation structure can be explained through the overcharging. For this we consider the overcharged polyelectrolyte as a dressed (or renormalized) chain \[bare chain + counterions\] with an (or renormalized) linear charge density $`\lambda _{PE}^{}=(\chi _{PE}1)\lambda _{PE}`$ that obviously has the opposite sign of $`\lambda _{PE}`$ NOTE\_Many\_Body . Similarly one can define the renormalized charge of a monomer as

$$q_m^{}=(\chi _{PE}1)q_m.$$
(16)
Using Eq. (16) and the results of Fig. 9 this shows that $`q_m^{}`$ increases with increasing $`1/f`$. The overcharging leads to an effective local repulsion of the monomers, and subsequently to a bond stiffening of the chain. This in turn explains why the chain expands with increasing $`1/f`$ (see Fig. 6 and Fig. 4 for the corresponding structures) NOTE\_Many\_Body\_b .

## IV Intermediate Coulomb coupling

In this section we are dealing with a higher dielectric constant ($`ϵ_r=40`$), meaning that we consider weaker Coulomb coupling ($`l_B=4\sigma `$). Experimentally this could correspond to using alcohol as a solvent. We consider a set of three runs $`EG`$ with $`l_B=4\sigma `$ (see Table 2). Thus these systems are, up to a shorter Bjerrum length $`l_B`$, identical to runs $`AC`$. It will be helpful to start the discussion with the description of the observed complex microstructures.

### IV.1 Complex microstructure

Typical equilibrium macroion-polyelectrolyte complex structures are sketched in Fig. 10. When the polyelectrolyte is fully charged ($`f=1`$, run $`E`$), Fig. 10(a) shows again a strongly compact chain conformation. But in the present situation the chain does not spread on the macroion surface as it was the case in the strong Coulomb coupling \[compare Fig. 10(a) with Fig. 4(a)\]. In fact the conformation of the charged chain in presence of the macroion is very similar to the bulk conformation \[compare 10(a) with Fig. 3\].

By reducing the monomer charge fraction, Figs. 10(b-c) show that the complex microstructure for runs $`F,G`$ is again qualitatively different from the fully charged case (run $`E`$). For these smaller polyelectrolyte linear charge densities ($`f=1/2`$ and $`f=1/3`$), the chain conformation is again almost wrapping around the colloid. For $`f=1/2`$ (run $`F`$) the peal-necklace structure observed in the strong Coulomb coupling \[see Fig. 4(b)\] does not appear here, instead small loops appear \[see Fig. 10(b)\]. For the smallest monomer charge fraction ($`f=1/3`$, run $`G`$) the monomers fully spread over the macroion surface and the conformation is not compact, and also small loops appear \[see Fig. 10(c)\]. Again it is observed that upon reducing the polymer charge density the chain expands, but this time it expands also into the radial direction away from the macroion.

The forthcoming sections are devoted to study in more detail the monomer and counterion distributions.

### IV.2 Adsorption profile

Integrated distribution $`P(r)`$, radial distribution $`n(r)`$ and fluid net charge $`Q(r)`$ profiles are given in Figs. 11(a-c) respectively. In a general manner, the fraction of monomers and counterions in the vicinity of the macroion surface is clearly smaller than the one obtained in the strong Coulomb coupling as expected \[compare Fig. 11(a) with Fig. 5(a)\]. Also the width in $`P(r)`$ profile of adsorbed ions is enlarged with decreasing Coulomb coupling \[compare Fig. 11(a) with Fig. 5(a)\]. These features show that the monomer adsorption is more diffuse (in the normal direction to the macroion sphere) as expected for a weaker Coulomb coupling. Concerning the ion density $`n(r)`$ profile \[see Fig. 11(b)\], it is interesting to note that the height of the first peak in the monomer density $`n_m(r)`$ profile is twice smaller for $`f=1`$ than for $`f<1`$, whereas the one from the counterion density profile is almost independent on $`f`$. In parallel, the macroion charge overcompensation as well as charge oscillation amplitudes are clearly reduced compared to the strong Coulomb regime \[compare Fig. 11(c) with Fig. 5(c)\].

For the fully charged polyelectrolyte case ($`f=1`$, run $`E`$) the $`n_m(r)`$ profile in Fig. 11(b) shows a strong second monomer peak and a weaker third one in agreement with the snapshot of Fig. 10(a). The radial monomer ordering naturally goes along with a counterion ordering in anti-phase. In other words, multilayering of different chain segments occurs, but without strong adsorption of the macroion \[compare Fig. 10(a) with Fig. 4(a)\]. Therefore we find three charge oscillations \[see Fig. 11(c)\] against only two in the strong Coulomb coupling \[see Fig. 5(c)\].

For smaller linear charge density, Fig. 11(a) and Fig. 11 (b) indicate that for runs $`F`$ ($`f=1/2`$) and $`G`$ ($`f=1/3`$) the chain is almost fully adsorbed to the macroion surface without monomer chain multilayering \[i. e., no appearance of monomer second peak in the $`n_m(r)`$ profile - see Fig. 11(b)\]. However, the conformation is a little bit swollen probably due to the onset of loop formation, compare the snapshots in Fig. 10. As in the strong Coulomb coupling case, we find here only one charge oscillation for $`f=1/2`$ and $`f=1/3`$, and the amplitude of the reduced net fluid charge decreases with decreasing $`f`$.

### IV.3 Polyelectrolyte chain radius of gyration

Results for the radius of gyration $`R_g`$ of the polymer chain are reported in Fig. 6 (for $`l_B=4\sigma `$). As for the high Coulomb coupling case with $`l_B=10\sigma `$, $`R_g`$ increases with decreasing $`f`$. However, for $`f=1`$, here we obtain $`R_g4.8\sigma `$ which is clearly smaller than the value $`R_g6.4\sigma `$ obtained in run $`A`$ (see Fig. 6). This proves that for $`l_B=4\sigma `$ the chain conformation stays as a globule, since we already found that for the same chain length and with $`l_B=10\sigma `$ the chain conformation was compact and two-dimensional. In the case under consideration ($`f=1`$, $`l_B=4\sigma `$), the value of $`R_g4.8\sigma `$ is almost identical to the one obtained in the bulk where $`R_g=4.4\sigma `$ (see Table 2).

Upon reducing $`f`$ (run $`F`$ and $`G`$), the chain is much more expanded and it is found that $`R_g9.4\sigma `$. Taking into account the fact the chain is still adsorbed for both systems (run $`F`$ and $`G`$) as was found in the analysis of the adsorption profile (see Fig. 11), one deduces that the spreading of the monomers is very important as soon as $`f<1`$. A comparison with the strong Coulomb coupling shows that values of $`R_g`$ for $`l_B=4\sigma `$ are systematically larger than those of $`R_g`$ with $`l_B=10\sigma `$ (see Fig. 6 and Table 2), indicating again that the chain fluctuates more in the outward macroion radial direction at weaker Coulomb coupling.

### IV.4 Polyelectrolyte overcharging

In order to check if the local polyelectrolyte overcharge is responsible for the expansion of the chain upon reducing $`f`$ as was demonstrated in the strong Coulomb coupling for $`l_B=10\sigma `$ in Sec. III.2.5, we again consider the overcharging ratio $`\chi _{PE}`$ defined by Eq. (13) with the same condensation distance $`r_c=1.2\sigma `$ as was done for $`l_B=10\sigma `$ in Sec. III.2.5.

Numerical values of $`\chi _{PE}`$ are can be found in Table 4. It clearly shows that polyelectrolyte overcharge is negligible (i. e., $`\chi _{PE}1`$) for the present Coulomb coupling regime whatever the value of $`f`$. Consequently one can not explain the expansion of the chain with increasing $`1/f`$ with a polyelectrolyte overcharge mechanism. We will give clear and qualitative arguments in Sec. VI that account for these conformations.

## V Weak Coulomb coupling

This part is devoted to aqueous solutions where the Bjerrum length is $`l_B=2\sigma =7.14`$ Å ccorresponding to the dielectric constant $`ϵ_r80`$ of water. Such systems will be referred to as the weak Coulomb coupling regime. We have considered a set of three runs $`HJ`$ (see Table 2) identical to the previous ones but with a shorter Bjerrum length $`l_B=2\sigma `$. Again it is helpful to start with the description of the observed complex microstructures.

### V.1 Complex microstructure

Typical equilibrium macroion-polyelectrolyte complex structures can be found in Fig. 12. For all investigated cases (runs $`HJ`$), one finds that the polymer never adopts a “two-dimensional” conformation. A comparison of the bulk value of $`R_g`$ and the $`R_g`$ of the chain in the complexed situation (compare Table 2) reveals that the chain conformation is only weakly affected by the macroion. For the fully charged polymer ($`f=1`$, run $`H`$), the conformation is again rather compact but without exhibiting a strong monomer-counterion ordering (within the polymeric aggregate) as it was the case for higher Coulomb coupling regimes \[compare Fig. 12(a) with Fig. 10(a) and Fig. 4(a)\]. However we do have an effective macroion-polyelectrolyte attraction, and the dense monomer-counterion aggregate is adsorbed onto the colloidal surface.

For $`f=1/2`$ (run $`I`$), the chain conformation is more expanded than for $`f=1`$ \[compare Fig. 12(b) with Fig. 12(a)\]. Nevertheless we do have polymer adsorption with the formation of chain loops. Therefore even for couplings which are typical of aqueous systems, our simulations show that like-charge complexation can occur for $`f=1`$ and $`f=1/2`$ with divalent ions ($`Z_m=Z_c=2`$).

For even lower linear charge density ($`f=1/3`$, run $`J`$), Fig. 12(c) shows polymer desorption from $`f=1/2`$ to $`f=1/3`$. In the same time there is a certain “counterion release” for $`f=1/3`$, meaning that not all counterions are in the vicinity of the highly charged objects (macroion and polyelectrolyte). We carefully checked that, with periodic boundary conditions, the same features qualitatively appear, namely chain desorption from $`f=1/2`$ to $`f=1/3`$.

### V.2 Adsorption profile

Integrated distribution $`P(r)`$, radial distribution $`n(r)`$ and fluid net charge $`Q(r)`$ profiles are depicted in Figs. (a-c) respectively. The ion fraction $`P(r)`$ profiles show that for $`f=1`$ (run $`H`$) and $`f=1/2`$ (run $`I`$) almost all atoms lie within a distance $`a<r<20\sigma `$ \[i. e. $`P(r=20\sigma )1`$\], corresponding to roughly one macroion diameter away from the colloidal surface \[see Fig. 13(a)\]. This is in contrast to what was previously found (with $`f=1`$ and $`f=1/2`$ ) at stronger Coulomb coupling regimes where almost all ions lie within a distance of a few monomer sizes from the macroion surface \[compare Fig. 13(a) with Fig. 5(a) and Fig. 11(a)\]. For $`f=1/3`$ (run $`J`$) only a very small fraction of monomers \[$`P_m(r=10\sigma )<5\%`$\] lie in the vicinity of the macroion surface. In this latter situation, the counterion $`P_c(r)`$ profile indicates that a larger fraction of counterions float in the solution. Because the $`R_g`$ of the chain is very large and some chain monomers might be interacting with the cell boundary we performed for this situation a simulation where we employed periodic boundary condition, and where the interactions were computed using the P3M algorithm deserno98a . With this run we found no chain monomers in the vicinity of the colloid surface, hence unambiguously found monomer desorption from the colloidal surface.

Concerning the intra-chain monomer ordering for $`f=1`$, Fig. 13(b) shows that, although the chain conformation is relatively dense, there is only one main peak in the monomer $`n_m(r)`$ profile (the second peak is marginal). This proves that there is no strong intra-chain monomer ordering (in the normal direction to the macroion sphere) in this weak Coulomb coupling in contrast with our observations at $`l_B=4\sigma `$ \[compare with Fig. 11(b)\]. Nevertheless a second counterion layer (third monomer layer) is build. The height $`h_m`$ of the monomer peak is identical (within the statistical uncertainty) for $`f=1`$ and $`f=1/2`$ and corresponds to $`h_m0.038/\sigma ^3`$, whereas for $`f=1/3`$ we have $`h_m0.01/\sigma ^3`$.

As far as the net fluid charge $`Q(r)`$ is concerned, Fig. 13(c) shows that for $`f=1`$ a weak charge oscillation appears with a marginal macroion overcharge compensation of 3%. For $`f=1/2`$, the same marginal macroion overcharging occurs but without exhibiting charge oscillation. Finally, for $`f=1/3`$ no overcharging appears and the the net charge increases monotonically.

### V.3 Polyelectrolyte chain radius of gyration

In Fig. 6 (for $`l_B=2\sigma `$) the chain radius of gyration $`R_g`$ as function of $`f`$ is plotted. It is found that $`R_g`$ increases almost linearly with $`1/f`$. This result fits well with the scaling theory in this regime from Ref.schiessel98a  where it is found that the chain extension shrinks proportionally with $`l_B`$, and we can assume for our purposes $`fl_B`$. Because the electrostatic interactions are weaker in the present case ($`l_B=2\sigma `$), the ion pair (monomer - condensed counterion) attractions are weaker which results in a higher $`R_g`$ value (at fixed $`f`$) than in the strong Coulomb coupling regime.

### V.4 Monovalent case, $`f=1`$

Our last result concerns the monovalent case ($`Z_m=Z_c=1`$ and $`f=1`$) corresponding to run $`K`$ (see Table 2). In this situation we have a strong macroion-polyelectrolyte repulsion, and one can not get like-charge complexation.

## VI Concluding remarks

We have carried out MD simulations to study the complexation of a charged colloid with a charged polyelectrolyte of the same charge for various Coulomb couplings $`l_B`$ and and varying charge fraction $`f`$.

For $`l_B=10\sigma `$ we gave a reasoning for the observed conformation in terms of overcharging of the single chain. However this argument only worked for the largest coupling parameter.

A complementary view of the observed conformations is to regard both macroions as being neutralized by their counterions The isolated chain would then collapse into a globule, and the colloid would be regularly covered by its counterions. By changing the Bjerrum length $`l_B`$ we change the correlations between the charges which lead in a first approximation to attractions of dipolar origin, and the attraction is roughly proportional to $`l_B`$. On the other hand, by varying $`f`$ we change the number of counterions of the chain, hence the number of available dipoles.

For $`f=1`$ we can regard the colloidal particle as exerting only a perturbation of the chain complex (which has a higher density of dipoles). For largest $`l_B`$ the strong attraction results in a flat disk, for weaker $`l_B`$ the disk swells back into the bulk structure, the globule. For smaller $`f`$ the number of counterions of the polyelectrolyte and the colloid become comparable in number, and both macroions can equally compete for the counterions leading to a greater freedom of both macroions to “move” in their common counterion cloud. For the largest value of $`l_B`$ we have again the strongest dipolar attractions leading to a purely 2D conformation, where the chain is wrapped around the colloid. For smaller values of $`l_B`$ the conformations become more and more 3D-like, but are still wrapping around the colloid. Of special interest is here the fact that even for a coupling strength which is typically for an aqueous solvent ($`l_B`$ = 7.1 Å) we find that like-charge complexation still occurs provided the linear charge density is sufficiently large. However the adsorption of the polymer chain onto the colloid is weaker than in the larger Coulomb coupling regimes. For $`f=1/2`$, we observe formation of large loops.

For $`l_B=2\sigma `$ and $`f=1/3`$ we find no complex, but end with two single macroions together with their counterion cloud which interact mainly with their bare charge, i.e. repulsive.

Our parameters concerning aqueous solutions should be experimentally accessible, typically for small highly charged colloids (micelles and relatively short polyelectrolyte chains).

###### Acknowledgements.

This work is supported by Laboratoires Européens Associés (LEA).


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# 𝐶𝐻𝐴𝑁𝐷𝑅𝐴 Detection of 16 New X-Ray Sources

## 1 Introduction

The imaging capability and high sensitivity of the $`Chandra`$ $`XRay`$ $`Observatory`$ offers significant advantages for source detection. The good instrumental response for photon energies up to 8 keV allows detection of faint sources even if the source is subject to high absorption. The main goal of this search was to detect faint and Super Soft X-ray Sources (SSS) using a 95 ks observation obtained by the $`CHANDRA`$ Advanced CCD Imaging Spectrometer (ACIS) detector. The original target of the observation was a classical nova Persei 1901 (GK Per; principal investigator= Ş. Balman). The scientific aim of the proposal was deriving and studying the spectrum of the first classical nova shell resolved and detected in the X-ray wavelengths (Balman & Ögelman bogel (1999)). The $`CHANDRA`$ data reveals for the first time a classical nova evolving like a young, miniature supernova remnant. The scientific results of the $`CHANDRA`$ observation can be found in Balman (balman1 (2001), balman2 (2002)).
As expected most of the sources we detected were faint sources, but we did not find any SSS above 5$`\sigma `$ confidence level. We analyzed the spectra of these new X-ray sources detected in two regions 8$`\mathrm{}`$.3$`\times `$16$`\mathrm{}`$.9 and 8$`\mathrm{}`$.3$`\times 33\mathrm{}`$.6 around the vicinity of the point with $`\alpha `$=03h31m02s.45 (J2000) and $`\delta `$=+43$`\mathrm{°}`$47$`\mathrm{}`$58$`\mathrm{}`$.54 (J2000) within an energy range of 0.3-10 keV in order to identify their nature.
Details of the observation and the analysis methods are given in Section 2. Section 3 discusses the detection properties of the sources and Section 4 is on the spectral analysis and discussion.

## 2 The Data and Analysis

The classical nova remnant of GK Per was observed with the $`CHANDRA`$ ACIS between 2000-02-10 and 2000-02-11.
ACIS contains 10 planar, 1024 $`\times `$ 1024 pixel CCDs; four arranged in a 2$`\times `$2 array (ACIS-I) used for imaging, and six arranged in a 1$`\times `$6 array (ACIS-S) used either for imaging or as a grating readout. Two CCDs are back-illuminated (BI) and eight are front-illuminated (FI). 6 CCDs (2,3,5,6,7,8) have been used during our observation. GK Per is on CCD number 7. The level 2 data were processed using CIAO software (version 2.0) . Bad pixels were removed and the latest suitable calibration files were used. In addition, we cleaned the data for the flaring effects of the ACIS-S3, and the exposure was reduced to 81 ks.
We ran the CELLDETECT111http://asc.harvard.edu/udocs/docs/swdocs/detect/html/ algorithm (or the ‘sliding cell’ method), a source detection algorithm for X-ray data. It was developed for use with the Einstein Observatory images and also employed by the standard processing of ROSAT data (Harnden et al. harnden (1984)). This method was tailored to optimize the detection of unresolved sources and had two variants, ‘local detect’ and ‘map detect’. In the local detect that is used for our data, the background is estimated in a frame around the detect cell. At each point where a cell is placed, a signal-to-noise ratio of source counts to background counts is computed. If this ratio is above the detection threshold, a candidate source is recorded. The CELLDETECT method is good for faint point sources, outside crowded fields.
The CELLDETECT algorithm, run on the exposure corrected 0.3-10 keV images with exposure maps derived separately for five of the CCDs (2,3,5,6,7), yielded 20 sources over 6$`\sigma `$ detection threshold (6$`\sigma `$ above the background). Since CELLDETECT divides extended sources into multiple point sources and thus requires fine tuning of the parameters, we have chosen different values for the fixedcell parameter for different CCDs. The findpeaks parameter was set to ‘yes‘ so that the adjacent detections were recognized as a single source and the cell with the largest S/N appeared in the source list. We have omitted three of the sources and include one source detected with CELLDETECT algorithm over 12 $`\sigma `$ threshold at CCD 8. We have increased the threshold sigma of the detection algorithm up to 12 $`\sigma `$ for CCD 8 because of the excess number of bad pixels. Exposure maps for each of the CCDs were prepared using the single-chip exposure map thread of CIAO 2.0 and used to eliminate the false detections near the edges.

## 3 Source Properties

The results of our analysis with the CELLDETECT algorithm yield 18 sources over 6 $`\sigma `$ detection threshold. Table-1 displays all 18 sources including the source designations and count rates. The right ascension and declination errors determined from the CELLDETECT algorithm are between 0$`\mathrm{}`$.5 and 0$`\mathrm{}`$.2. The spatial resolution of $`CHANDRA`$ is 0$`\mathrm{}`$.49 pixel-1. The source count rates vary in a range 0.5$`\times `$10-3 \- 5$`\times `$10-3 counts/s.
After searching the HEASARC data archive222http://heasarc.gsfc.nasa.gov/docs/corp/data.html including multi-wavelength catalogs and mission catalogs, two of the sources were found to be detected before with $`ROSAT`$ HRI and one source (Src 9) can be closely identified (with 0$`\mathrm{}`$.3 offset) with the source in the optical USNO A-2 Catalog (Monet et al. monet (1998)). The red and blue magnitude of the USNO source associated with Src 9 is mr=14.7, mb=16.2 . For offset radii up to 2$`\mathrm{}`$.5 we obtain 5 more possible candidate associations with the stars in USNO A-2 Catalog. However, we exclude these possibilities since the error in RA and DEC determined by CELLDETECT is lower than 2$`\mathrm{}`$.5.

## 4 Spectral Analysis and Discussion

The source spectra and insturment responses are generated using CIAO (version 2.0) and analyzed using XSPEC (version 11.0.1) applying four models to the source data between 0.3 and 10 keV: blackbody, bremsstrahlung, powerlaw and VMEKAL with absorption. Spectra were grouped to have 5-10 counts per energy bin. The absorbed fluxes are found to be in a range 1$`\times `$10-16 \- 3$`\times 10^{14}`$ erg cm-2 s-1.
Table-2 shows the spectral parameters of the blackbody and power law models and Table-3 shows the spectral parameters of the bremsstrahlung and VMEKAL models. The errors on the spectral parameters are at 2$`\sigma `$ confidence level. Figure 1 shows the fitted source spectra of all the 18 sources that has the best $`\chi _\nu ^2`$s. The residuals in the figures are omitted since they were in a range of 2$`\sigma `$ \- -2$`\sigma `$, and did not show significant fluctuations.
Three of the sources (Src 4,12,16) are fitted using a power law model with photon indicies between 2.5 - 4 and have blackbody temperatures around 0.5 keV resembling the spectra of the Anomolous X-Ray Pulsars (AXPs) (Israel et al.israel (1999)). At a distance of 10 kpc, the luminosities of these three sources are found to be around 1032 ergs/s, and thus we exclude the possible AXP connection because the X-ray luminosities of AXPs are around 1035 ergs/s. Assuming a source distance of 10 kpc the luminosities of all the 18 sources are calculated to be around 1032 \- 1033 ergs/s. Such luminosities are consistent with galactic quiescent CV and quiescent LMXB origin. Two of the sources (Src 11,13) show evidence for line emmision with high absorbtion ( $`N_H>`$ 3$`\times `$ 1021 cm-2) and the best fit is the absorbed VMEKAL model. These sources are strong Cataclysmic Variable and quiescent LMXB candidates (Warner warner (1995); Verbunt et al. verbunt (1997); Guseinov et al. guseinov (2000)). In addition, luminosities around 1032 ergs/s could be attained by type O, B or giant stars as a consequence of shocks in the stellar winds or coronal emission (Cassinelli et al. cassinelli (1981); Schmitt et al. schmitt (1993)). When we exclude the sources with bremsstrahlung temperatures above 1 keV (since almost all of O, B type or giant stars have temperatures below 1 keV), we are left with 3 candidates for galactic stars; Src 6, 9 and 12. In general, we reject an HMXB origin for our sources, since their luminosities are low compared with an HMXB where the luminosity is $``$1036 ergs/s (Guseinov et al. guseinov (2000)). The luminosities of the sources are around 1037 ergs/s at 4 Mpc in agreement with the luminosities of the X-ray Binaries in other local galaxies, however we do not observe any host galaxy at those directions (Bauer et al. bauer (2001)). As noted in Section 1, none of these sources can be SSSs. The luminosities of the SSSs are around Eddington Luminosity (1038ergs/s) and the blackbody temperatures are between 10-60 eV with almost no emmision above 1 keV (Kahabka & van den Heuvel kahabka (1997)). None of our 18 sources have such spectral characteristics. For the case of Dim Thermal Neutron stars (DTNs) or cooling neutron stars, the spectra of DTNs and cooling neutron stars are very soft and almost all of them are within 100 pc distance (Alpar alpar (2001); Ögelman ogelman (1995)). A neutron star with a surface temperature around 106 K and a 10 km radius has an expected luminosity around 1033 ergs/s. The observations on cooling neutron stars depend on the sensitivity of the X-ray telescopes. Among our 18 sources, the softest two (Src 6,11) have blackbody temperatures of 0.19 keV. This temperature is relatively high for a DTN or a cooling neutron star, however we do not exclude the possible DTN or cooling neutron star connection since the sensitivity of $`CHANDRA`$ allows us to observe fluxes around 10-15 ergs cm-2 s-1 consistent with observation of a neutron star at 10 kpc with a temperature $``$0.1 keV. Due to the relative hardness of the spectra of these 18 sources, we can also say that none of these sources are isolated hot white dwarf candidates since the temperatures of the hot white dwarfs are ultrasoft; a few eVs (Vennes vennes (1999); Finley et al. finley (1997)).
We searched for the extragalactic origins of all the 18 sources. The rest frame luminosities of AGNs and galaxies are known to be between 1039 and 1045 ergs/s, and their spectra are best fitted with power law models having photon indicies around 1.7 - 2 (Brandt et al. brandt (2001); Ishisaki et al. ishisaki (2001)). The rest frame luminosities of nearly all of the 18 sources are calculated to be around 1042 \- 1044 ergs/s after fitting zmodels using XSPEC. Thus, we can not exclude the possibility of extragalactic origin for any of the sources. Two highly absorbed sources Src 3 and 5 have rest frame luminosities around 1042 ergs/s (redshift=0.206) and 1043 ergs/s (redshift=0.500) respectively. The photon indicies of these two sources are 1.61 and 1.89 respectively. Hence, we might categorize these two sources as strong AGN and galaxy candidates. Additionally, the NH values may be further evidence to exclude the extragalactic connection. The sources with NH higher than the value of the galactic NH in the direction of GK Per are more likely to be of extragalactic origin than the sources having the same order of NH with the galactic value. We may say that none of these sources are clusters since they are not extended and the rest frame luminosities of the clusters are usually higher than these values (Schindler schindler (1999)).
In addition, we searched for temporal characteristics of the new sources. We performed power spectrum analysis on three of the sources with the highest count rates (Src 4, 6, 18). However we could not find any significant periods. The 3$`\sigma `$ \- 4$`\sigma `$ detection threshold of power is around 40 in our data, and the power upper limit of the three sources is found to be 20.
Drawing conclusions about the classification of all the 18 sources is difficult using the X-ray data at hand. We can not study their temporal characteristics due to low count-rates, and we do not have detailed spectra. We have planned further deep observations of this field in the optical wavelengths with the 1.5 m telescope of the National Observatory at Antalya, Turkey to ensure optical identification. Complementary observations in other wavelengths are necessary for proper classification of these 18 sources.


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# Can a quantum measurement be cancelled in a very short period of time?

## Abstract

A test is suggested for whether the obtaining of certain information, and then deleting it too quickly to be retained, constitutes a quantum measurement of that information.

The question of what exactly constitutes a measurement, and when it takes place, remains debatable after more than 75 years of quantum mechanics. Here a method will be suggested for testing whether the capture of certain information by macroscopic instruments, followed by its partial erasure after a very short period of time, constitutes a measurement of all the information that was first captured, or only of the information which remains after the erasure.

Consider a system of two 2-level particles, for instance two spin-$`\frac{1}{2}`$ particles, and suppose them in an entangled state. Then if the particle spins are measured in directions $`\theta `$ and $`\varphi `$ respectively, this is a measurement of the two commuting observables

$$(\sigma _\theta ^Aid,id\sigma _\varphi ^B)$$
(1)
and we can deduce, in the usual way, that measurement of even one of these observables projects both particles into two definite unentangled states, and measurements can be made which will confirm, for instance, the correlations between them.

Suppose instead that we measured

$$\sigma _\theta ^A\sigma _\varphi ^B$$
(2)
This observable represents (as it indicates) the product of the individual particles’ outcomes, and, if the outcomes are treated as $`\pm `$1, can be regarded as measuring whether their results are the same (eigenvalue +1) or opposite (eigenvalue $``$1).

If a measurement is made, choosing either the observables (1) or the observable (2), the results are compatible, in that the probabilities of getting the results “same” or “opposite” are the same. But if two successive such measurements are made at different angles, incompatible results can be obtained222This was brought to my attention by G. Adenier , though Adenier argued for a viewpoint which is not adopted here.. For example, suppose the two particles are initially in the (normalized) state

$$\underset{i,j=\pm 1}{}\alpha _{ij}|i,j$$
(3)
with respect to z-direction eigenstates, and that, first, both are measured in the z-direction, and then, second, a measurement is made of the observables in (1) using the x-direction. If the first measurement is of the observables (1), the system is projected into one of the states $`|i,j`$ with probabilities $`\left|\alpha _{ij}\right|^2`$, and if both particles are then measured in the x-direction, each x-eigenstate is obtained with equal probability, and so in an ensemble of the two successive measurements there will be equal probability for each of the four outcomes at the end of the second measurement. But if the first measurement (in the z-direction) is of the observable in (2), then the system is projected into one of the states

$$\frac{1}{\sqrt{p_1}}\left\{\alpha _{11}|1,1+\alpha _{11}|1,1\right\},\frac{1}{\sqrt{p_1}}\left\{\alpha _{11}|1,1+\alpha _{11}|1,1\right\}$$
(4)
where $`p_1,p_2`$ are the respective probabilities, given by

$$p_1=\left|\alpha _{11}\right|^2+\left|\alpha _{11}\right|^2,p_1=\left|\alpha _{11}\right|^2+\left|\alpha _{11}\right|^2$$
(5)
and then the probability of, for instance, obtaining the x-eigenstate $`|1,1_x`$ at the end of the second measurement is

$$\frac{1}{4}\left\{\left|\alpha _{11}+\alpha _{11}\right|^2+\left|\alpha _{11}+\alpha _{11}\right|^2\right\}$$
(6)
which is clearly $`\frac{1}{4}`$ (except for special values of the $`\alpha _{ij}`$. It is also generally different to the probability of $`|1,1_x`$ if the first measurement is omitted, which is

$$\frac{1}{4}\left\{\left|\alpha _{11}+\alpha _{11}+\alpha _{11}+\alpha _{11}\right|^2\right\}$$
(7)
If we consider how this could be verified by experiment, the obvious question is how to measure whether the observers’ results are the same or opposite while leaving the individual results themselves unknown, and indeed unknowable.333But see in this context Ref  But this question can be turned into a test of quantum measurement. Suppose the particles are brought together (rather then being measured while spacelike-separated), and the measurement is made by an apparatus which is considered macroscopic, and which measures the two outcomes, multiplies them and retains that result, then irretrievably deletes the original individual results. If more than a very short time elapses between making the individual measurements and deleting them, the results must be appropriate to a measurement of (1), since the individual results could have been noted and recorded (whether they actually were or not). But if deletion takes place in a time so short that it was impossible to record the original results, then we are in the area of ignorance about what exactly constitutes a quantum measurement, and it is conjectural whether the results would be appropriate to (1) or to (2).

The situation can obviously be generalised, and does not necessarily need entangled states. Suppose $`\widehat{A}`$ and $`\widehat{B}`$ are a complete set of commuting observables on a system, i.e. $`\widehat{A}`$ and $`\widehat{B}`$ are degenerate but the degeneracy is lifted when both are measured. Suppose the joint measurement is made, and then, very quickly, a function $`f(\widehat{A},\widehat{B})`$ is evaluated from the outcomes, and recorded by methods which would usually be regarded as classical, while the values of $`\widehat{A}`$ and $`\widehat{B}`$ themselves are discarded irreversibly. Provided $`f(\widehat{A},\widehat{B})`$ is also degenerate, the projection by $`f(\widehat{A},\widehat{B})`$ is not generally the same as projection by the pair $`(\widehat{A},\widehat{B})`$. So would subsequent measurements give the results expected if the first measurement was of $`(\widehat{A},\widehat{B})`$, or $`f(\widehat{A},\widehat{B})`$?

This article will not attempt to design a specific experimental apparatus, but the requirements of an apparatus are as follows. We want the calculation and recording of the value of $`f(\widehat{A},\widehat{B})`$ from $`(\widehat{A},\widehat{B})`$ to take place by classical means, and we want the subsequent deletion of $`(\widehat{A},\widehat{B})`$ to be classical, yet irreversible. So suppose that the multiplication is carried out by some standard type of computer or calculator, while the deletion of the original results takes place before any signal could reach the memory section of the apparatus, and/or could be retained by the memory in view of the known volatility and other properties of the materials used. Of course it might be that a different design of apparatus and different materials could change the time threshold for the deletion, but that would be a different experiment; what matters is that with the particular design of apparatus which has been chosen, the information has been discarded irretrievably before it could be recorded, even if the apparatus was working at maximum efficiency.

If there is considered to be a difficulty in measuring a degenerate observable without lifting the degeneracy by co-measuring a compatible observable (at least accidentally), we may regard the measurement of $`f(\widehat{A},\widehat{B})`$ as part of a non-degenerate measurement one of whose outcomes in each degeneracy eigenspace, and the only one which can be obtained from the initial state since the others are orthogonal to it, is the same state as a direct application of the projector into the degeneracy eigenspace. For instance in the entangled particles example, if the outcomes of projection by $`\left(\sigma _z^A\sigma _z^B\right)`$ which are given in (4) are supplemented by orthogonal states, i.e. by

$$\frac{1}{\sqrt{p_1}}\left\{\alpha _{11}|1,1+\alpha _{11}|1,1\right\},\frac{1}{\sqrt{p_1}}\left\{\alpha _{11}|1,1+\alpha _{11}|1,1\right\}$$
(8)
we have a basis for a degeneracy-lifting co-measurement of $`\left(\sigma _z^A\sigma _z^B\right)`$ which gives the same outcomes, with the same probabilities, as a measurement of $`\left(\sigma _z^A\sigma _z^B\right)`$ on its own.

If this experiment, or more generally an experiment for $`f(\widehat{A},\widehat{B})`$ versus $`(\widehat{A},\widehat{B})`$, showed that the second measurement gave results appropriate to the first measurement being of $`f(\widehat{A},\widehat{B})`$, despite the fact that the only way $`f(\widehat{A},\widehat{B})`$ could have been evaluated was from the lost results of $`(\widehat{A},\widehat{B})`$ (nor could the recorded value of $`f(\widehat{A},\widehat{B})`$ be simply a mistake, with no first measurement having really happened in the circumstances), it must mean that what was measured was somehow relative to events at the macroscopic level. This would be compatible with the Copenhagen view that a quantum situation resides partly in the macroscopic context, and is also consistent with the “irreversible record” viewpoint that a measurement takes place when a record is created by an irreversible process. If the second measurement showed that the first measurement was of $`(\widehat{A},\widehat{B})`$, this would be consistent with “realist” pictures, decoherence, and also the many-worlds interpretation, since a splitting of observers should take place when $`(\widehat{A},\widehat{B})`$ is measured, with no splitting for the classical process of evaluating $`f(\widehat{A},\widehat{B})`$ and discarding $`(\widehat{A},\widehat{B})`$. Which of the two possibilities would be found seems to be an open question.


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# Imperfect Detectors in Linear Optical Quantum Computers

## I Ideal Linear Optical Quantum Computing

The goal of LOQC is to build a quantum computer that uses photons to encode information, but does not require any nonlinear medium to allow the photons to interact. Instead, we will only use single photon sources, beam splitters, phase shifters, and photon detectors which are able to distinguish between $`0`$, $`1`$, $`2`$, … photons. According to the original scheme for LOQC, each qubit is represented by a single photon in a superposition of two optical modes. The conventional notation is

$$|Q=a|0_1,1_2+b|1_1,0_2.$$
(1)
Here the logical value of $`0`$ corresponds to the eigenstate that has zero photons in optical mode $`1`$ and one photon in optical mode $`2`$, and the logical $`1`$ state has one photon in mode $`1`$ and zero photons in mode $`2`$. We will describe a phase shifter using the phase angle $`\varphi `$ that it imparts to a single photon, and $`\widehat{𝐏}_\varphi `$ is the unitary transformation that acts on the state of the photons traveling through the phase shifter $`𝐏_\varphi `$. For example $`\widehat{𝐏}_\varphi |0=|0`$, and $`\widehat{𝐏}_\varphi |1=e^{i\varphi }|1`$. Beam splitters $`𝐁_{\theta ,\varphi }`$ are similarly described using two angles, $`\theta `$ and $`\varphi `$. They are usually represented by the rotation matrix that transforms the photon creation operators $`a_n^{}`$ into their primed versions in the Heisenberg picture

$$\left(\begin{array}{c}a_{1}^{}{}_{}{}^{}\\ a_{2}^{}{}_{}{}^{}\end{array}\right)=\left(\begin{array}{cc}\mathrm{cos}(\theta )& e^{i\varphi }\mathrm{sin}(\theta )\\ e^{i\varphi }\mathrm{sin}(\theta )& \mathrm{cos}(\theta )\end{array}\right)\left(\begin{array}{c}a_1^{}\\ a_2^{}\end{array}\right)$$
(2)
Because any large unitary matrix can be written as a direct product of two by two unitary matrices, we can describe the action of many beam splitters on any number of optical modes by giving the matrix that is the direct product of the matrices describing each beam splitter and phase shifter. Suppose then that $`G`$ is such a matrix describing the transformation of many optical modes; the elements of $`G`$ are written as $`g_{ij}`$; and $`\widehat{G}`$ is the unitary operator acting on photon states in the Schrödinger picture. To find how a Fock state is transformed by $`\widehat{G}`$ we must compute

$$\widehat{G}|n_1,n_2,\mathrm{},n_m=\left(\underset{i=1}{\overset{m}{}}\frac{1}{\sqrt{n_i!}}\left(g_{i1}a_1^{}+g_{i2}a_2^{}+\mathrm{}+g_{im}a_m^{}\right)^{n_i}\right)|0_1,0_2,\mathrm{},0_m$$
(3)
This formalism allows us to generalize the concept of beam splitters to include a much wider class of devices, all of which can be constructed by collections of single mode phase shifters and conventional two mode beam splitters .

The first element of a LOQC is a device called $`NS_1`$ that will shift the phase of a mode containing two photons, but will leave a single photon undisturbed. $`NS_1`$ performs the transformation

$`|0_0`$ $``$ $`|0_0`$ (4)
$`|1_0`$ $``$ $`|1_0`$ (5)
$`|2_0`$ $``$ $`|2_0.`$ (6)
Performing this operation requires the preparation of two ancillary modes containing the state $`|1_1,0_2`$. The three modes are then sent through a network of beam splitters described by the matrix

$$\left(\begin{array}{ccc}1\sqrt{2}& 2^{1/4}& \sqrt{3/\sqrt{2}2}\\ 2^{1/4}& 1/2& 1/21/\sqrt{2}\\ \sqrt{3/\sqrt{2}2}& 1/21/\sqrt{2}& \sqrt{2}1/2\end{array}\right).$$
(7)
After passing through the network, the state of the three modes will be very complicated, but we then measure the number of photons contained in modes $`1`$ and $`2`$. If we measure the state $`|1_1,0_2`$, then the operation $`NS_1`$ was successfully performed. The probability that we measure the desired result is $`1/4`$. If some other number of photons is detected then the operation has failed, and the information contained in mode $`0`$ has been destroyed.

One of the fundamental universal gates for quantum computation is the controlled sign flip, which shifts the phase of a two qubit state when both qubits have the logical value of $`1`$ but does nothing if one of the qubits is $`0`$. In our LOQC notation, this is the transformation

$`|0_1,1_2,0_3,1_4`$ $``$ $`|0_1,1_2,0_3,1_4`$ (8)
$`|0_1,1_2,1_3,0_4`$ $``$ $`|0_1,1_2,1_3,0_4`$ (9)
$`|1_1,0_2,0_3,1_4`$ $``$ $`|1_1,0_2,0_3,1_4`$ (10)
$`|1_1,0_2,1_3,0_4`$ $``$ $`|1_1,0_2,1_3,0_4.`$ (11)
To execute this we must first prepare four ancilla modes containing the state $`|1_5,0_6,1_7,0_8`$. Then we follow the procedure:

1. Apply the beam splitter $`𝐁_{\pi /4,0}`$ to modes $`1`$ and $`3`$.
2. Perform the $`NS_1`$ operation on modes $`1`$, $`5`$, and $`6`$.
3. Perform the $`NS_1`$ operation on modes $`3`$, $`7`$ and $`8`$.
4. Apply the beam splitter $`𝐁_{\pi /4,0}`$ to modes $`1`$ and $`3`$.
5. Measure the number of photons in modes $`5`$ through $`8`$.

If the state $`|1_5,0_6,1_7,0_8`$ is detected, then the controlled phase shift has been performed correctly. If some other state is detected, then the qubits have been destroyed. This will succeed with probability $`(1/4)^2=1/16`$, so we call this protocol for the controlled sign flip $`\mathrm{c}z_{1/16}`$. Soon we will discuss other protocols that will increase the success probability, but these are more easily understood in the context of quantum teleportation.

The goal of quantum teleportation in a LOQC is to transfer the photon state of one mode to some other mode without directly connecting the two through a beam splitter. The following procedure will transfer the state $`|\psi =a|0_0+b|1_0`$ of mode $`0`$ to mode $`2`$.

1. Prepare the state $`|1_1,0_2`$.
2. Apply the beam splitter $`𝐁_{\pi /4,0}`$ to modes $`1`$ and $`2`$. This creates the state $`|t_1=1/\sqrt{2}(|0_1,1_2+|1_1,0_2)`$.
3. Apply the beam splitter $`𝐁_{\pi /4,0}`$ to modes $`0`$ and $`1`$.
4. Measure the number of photons in modes $`0`$ and $`1`$.

If the measurement yields $`|1_0,0_1`$ the mode $`2`$ will contain the state $`a|0_0b|1_0`$, so to return this to the original state $`|\psi `$, apply the phase shifter $`𝐏_\pi `$ to mode $`2`$. If the measurement yields $`|0_0,1_1`$ mode $`2`$ will contain $`|\psi `$ and nothing must be done. If the measurement has some other result, the operation has failed. This procedure will succeed with probability $`1/2`$, but it can be increased with the following method:

1. Prepare the state

$$|t_n=\frac{1}{\sqrt{n+1}}\underset{i=0}{\overset{n}{}}|1^i|0^{ni}|0^i|1^{ni},$$
(12)
where $`|x^i=|x|x|x\mathrm{}`$ $`i`$ times. $`|t_n`$ requires $`2n`$ optical modes, and they should be numbered from left to right in each term of the sum. $`|t_n`$ can be prepared using only beam splitters and the state $`|1^n|0^n`$.
2. Operate on modes $`0`$ through $`n`$ with the beam splitter network $`𝐅_𝐧`$, where the elements of the matrix describing $`𝐅_𝐧`$ are $`(F_n)_{j,k}=(e^{i2\pi /(n+1)})^{jk}/\sqrt{n+1}`$
3. Measure the photons in modes $`0`$ through $`n`$.

If the number of photons detected is $`m`$, and $`1mn`$, then the teleportation procedure has succeeded. The original state occupying mode $`0`$ is found in mode $`n+m`$, but this state may need to be corrected with a known phase shifter. The probability that $`1mn`$ is $`n/(n+1)`$.

To improve the success of the controlled sign flip, we will perform the teleportation procedure on each qubit, but rather than use two copies of the state $`|t_n`$ we will use the state

$$|\mathrm{cs}_n=\underset{i,j=0}{\overset{n}{}}(1)^{(ni)(nj)}|1^i|0^{ni}|0^i|1^{ni}|1^j|0^{nj}|0^j|1^{nj}.$$
(13)
Knill, Laflamme, and Milburn give an algorithm for the preparation of this state in . According to their algorithm, the preparation of $`|\mathrm{cs}_n`$ requires $`6n3`$ controlled phase shift operations  each of which succeeds only probabilistically by performing the $`\mathrm{c}z_{1/16}`$ operation or by preparing $`|\mathrm{cs}_m`$ for $`m<n`$ and executing this teleportation method. They provide no proof that their method is optimal, and we believe that finding the optimal procedure for preparation of $`|\mathrm{cs}_n`$ is a fruitful open problem. Imagine that qubit one occupies modes $`q_1`$ and $`q_2`$, qubit two occupies modes $`q_3`$ and $`q_4`$, and $`|\mathrm{cs}_n`$ occupies modes $`1`$ through $`4n`$. The algorithm is:

1. Operate on modes $`q_1`$ and the first $`n`$ modes of $`|\mathrm{cs}_n`$ with the beam splitter network $`𝐅_𝐧`$.
2. Operate on modes $`q_3`$ and the third $`n`$ modes of $`|\mathrm{cs}_n`$ with $`𝐅_𝐧`$.
3. Measure modes $`q_1`$ and $`1`$ through $`n`$. If $`1k_1n`$ photons are detected. The contents of mode $`q_1`$ are now found in mode $`n+k_1`$.
4. Measure modes $`q_3`$ and $`2n+1`$ through $`3n`$. If $`1k_2n`$ photons are detected, then the contents of mode $`q_3`$ are now found in mode $`3n+k_2`$.
5. Depending on $`k_1`$ and $`k_2`$, apply correcting phase shifters to $`n+k_1`$ and $`3n+k_2`$.

Provided that $`k_1`$ and $`k_2`$ satisfy the above conditions, this procedure will perform the controlled sign flip on the qubits rather than simply teleporting them. The probability that both teleportations succeed is $`(n/(n+1))^2`$, and we will refer to this procedure as $`\mathrm{c}z_{(n/(n+1))^2}`$. To increase this probability beyond 95% would require $`n39`$, and to prepare the necessary state $`|\mathrm{cs}_{39}`$ involves $`231`$ uses of the controlled sign flip operation each of which succeeds probabilistically.

## II Simulation of LOQC with imperfect detectors

In order to investigate the effects of imperfect photon detectors on the operation of the LOQC, we have developed a computer simulation using Mathematica.  The simulation represents the state of the LOQC in the Fock basis in which a basis state assigns an integer number of photons to each optical mode. Then superpositions are built out of the basis states in the usual manner. The simulation can then calculate how the operation of a collection of beam splitters and phase shifters transform the states. To simulate ideal measurement the simulation will generate a table displaying the probability to measure all possible numbers of photons in each mode being measured, the number of measured photons, and the collapsed state produced after the measurement. At this stage the simulation has calculated the probabilities that the measured modes of the computer contain 0, 1, 2, …, or $`N`$ photons, we must now calculate the probability that these photons are registered by the detectors.

We model photon loss using a binomial distribution.  If $`N`$ photons enter a detector, the probability that $`n`$ photons are registered by the detector is

$$p_{loss}(n,N,l)=\left(\begin{array}{c}N\\ n\end{array}\right)\left(1l\right)^nl^{Nn}$$
(14)
when $`nN`$, and $`p_{loss}(n,N,l)=0`$ when $`n>N`$. The inefficiency of the detectors is described with the parameter $`l`$ which is the probability that any given photon will be missed by the detector.

The photon detections may also be corrupted by noise photons. To calculate the probability that $`n`$ noise photons are added to the number of “real” photons each detector registers, we apply the Poisson distribution.

$$p_{noise}(n,g)=\frac{g^ne^g}{n!},$$
(15)
where $`g`$ is mean number of noise photons each detector is expected to register. Note that this Poisson distribution does not represent “quantum noise” in the photon field. Instead, we imagine it to represent accidental, for example thermal, excitations inside the detector which are independent of the incoming photons.

The exact physics of the atom-photon interactions in a photon detector are very complicated, and we make no attempt to model them here. Our goal is only to describe the interactions using the two phenomenological parameters $`l`$ and $`g`$. It is difficult to imagine how a more detailed understanding of photon detector physics would yield wildly different probability distributions, so we are confident that our treatment will give a good understanding of the reliability of LOQC.

We can apply these probability distributions to the photons entering each detector to build a table that shows the probability that each detector registers 1, 2, 3, … photons and the number of “real” photons that arrived at each detector. By adding the probabilities for the cases in which the number of photons registered by each detector and the number of photons that arrived at each detector are equal to one another and are both equal to the number prescribed by the LOQC protocol we can calculate $`p_s(l,g)`$ the probability that a given operation will succeed and the detectors will correctly detect the success. We also calculate $`p_d(l,g)`$, the probability that the detectors report that a given operation has succeeded, when in fact it may have failed, by adding the probabilities that the detectors register the number of photons prescribed by the LOQC protocol without regard to the number of “real” photons that arrived at the detectors. Using $`p_s`$ and $`p_d`$, we can also calculate $`p_f(l,g)=1\frac{p_s}{p_d}`$ the probability that the detectors register a false positive result, when the detectors register the number of photons prescribed by the LOQC protocol but the number of photons that arrived at the detectors is not equal to the prescribed number. This is surely the most damaging sort of error, because it is disguised as a successful calculation.

We first applied this analysis to the $`NS_1`$ operation, which succeeds when one photon is detected in mode $`1`$ and zero photons are detected in mode $`2`$. For an ideal device this should happen with probability $`\frac{1}{4}`$. The results of our simulation appear in Fig. 1, where we have plotted the $`p_s(l,g)`$ and $`p_f(l,g)`$ for the case when the input mode contains two photons.

We have also applied a similar simulation to the conditional sign flip $`\mathrm{c}z_{1/16}`$, when both entering qubits are in the logical $`|1`$ state. Plots showing the success probability and false success probability are shown in Fig. 2. We find that for detectors with $`l=0.1`$ and $`g=0.1`$, the operation will succeed in only 3.5% of its operations, and 35% of its apparent successes are in fact failures. The probability of obtaining false positive results will be below 1% for detectors better than those for which $`l=g=0.0025`$; $`l=0`$ and $`g=0.0033`$; or $`l=0.0099`$ and $`g=0`$.

The third system to which we apply our simulation is the controlled sign flip, $`\mathrm{c}z_{1/4}`$, in which the state $`|\mathrm{cs}_1=\frac{1}{2}\left(|11+|10+|01+|00\right)`$ is prepared using a single operation of the $`\mathrm{c}z_{1/16}`$ gate. The two qubits, both in the logical $`|1`$ state, are then teleported using the $`|\mathrm{cs}_1`$ state. Using perfect components, the probability of preparing $`|\mathrm{cs}_1`$ is $`1/16`$, and the probability of teleporting both qubits is $`1/4`$. Given detectors with $`l=g=0.1`$ we find that the probability to prepare $`|\mathrm{cs}_1`$ is 0.035, slightly more than half of the ideal probability, and 42% of the apparent successes are failures. Using these detectors the probability to both prepare $`|\mathrm{cs}_1`$ and to teleport the qubits is 0.0048, only one third of the ideal success rate. False positive results can be expected in 58% of the attempts. False positive rates lower than 1% can be achieved with detectors better than $`l=g=0.0012`$, $`l=0.0020`$ and $`g=0`$, or $`l=0`$ and $`g=0.0033`$. The less ambitious goal of lowering the false positive rate to 10% would be possible with detectors better than $`l=g=0.013`$, $`l=0.021`$ and $`g=0`$, or $`l=0`$ and $`g=0.036`$. These results are plotted in Fig. 3

## III Near deterministic teleportation with imperfect detectors

Because quantum teleportation is such an integral part of the improved versions of the controlled sign flip $`\mathrm{c}z_{(n/(n+1))^2}`$, we sought to understand the rate at which detector related errors grows as $`n`$ the size of the prepared teleportation state increases. Provided that the state $`|t_n`$ has been successfully prepared, we want to examine the probability that the state $`|1_0`$ can be teleported when using detectors with inefficiency $`l`$. For simplicity we assume that the detectors are noiseless. By examining several cases we have found a general formula for $`p_s(n,l)`$ the probability that the teleportation succeeds and is correctly registered by the detectors:

$$p_s(n,l)=\frac{1}{n+1}\underset{i=1}{\overset{n}{}}(1l)^i=\frac{\left(1\left(1l\right)^n\right)\left(1l\right)}{\left(1+n\right)l}.$$
(16)
The probability that exactly $`i=1,2,\mathrm{},`$ or $`n`$ photons arrive at the detectors is $`\frac{1}{n+1}`$, and the probability that all of the $`i`$ arriving photons are registered by the detectors is $`(1l)^i`$. According to this expression, for a given detector inefficiency $`l`$, there is a critical $`n=n_c`$ for which $`p_s`$ is maximized, and increasing $`n`$ past $`n_c`$ will actually decrease the probability that the teleportation will succeed and be correctly registered by the detectors. In Fig. 4 we plot the maximum achievable $`p_s`$ and the $`n_c`$ yielding this probability for a range of detector inefficiencies.

Of course, any increase in the number of detectors involved in the teleportation effort will increase the probability $`p_f(n,l)`$ that the detectors report that the teleportation has succeeded, when it has not. To find $`p_f(n,l)`$ we first calculate $`p_d(n,l)`$ the probability that the detectors report that the teleportation was successful. This includes all of the events counted in $`p_s(n,l)`$ and all of the ways that photons may be lost so that the detectors register $`1,2,3,\mathrm{},`$ or $`n`$ photons.

$$p_d(n,l)=\frac{1}{n+1}\underset{i=1}{\overset{n}{}}\left(\underset{j=0}{\overset{n+1i}{}}\left(\begin{array}{c}j+i\\ j\end{array}\right)p^j\right)\left(1p\right)^i$$
(17)
$`p_f(n,l)`$ is then given by

$$p_f(n,l)=1\frac{p_s(n,l)}{p_d(n,l)}.$$
(18)
Any increase in $`n`$ will always increase the probability of receiving false positive results from the detectors. In Fig. 4c we have plotted $`p_f(n_c,l)`$. To build a teleportation device with a success probability of 0.9 requires detectors with $`l=0.0055`$ and $`n=19`$, and for 0.99 success rate requires $`l=0.00006`$ and $`n=182`$. Fig. 5 shows how quickly $`p_f`$ increases with $`n`$ for detector inefficiencies of 1% and 0.01%.

Construction of the near deterministic controlled sign flip requires the preparation of the state $`|\mathrm{cs}_n`$, which contains $`2n`$ photons distributed throughout $`4n`$ modes. The first $`2n`$ modes are used to teleport the first qubit and the second $`2n`$ modes to teleport the second qubit, and after the teleportation the qubits will have received a controlled sign flip. The probability that each of these teleportations succeeds is equal to $`p_s(n,l)`$, and the probability that detectors report that each teleportation succeeds is just $`p_d(n,l)`$. The probabilities of detecting the various possible numbers of photons during the teleportation of each qubit are independent of one another, so the probability to successfully implement the controlled sign is $`\left(p_s(n,l)\right)^2`$, and the probability of obtaining false positive results is

$$p_f(n,l)=1\left(\frac{p_s(n,l)}{p_d(n,l)}\right)^2$$
(19)
For detectors with $`l=0.1`$ the maximum achievable success rate is 0.38, which is obtained when $`n=4`$, but 48% of apparent successes are false. To build a controlled sign teleportation that succeeds 90% of attempts requires detectors with loss $`l0.0014`$ and $`n37`$. A 99% reliable gate needs $`l0.000013`$ and $`n392`$.

All of the results in this section rely on the assumption that the detectors produce zero noise. We chose to omit noise because of the complexity it adds to the calculations, because based on our simulations the errors caused by noise are very similar to those caused by loss when both the noise and loss are small, and because of the difficulty of displaying the results when varying inefficiency, $`n`$, and noise. Knill, Laflamme, and Milburn mention in  that one possible way to reduce the occurrence of false positive results in the teleportation procedure is to, after measuring $`k`$ photons in modes $`0`$ through $`n`$, also measure the photons in modes $`n+1`$ through $`n+k1`$ and modes $`n+k+1`$ through $`2n`$ (all of the ancillary modes that do not contain the teleported qubit). Then the total number of detected photons should equal the number of photons in $`|t_n`$, otherwise one or more has been lost. Although this would reduce false positive results it will also reduce the device’s success probability because sometimes the $`n1`$ detectors in the second stage will lose photons when the $`n+1`$ primary detectors monitoring modes $`0`$ through $`n`$ function correctly, in which case good events would be discarded. If we naively imagine that each detector has the same probability $`p`$ to lose at least one photon, then using this method would reduce the success rate of the teleportation from $`(1p)^{n+1}`$ to $`(1p)^{2n}`$. From all successful teleportations, a fraction of $`1(1p)^{n1}`$ would be rejected because some of the secondary detectors may malfunction.

## IV Conclusions

In  Knill, Laflamme, and Milburn conservatively estimate that an accuracy threshold better than 99% for controlled sign flip operations is required to construct a reliable LOQC. The main result of this paper is the calculation that to achieve this threshold when performing the $`\mathrm{c}z_{(n/(n+1))^2}`$ with a perfectly prepared $`|\mathrm{cs}_n`$ state requires photon detectors with inefficiencies lower than $`l=0.000013`$, which are much superior to today’s best photon detectors. This leads us to search for LOQC schemes that do not rely so heavily on the detection of single photons. One such possibility may be the use of coherent state qubits as outlined in . In their scheme all detectors except one receive a large number of photons, and success or failure decisions are based on identifying the detector that registered zero photons compared to those detectors that registered a number of photons proportional to the (assumed to be large) amplitude of the coherent state.

This work has made no attempt to analyze the effect of unreliable photon sources and beam splitters, which would greatly complicate the analysis. Another open problem is the analysis of the many error correction procedures outlined in , to understand their vulnerability to photon loss and noise.

Lastly, we should note that this work should not be interpreted as a criticism of the many current experimental efforts  to build some basic LOQC elements. Most of these experiments apparently plan to use coincidence measurements, which are largely impervious to corruption by photon loss or noise because those events can be discarded. However this is not a practical strategy to incorporate in a large scale quantum computer, because the qubits cannot be measured until the entire calculation involving very large numbers of controlled sign flip operations is complete.

## V Acknowledgments

S. G. thanks the Arthur J. Schmitt Foundation for fellowship support. J. M. L. is supported in part by the Division of High Energy Physics, Office of Science, U. S. Department of Energy under contract number DE-FG02-00ER41145. C. E. T. is supported in part by the Division of Chemical Sciences, Office of Basic Energy Sciences, Office of Energy Research, U. S. Department of Energy under contract number DE-FG02-95ER14579 and in part by the Atomic and Molecular Physics Program of the National Science Foundation under contract number PHY99-87984.


text:
# Nuclear shell effects near the r-process path This work is supported by the Project No. SP056 of the Research Administration, Kuwait University.

## 1 INTRODUCTION

The $`N=82`$ nuclei at r-process path are assumed to play a significant role in providing nuclear abundances about $`A130`$ . Since nuclei contributing to this peak are extremely neutron-rich and are not accessible experimentally, there prevail conflicting view points  on the strength of the shell effects near the neutron drip line. In this work, we examine how the shell effects evolve with isospin in the region of the astrophysically important magic number $`N=82`$ near the neutron drip line. Using the experimental data on the waiting-point nucleus 80Zn ($`N=50`$), we explore the shell effects near the r-process path in the framework of the Relativistic Hartree-Bogoliubov (RHB) theory with the vector self-coupling of $`\omega `$ meson. In this approach, the shell effects about the stability line have been described successfully .

## 2 THE RMF AND THE RHB APPROACH

The RMF Lagrangian describes the nucleons as Dirac spinors moving in meson fields and is given by

$``$ $`=`$ $`\overline{\psi }\left(\text{/}pg_\omega \text{/}\omega g_\rho \text{/}\stackrel{}{\rho }\stackrel{}{\tau }{\displaystyle \frac{1}{2}}e(1\tau _3)\text{ /}Ag_\sigma \sigma M_N\right)\psi `$
$`+{\displaystyle \frac{1}{2}}_\mu \sigma ^\mu \sigma U(\sigma ){\displaystyle \frac{1}{4}}\mathrm{\Omega }_{\mu \nu }\mathrm{\Omega }^{\mu \nu }+{\displaystyle \frac{1}{2}}m_\omega ^2\omega _\mu \omega ^\mu `$
$`+{\displaystyle \frac{1}{2}}g_4(\omega _\mu \omega ^\mu )^2{\displaystyle \frac{1}{4}}\stackrel{}{R}_{\mu \nu }\stackrel{}{R}^{\mu \nu }+{\displaystyle \frac{1}{2}}m_\rho ^2\stackrel{}{\rho }_\mu \stackrel{}{\rho }^\mu {\displaystyle \frac{1}{4}}F_{\mu \nu }F^{\mu \nu }`$
where $`M_N`$ is the bare nucleon mass and $`\psi `$ is its Dirac spinor. In addition, we have the scalar meson ($`\sigma `$), isoscalar vector mesons ($`\omega `$), isovector vector mesons ($`\rho `$) and the photons $`A^\mu `$, with the masses $`m_\sigma `$, $`m_\omega `$ and $`m_\rho `$ and the coupling constants $`g_\sigma `$, $`g_\omega `$, $`g_\rho `$, respectively. A nonlinear scalar potential $`U(\sigma )=\frac{1}{2}m_\sigma ^2\sigma ^2+\frac{1}{3}g_2\sigma ^3+\frac{1}{4}g_3\sigma ^4`$ for $`\sigma `$-mesons is used for a realistic description of finite nuclei. Recently, we have also added the non-linear vector self-coupling of $`\omega `$-meson  which is represented by $`g_4`$.

For nuclei near a drip line, a coupling to the continuum is required. A self-consistent treatment of pairing is also necessary. We employ the framework of RHB theory which takes into account both these features. The corresponding relativistic Dirac-Hartree-Bogoliubov (RHB) equations are obtained as

$$\left(\begin{array}{cc}h& \mathrm{\Delta }\\ \mathrm{\Delta }^{}& h^{}\end{array}\right)\left(\begin{array}{c}\hfill U\\ \hfill V\end{array}\right)_k=E_k\left(\begin{array}{c}\hfill U\\ \hfill V\end{array}\right)_k,$$
(2)
where $`E_k`$ are quasiparticle energies and the coefficients $`U_k`$ and $`V_k`$ are four-dimensional Dirac spinors. The pairing potential $`\mathrm{\Delta }`$ in Eq. (2) is given by

$$\mathrm{\Delta }_{ab}=\frac{1}{2}\underset{cd}{}V_{abcd}^{pp}\kappa _{cd}$$
(3)
The RHB calculations are performed by expanding fermionic and bosonic wavefunctions in 20 oscillator shells for a spherical configuration. We have used the force NL-SH  with the non-linear scalar self-coupling and the forces NL-SV1 and NL-SV2 with both the scalar and the vector self-couplings. The forces NL-SV1 and NL-SV2 have recently been developed in order to soften the high-density equation of state of nuclear matter and are shown to improve the ground-state properties of nuclei .

## 3 RESULTS AND DISCUSSION

In our previous work, it was shown that the existing nuclear forces based upon the nonlinear scalar self-coupling of $`\sigma `$-meson exhibit shell effects which were stronger than suggested by the experimental data. This problem was solved by introducing the nonlinear vector self-coupling of $`\omega `$-meson in the RHB theory . Having our working basis established, we explore the shell effects about 80Zn ($`N=50`$). 80Zn is a waiting point nucleus and here the r-process path comes closest to the $`\beta `$-stability line. We show in Fig. 1 the results on $`S_{2n}`$ values for the Zn isotopes. The kink at $`N=50`$ (Fig 1.a) shows that NL-SH (scalar self-coupling only) exhibits shell effects which are much stronger than the experimental data. In comparison, the shell gap with NL-SV2 (both the scalar and vector self-couplings)  is reduced as compared to NL-SH. The shell gap is, however, still larger than the experimental one. In Fig. 1(b) we show the $`S_{2n}`$ values obtained with the force NL-SV1. The slope of the kink shows that NL-SV1 is able to reproduce well the empirical shell effects in the waiting point region. A comparison with the HFB+SkP results shows that the shell effects with SkP are strongly quenched. The shell effects were shown to be quench with SkP already at the stability line . This behaviour is evidently due to the high effective mass $`m^{}1`$.

With the formalism established in  and tested in Fig. 1, we extend it to explore the inaccessible region of the neutron drip-line about $`N=82`$. In order to visualize the evolution of shell effects, we have chosen the isotopic chains of Kr, Sr, Zr and Mo ($`Z=3642`$). The results with RHB using various forces are shown in Fig. 2. For a given force, the shell gap at $`N=82`$ shows a steady decrease in moving from Mo (a) to Kr (d). Nuclei become increasingly unbound and a coupling to the continuum arises in going to larger neutron to proton ratios. The results with the non-linear scalar coupling (NL-SH) show a shell gap at $`N=82`$, which is largest amongst all the forces. Similarly strong shell effects with NL-SH were also shown for $`N=82`$ nuclei near the drip line in ref.  within the BCS pairing. With the force NL-SV2 with the vector self-coupling of $`\omega `$-meson, the shell effects are milder as compared to NL-SH for all the chains. The results (Fig. 2) with our benchmark force NL-SV1 show that the shell gap at $`N=82`$ is reduced as compared to NL-SV2. This is again similar to that observed for the Zn isotopes. However, the shell effects with NL-SV1 are still stronger as compared to the HFB+SkP results as shown in the figure. This is especially true for Mo and Zr isotopes at N=82, where the r-process path is assumed to pass through. The quenching shown by SkP in this region is as expected. This is consistent with a strong quenching exhibited by HFB+SkP at the stability line  and also near the waiting-point nucleus 80Zn as shown in Fig. 1(b). In comparison, the RHB approach with NL-SV1 shows stronger shell effects about the stability line  as well as in the waiting-point region at $`N=50`$, which is consistent with the experimental data.

The shell effects with NL-SV1 become successively weaker as one moves to nuclei with higher isospin such as 120Sr (Fig. 2(c)) and 118Kr (Fig. 2(d)). It is worth making a special mention of the Kr nucleus. All the forces (except NL-SH) show a complete washing out of the shell effects. This stems from the fact that for 118Kr the Fermi energy is very close to the continuum. The shell gap ceases to exist and consequently binding energy of an extra neutron is nearly zero. This implies that the shell effects for 118Kr ($`N=82`$) are washed out. Such nuclei at the drip line ($`\lambda _n0`$) are of little interest to the r-process as these nuclei can not bind an additional neutron. However, as the r-process path passes through $`S_n24`$ MeV, it is seen (Figs. 2.a and 2.b) that nuclei which would contribute to the r-process show a persistence of stronger shell gaps in contrast to that seen for Kr and Sr. Figures 2(a) and 2(b) show that with NL-SV1 the shell effects for Mo (Z=42) and Zr (Z=40) nuclei at $`N=82`$ are much stronger than with SkP. For r-process nuclei with $`Z>42`$, the shell gaps are expected to be even larger.

## 4 CONCLUSION

We have reproduced the shell effects about the waiting-point nucleus 80Zn with the vector self-coupling of $`\omega `$-meson in the RHB theory. With this basis, it is shown that the shell effects near the r-process path about $`N=82`$ remain strong vis-a-vis a quenching exhibited by HFB+SkP. The quenching shown by SkP is not consistent with the available data. It is noteworthy that on the basis of the results with SkP, a quenching has been requested for an improved fit to the global r-process abundances . Since SkP is not able to reproduce the shell effects at the stability line and in the waiting-point region, an improved fit alone does not necessarily imply a shell quenching near the r-process path. Thus, alternative mechanisms for nucleosynthesis need to be looked into.