text:
# Diffusive grain-surface chemistry involving the atoms and diatomic molecules of two elements

## 1 Introduction

If species accrete from the gas phase onto the surfaces of grains more quickly than they diffuse across a grain surface and react with each other, the surface chemistry is said to be taking place in the reaction limit. Such chemistry has been treated by Pickles & Williams (1977), who used a system of rate equations similar to those employed in gas-phase chemistry. This approach is often referred to as the standard deterministic rate equation method.

In some cases, species diffuse across grain surfaces and react with each other faster than they accrete. Therefore, when a species is accreted, and there is already another reactive species on the grain, they are likely to react before another particle accretes. The rates of reaction are therefore limited by the rates of accretion; the chemistry is said to be occurring in the accretion limit. Under these conditions, the average numbers of reactive species on a grain are small, and a stochastic model is required. The first attempts at stochastic modelling of interstellar grain surface chemistry in the accretion limit were made by Allen & Robinson (1977) and Tielens & Hagen (1982). The model of Allen & Robinson (1977) was constructed under the assumption that when a molecule is produced in a grain surface reaction, it immediately enters the gas phase; the model was extended by Tielens & Hagen (1982) to allow for the accumulation of grain mantles. In their model, Tielens & Hagen (1982) used Monte Carlo techniques to calculate the steady-state concentrations of mantled species. Later, various other authors constructed Monte Carlo models of grain surface chemistry (e.g. Tielens & Allamandola 1987; Tielens 1995 (unpublished); Charnley et al. 1997; Tielens & Charnley 1997; Charney 2001). Charnley (1998) used Monte Carlo methods to solve the master equation (which gives the probability that there is a certain number of particles of each species) governing gas-phase chemistry, and suggested that a similar approach may be applicable to grain surface chemistry.

As Monte Carlo simulations are computationally too expensive to use in the study of large systems, Caselli et al. (1998; 2002) and Shalabiea et al. (1998) introduced semi-empirical modifications to the standard determininstic rate equations, with the aim of solving the problem of inaccuracy of rate equation methods in the accretion limit.

Biham et al. (2001) and Green et al. (2001) studied, with a master equation approach, the production rate of H2 on surfaces. Green et al. (2001) used a generating function method to obtain an analytic solution for the H2 production rate. They also investigated more complex chemistries, using sparse matrix techniques to obtain the probabilities that a grain contains given numbers of particles of each species. With this approach, the calculation must be truncated at a certain maximum number of particles of each species, i.e. there is some truncation value for the number of particles, above which the probabilities are assumed to be zero. With a high enough truncation value, the results are almost exact. Green et al. (2001) used the probabilities obtained in this way to calculate the rates of production of molecules on grain surfaces. They solved the master equation numerically for the system of H and O, reacting on grain surfaces to form H2, O2, and OH, and also for the system of H, O, and N, reacting to form H2, O2, OH, NH, N2, NO, NO2, H2O, and NH3. They compared the results given by the solution of the master equation with a high truncation value, to those given by (i) the use of the master equation method with a low truncation value; (ii) the standard deterministic rate equation; and (iii) an approximate method, based on the assumption that the sweeping rate of atomic hydrogen on grain surfaces is so great that a reactive species already on the surface of a grain will react as soon as an H atom is accreted.

Stantcheva et al. (2002) solved the master equation for the system of H, O, and CO reacting on the surfaces of grains to produce O2, H2, H2O, CO2, H2CO, and CH3OH. They investigated the accuracy of results given by the method for different truncation values and also the accuracies of results given by other approaches.

In this paper, we examine the system of atoms X and Y reacting to form X2, XY, and Y2 on grain surfaces. We study a wide variety of adsorption, desorption, and diffusion rates, covering the accretion limit, the reaction limit, and cases intermediate between them. We compare the almost exact results, obtained through the solution of the master equation for high truncation values, with the results obtained (i) through the solution of the master equation with low truncation values; (ii) with the approximate method used by Green et al. (2001); (iii) with the standard deterministic rate equation approach; and (iv) with a modified rate equation approach similar to that employed by Caselli et al. (2002). Although the network we study is smaller than that of Stantcheva et al. (2002), we examine a much larger range of adsorption, desorption, and diffusion rates, thereby gaining insight into the parameter ranges in which each method may be applied.

In Sect. 2, the various approaches to the problem are discussed. We present our results in Sect. 3, and Sect. 4 concludes the paper.

## 2 The various approaches to the problem

We consider a system in which atoms X and Y accrete from the gas phase onto the surfaces of grains, diffuse across the grain surfaces, and react with each other to form X2, Y2, and XY, i.e. in which the following reactions take place:

$`\mathrm{X}+\mathrm{X}`$ $``$ X2 (1)
$`\mathrm{Y}+\mathrm{X}`$ $``$ $`\mathrm{XY}`$ (2)
$`\mathrm{Y}+\mathrm{Y}`$ $``$ $`\text{Y}\text{2}.`$ (3)
We assume that the X2, XY, and Y2 molecules remain on the grain surfaces, but that they do not react with each other or with X or Y. We allow for desorption of X from grains, but assume that desorption of Y is negligible. Let $`a_\mathrm{X}`$ and $`a_\mathrm{Y}`$ be the rates of accretion of X and Y respectively, and $`d_\mathrm{X}`$ be the rate of desorption of X. Let $`t_\mathrm{s}(\mathrm{X})`$ and $`t_\mathrm{s}(\mathrm{Y})`$ be the grain surface sweeping times for X and Y respectively. To reduce the number of free parameters, we assume

$$a_\mathrm{X}=a_\mathrm{Y}$$
(4)
This assumption is likely to be reasonable at some densities in dense cores if X is hydrogen and Y is oxygen. Furthermore, in a number of previous studies (e.g. Stantcheva et al. 2002), the ratio of accretion rates has been varied.

We normalise with respect to $`t_\mathrm{s}(\mathrm{X})`$ as follows.

$`\alpha `$ $`=`$ $`a_\mathrm{X}`$$`t_\mathrm{s}(\mathrm{X})`$ (5)
$`\delta `$ $`=`$ $`d_\mathrm{X}`$$`t_\mathrm{s}(\mathrm{X})`$ (6)
$`\tau `$ $`=`$ $`{\displaystyle \frac{t_\mathrm{s}(\mathrm{Y})}{t_\mathrm{s}(\mathrm{X})}}`$ (7)
The dimensionless rates for Reactions (1) to (3) are

$`\kappa _{\mathrm{XX}}`$ $`=`$ $`2`$ (8)
$`\kappa _{\mathrm{XY}}`$ $`=`$ $`1+\tau ^1`$ (9)
$`\kappa _{\mathrm{YY}}`$ $`=`$ $`2\tau ^1`$ (10)
Eqs. (8) to (10) may be compared to the rates given by Eq. (9) of Caselli et al. (1998) for two arbitrary species I and J.

The production rates of X2, XY, and Y2 were calculated with the various approaches for $`13\times 13\times 13`$ sets of values of $`\alpha `$,$`\delta `$,$`\tau `$ between 0.1 and 10. Calculations were also performed for $`9\times 13\times 9`$ sets of $`0.01\alpha 0.09`$, $`0.1\delta 10.0`$, $`0.01\tau 0.09`$.

We now discuss in detail the master equation approach, the standard and modified rate equation approaches, and the approximate method of Green et al. (2001).

### 2.1 Master equation approach

Green et al. (2001) gave the master equation for the hydrogen and oxygen system in their Eq. (29), and the rates of production of H2, OH, and O2 in their Eqs. (26) to (28). The generalisation of their equations to species X, Y, X2, XY, and Y2 is trivial. The average numbers of X and Y atoms on the surface of a grain are:

$`N(\mathrm{X})`$ $`=`$ $`{\displaystyle \underset{\stackrel{i=0}{j=0}}{\overset{\mathrm{}}{}}}iP(i,j)`$ (11)
$`N(\mathrm{Y})`$ $`=`$ $`{\displaystyle \underset{\stackrel{i=0}{j=0}}{\overset{\mathrm{}}{}}}jP(i,j)`$ (12)
where $`P(i,j)`$ is the probability that on the surface of a grain there are $`i`$ atoms of species X and $`j`$ atoms of species Y. We assumed the system to be in steady state, so that $`\frac{\mathrm{d}P(i,j)}{\mathrm{dt}}=0`$ for all $`i,j`$, and followed Green et al. (2001) in solving the master equation through the inversion of a sparse matrix by the row-indexed method. As discussed in Sect. 1, with this approach it is necessesary to truncate the sums at particular values of $`i`$ and $`j`$. They were truncated first at $`i=j=2`$ (which will be referred to as the low truncation case), and then at higher values (which will be referred to as the high truncation case), above which the results did not change appreciably if $`i`$ and $`j`$ were increased further. The results given by the master equation approach with high truncation values of $`i`$ and $`j`$ – typically $`i=j5`$ – can be considered to be exact, and will be referred to as the exact results.

### 2.2 Standard rate equation approach

The standard deterministic rate equations for the H, O, H2, OH, and O2 system are given by Caselli et al. (1998) in their Eqs. (4) to (8). They can be generalised easily to the X, Y, X2, XY, and Y2 system. The rate equations for X and Y were integrated with a Gear algorithm until the system reached steady state. Then, the production rates of X2, XY, and Y2 were calculated from their rate equations.

### 2.3 Modified rate equation approach

We introduced modifications to the rate equations, similar to those suggested by Caselli et al. (1998, 2002) in their attempt to develop a set of deterministic equations appropriate in both the reaction limit and the accretion limit. The modifications we used were based on those used by Caselli et al. (2002).

We define $`\theta _1`$ and $`\theta _2`$ as

$`\theta _1`$ $`=`$ $`{\displaystyle \frac{\kappa _{\mathrm{X},\mathrm{X}}N(\mathrm{X})+\kappa _{\mathrm{X},\mathrm{Y}}N(\mathrm{Y})}{\alpha }}`$ (13)
$`\theta _2`$ $`=`$ $`{\displaystyle \frac{\kappa _{\mathrm{Y},\mathrm{Y}}N(\mathrm{Y})+\kappa _{\mathrm{X},\mathrm{Y}}N(\mathrm{X})}{\alpha }}`$ (14)
In cases in which $`\theta _11`$ and $`\theta _21`$, the standard deterministic rate equations were used. Otherwise, the equations were modified as follows.

In the case that $`\theta _1>1`$ and $`\theta _21`$, the probability that species Y reacts is either less than or equal to 1, so that for Y2 formation the standard deterministic rate equation approach can be used. However the probability that species X reacts is greater than 1, and the equations for the production of X2 and XY must be modified. The rate coefficients $`\kappa _{\mathrm{X},\mathrm{X}}`$ and $`\kappa _{\mathrm{X},\mathrm{Y}}`$ are replaced by the larger of $`\alpha `$ and $`\delta `$ (Caselli et al. 1998, 2002); this quantity will be denoted by $`\kappa _\mathrm{X}^{}`$. In addition, the formation rate of X2 is multiplied by the probability that X reacts with another X instead of with a Y, and the rate of formation of XY is multiplied by the probability that X reacts with Y and not with another X (following Caselli et al. 2002). The production rates, $`\mathrm{\Gamma }`$(X2) and $`\mathrm{\Gamma }`$(XY), of X2 and XY, in this approach become

$`\mathrm{\Gamma }(\mathrm{X}_2)`$ $`=`$ $`\kappa _\mathrm{X}^{}N(\mathrm{X}){\displaystyle \frac{\kappa _{\mathrm{X},\mathrm{X}}N(\mathrm{X})}{\kappa _{\mathrm{X},\mathrm{X}}N(\mathrm{X})+\kappa _{\mathrm{X},\mathrm{Y}}N(\mathrm{Y})}}`$ (15)
$`\mathrm{\Gamma }(\mathrm{XY})`$ $`=`$ $`\kappa _\mathrm{X}^{}N(\mathrm{X}){\displaystyle \frac{\kappa _{\mathrm{X},\mathrm{Y}}N(\mathrm{Y})}{\kappa _{\mathrm{X},\mathrm{Y}}N(\mathrm{Y})+\kappa _{\mathrm{X},\mathrm{X}}N(\mathrm{X})}}`$ (16)
After (15), (16), and the standard rate equation for Y2 are used, $`\theta _2`$ is recalculated; if it is found to exceed unity then the approach described below for cases in which $`\theta _1>1`$ and $`\theta _2>1`$ is applied.

The case in which $`\theta _11`$ and $`\theta _2>1`$ is the same as the previous case, except that X is replaced by Y and vice versa. So $`\mathrm{\Gamma }`$(X2) can be calculated with the standard determistic rate equation approach, and the rates of formation, $`\mathrm{\Gamma }`$(XY) and $`\mathrm{\Gamma }`$(Y2), of XY and Y2, are

$`\mathrm{\Gamma }(\mathrm{XY})`$ $`=`$ $`\kappa _\mathrm{Y}^{}N(\mathrm{Y}){\displaystyle \frac{\kappa _{\mathrm{X},\mathrm{Y}}N(\mathrm{X})}{\kappa _{\mathrm{X},\mathrm{Y}}N(\mathrm{X})+\kappa _{\mathrm{Y},\mathrm{Y}}N(\mathrm{Y})}}`$ (17)
$`\mathrm{\Gamma }(\mathrm{Y}_2)`$ $`=`$ $`\kappa _\mathrm{Y}^{}N(\mathrm{Y}){\displaystyle \frac{\kappa _{\mathrm{Y},\mathrm{Y}}N(\mathrm{Y})}{\kappa _{\mathrm{Y},\mathrm{Y}}N(\mathrm{Y})+\kappa _{\mathrm{X},\mathrm{Y}}N(\mathrm{X})}}`$ (18)
where $`\kappa _\mathrm{Y}^{}`$is the larger of the accretion rate and the desorption rate of Y; however because we are neglecting desorption of Y, $`\kappa _\mathrm{Y}^{}=\alpha `$. After Eqs. (17) and (18) and the standard rate equation for X2 production are used, $`\theta _1`$ is recalculated; if it is found to be greater than unity then the approach described below for cases in which $`\theta _1>1`$ and $`\theta _2>1`$ is applied.

In the case in which both $`\theta _1`$ and $`\theta _2`$ are greater than 1, the rate equations for X2, XY, and Y2 must be modified. For the formation rates of X2 and Y2 we used Eqs. (15) and (18), respectively. For the XY formation rate, we used Eq. (16) when $`\theta _1>\theta _2`$, and Eq. (17) when $`\theta _1<\theta _2`$.

In all cases, the rates of change of $`N(\mathrm{X})`$ and $`N(\mathrm{Y})`$ are

$`{\displaystyle \frac{\mathrm{d}N(\mathrm{X})}{\mathrm{d}t}}`$ $`=`$ $`\alpha \delta N(\mathrm{X})2\mathrm{\Gamma }(\mathrm{X}_2)\mathrm{\Gamma }(\mathrm{XY})`$ (19)
$`{\displaystyle \frac{\mathrm{d}N(\mathrm{Y})}{\mathrm{d}t}}`$ $`=`$ $`\alpha 2\mathrm{\Gamma }(\mathrm{Y}_2)\mathrm{\Gamma }(\mathrm{XY})`$ (20)
Eqs. (19) and (20) were integrated with a Gear algorithm until the system reached steady state. At each step in the integration, the rates of production of X2, XY, and Y2 were calculated using the standard deterministic, or modified, rate equations as appropriate, and were used in the calculations of $`\frac{\mathrm{d}N(\mathrm{X})}{\mathrm{d}t}`$ and $`\frac{\mathrm{d}N(\mathrm{Y})}{\mathrm{d}t}`$.

### 2.4 Approximate Method

Green et al. (2001) introduced an analytic approximation to the master equation method, based on the assumption that the sweeping rate of X is so fast that if there is a reactive species (X or Y in this case) on the surface of a grain, a X atom accreting onto the grain will react immediately. This is equivalent to assuming that $`\kappa _{\mathrm{X},\mathrm{X}}\alpha `$, and that the probability of there being more than one reactive species on the surface of a grain is small. Green et al. (2001) showed that, under these assumptions

$`\mathrm{\Gamma }(\mathrm{X}_2)`$ $``$ $`{\displaystyle \frac{\alpha ^2P(0,0)}{2\alpha +\delta }}`$ (21)
$`\mathrm{\Gamma }(\mathrm{XY})`$ $``$ $`\alpha ^2\left[{\displaystyle \frac{1}{2\alpha +\delta }}+{\displaystyle \frac{1}{2\alpha }}\right]P(0,0)`$ (22)
$`\mathrm{\Gamma }(\mathrm{Y}_2)`$ $``$ $`{\displaystyle \frac{\kappa _{\mathrm{Y},\mathrm{Y}}}{\kappa _{\mathrm{Y},\mathrm{Y}}+2\alpha }}{\displaystyle \frac{\alpha }{2}}P(0,0)`$ (23)
where

$$P(0,0)\left[\frac{3}{2}+\frac{\alpha }{2\alpha +\delta }\right]^1$$
(24)
## 3 Results and discussion

For each of the methods described in Sect. 2, the production rates of X2, XY, and Y2 were evaluated with $`\alpha `$, $`\delta `$, $`\kappa _{\mathrm{X},\mathrm{X}}`$, $`\kappa _{\mathrm{X},\mathrm{Y}}`$, and $`\kappa _{\mathrm{Y},\mathrm{Y}}`$ given by Eqs. (5) to (10), with $`\alpha `$, $`\delta `$, and $`\tau `$ having various values, as described in Sect. 2.

Following Caselli et al. (1998), we calculated the relative abundances of X2, XY, and Y2 on the surfaces of grains as

$`x(\mathrm{H}_2)`$ $`=`$ $`{\displaystyle \frac{\mathrm{\Gamma }(\mathrm{X}_2)}{\mathrm{\Gamma }(\mathrm{X}_2)+\mathrm{\Gamma }(\mathrm{XY})+\mathrm{\Gamma }(\mathrm{Y}_2)}}`$ (25)
$`x(\mathrm{XY})`$ $`=`$ $`{\displaystyle \frac{\mathrm{\Gamma }(\mathrm{XY})}{\mathrm{\Gamma }(\mathrm{X}_2)+\mathrm{\Gamma }(\mathrm{XY})+\mathrm{\Gamma }(\mathrm{Y}_2)}}`$ (26)
$`x(\mathrm{O}_2)`$ $`=`$ $`{\displaystyle \frac{\mathrm{\Gamma }(\mathrm{Y}_2)}{\mathrm{\Gamma }(\mathrm{X}_2)+\mathrm{\Gamma }(\mathrm{XY})+\mathrm{\Gamma }(\mathrm{Y}_2)}}`$ (27)
We calculated the difference between the exact results, and the results obtained (i) through the solution of the master equation for the low-truncation case; (ii) with the standard rate equation approach; (iii) with the modified rate equation approach; and (iv) with the approximate method. The results are plotted against $`\alpha `$ and $`\delta `$, for $`\tau =1.0`$, in Figs. 1 to 4.

Figs. 1 to 4 show the magnitudes of the percentage discrepancies between: the results given by the standard rate equation approach, and the exact results (Fig. 1); the results given by the modified rate equation approach, and the exact results (Fig. 2); the results given by the approximate method, and the exact results (Fig. 3); and the results given by the master equation approach for the low truncation case, and the exact results (Fig. 4).

Due to lack of space, the results are plotted against $`\alpha `$ and $`\delta `$ for $`\tau =1.0`$ only. Results for other values of $`\tau `$ can be found at http://ast.leeds.ac.uk/$``$jglr. In each of Figs. 1 to 4, plot (a) shows the discrepancies in $`x`$(X2); plot (b) shows the discrepancies in $`x`$(XY); and plot (c) shows the discrepancies in $`x`$(Y2).

In Fig. 5, the percentage discrepancies are plotted against $`N(\mathrm{X})`$ and $`N(\mathrm{Y})`$, the average numbers of X and Y atoms on the surface of a grain, as given by the exact method and Eqs. (11) and (12). The white gaps at the top left-hand and bottom left-hand corners of the plots in Fig. 5 are caused by the fact that we did not explore regions of $`\alpha `$$`\delta `$$`\tau `$ space that yielded these values of $`N(\mathrm{X})`$ and $`N(\mathrm{Y})`$. The uneven contours in Fig. 5 are caused by the fact that any point in $`N(\mathrm{X})`$$`N(\mathrm{Y})`$ space does not correspond to a single point in $`\alpha `$$`\delta `$$`\tau `$ space, and therefore the discrepancies do not depend only on $`N(\mathrm{X})`$ and $`N(\mathrm{Y})`$. In Fig. 6 the discrepancies are plotted against $`N(\mathrm{X})`$ and $`N(\mathrm{Y})`$ for $`\tau =1.0`$ only. Again the white areas are regions of $`N(\mathrm{X})`$$`N(\mathrm{Y})`$ space to which no point in $`\alpha `$$`\delta `$ space corresponds for $`\tau =1.0`$. In Figs. 5 and 6, plots (a), (b) and (c) are for the standard rate equation approach, plots (d), (e), and (f) for the modified rate equation approach, plots (g), (h), and (i) for the approximate method, and plots (j), (k), and (l) for the low-truncation case of the master equation approach. Plots (a), (d), (g), and (j) give the percentage discrepancy in $`x`$(X2), plots (b), (e), (h), and (k) the percentage discrepancy in $`x`$(XY), and plots (c), (f), (i), and (l) the percentage discrepancy in $`x`$(Y2). In Figs. 5 and 6, the ranges of $`N(\mathrm{X})`$$`N(\mathrm{Y})`$ are different because there is no desorption of Y, so X and Y are not symmetric.

In all of Figs. 1 to 6, lighter regions indicate lower percentage discrepancies, and darker regions higher percentage discrepancies.

Although only the results for $`\tau =1.0`$ are shown in Fig. 1, it was found that the results given by the rate equation approach are inaccurate for the case of low $`\alpha `$, high $`\delta `$, and low $`\tau `$, corresponding to situations in which the rates of accretion are low and the rates of X desorption, and of Reactions (2) and (3), are high, so that the average surface population on a grain is low. This conslusion is confirmed by Figs. 5a–c and 6a–c, which show that this approach is least accurate for small $`N(\mathrm{X})`$ and $`N(\mathrm{Y})`$. These are the conditions under which it is known that the rate equation approach breaks down.

The inaccuracies in the results given by the modified rate equation approach are shown in Fig. 2 for $`\tau =1.0`$, and in Figs. 5d–f and 6d–f. In most cases these results are no more accurate than those of the standard rate equation approach, and sometimes the accuracy is much less. Stantcheva et al. (2002) studied the system of H and O reacting on the surfaces of grains to form H2, OH, and O2, and gave in their Figs. 1 to 3 results for the values of $`x`$(H2), $`x`$(OH), and $`x`$(O2) calculated by various different methods including the modified rate equation approach and the master equation method. The modified rate equation approach they used was the same as that used by Stantcheva et al. (2001), which was based on that used by Caselli et al. (1998). They found good agreement between results obtained with these two approaches for the parameters they considered, which were mostly rather different from those used by us. They used the same values for $`a_\mathrm{X}`$, $`a_\mathrm{Y}`$, $`d_\mathrm{X}`$, $`t_\mathrm{s}(\mathrm{X})`$, and $`t_\mathrm{s}(\mathrm{Y})`$as Hasegawa et al. (1992), Caselli et al. (1998), and Green et al. (2001). The accretion rate they used for oxygen was different from that used for hydrogen. Their parameters were equivalent to $`10^{12}<a_\mathrm{H}t_\mathrm{s}(\mathrm{H})<10^5`$; $`a_\mathrm{O}t_\mathrm{s}(\mathrm{H})10^{10}`$; $`d_\mathrm{H}t_\mathrm{s}(\mathrm{H})10^8`$; and $`\frac{t_\mathrm{s}(\mathrm{O})}{t_\mathrm{s}(\mathrm{H})}10^9`$. This corresponds to a region below and to the left of that shown in the plots in Fig. 2, and for a higher value of $`\tau `$. It can be seen that towards the bottom left-hand corner of Fig. 2a, the results are more accurate than elsewhere, which is consistent with the findings of Stantcheva et al. (2002).

Fig. 3 shows that the approximate method gives inaccurate results for $`x`$(X2) when $`\delta `$ is high. If the desorption rate is high, the assumption that an X atom will always react if it accretes onto a grain that is already populated is invalid. It was also found that there are inaccuracies in the values calculated for $`x`$(Y2) for high $`\alpha `$, for all values of $`\tau `$. In these cases, the accretion rate is comparable to, or greater than, the rate of reaction of Y, and the population of grains containing several Y atoms is non-negligible. At high values of $`\tau `$, the results were found to be inaccurate for a wide range of values of $`\alpha `$ and $`\delta `$, particularly for $`x`$(X2) and $`x`$(Y2); $`x`$(XY) is only inaccurate for high $`\delta `$ and low $`\alpha `$. The approximate equations were constructed under the assumption that if there are two atoms of species Y on the surface of a grain, and a third accretes, Y2 will not be formed. If we instead assume that a grain surface containing no atoms of X and more than two atoms of Y will always be a site of Y2 formation, Eq. (23) should be replaced with

$$\mathrm{\Gamma }(\mathrm{Y}_2)\frac{\kappa _{\mathrm{Y},\mathrm{Y}}+\alpha }{\kappa _{\mathrm{Y},\mathrm{Y}}+2\alpha }\frac{\alpha }{2}P(0,0)$$
(28)
In the case of $`\alpha =0.3`$, $`\delta =0.1`$, $`\tau =10`$, this results in an improvement of a factor of about 2.4 in the value obtained for the production rate of Y2. This results in X2, XY, and Y2 abundances, calculated with Eqs. (25) to (27), which differ from the exact results by 42%, 3%, and 26%, respectively; for X2 and Y2 this is a vast improvement from the results obtained when $`\mathrm{\Gamma }(\mathrm{Y}_2)`$ was calculated with Eq. (23). The inaccuracy at high values of $`\tau `$ also causes an inaccuracy in $`x`$(Y2) at high $`N(\mathrm{Y})`$, which can be seen in Fig. 5i, and probably contributes to the inaccuracies seen in $`x`$(X2) and $`x`$(XY) in Figs. 5g and 5h, at least at higher values of $`N(\mathrm{Y})`$. In Fig. 5g–i, one can see that the results given by this approach for $`x`$(X2) are inaccurate for low $`N(\mathrm{X})`$, at all values of $`<N`$(Y)$`>`$; at higher values of $`N(\mathrm{Y})`$ the results are inaccurate for a larger range of $`N(\mathrm{X})`$. The results for $`x`$(XY) are also inaccurate for low $`N(\mathrm{X})`$ for a range of $`N(\mathrm{Y})`$.

Fig. 4 shows that the inaccuracy in the results given by the master equation method with low truncation values is high for high $`\alpha `$. In particular, the inaccuracy was found to be high in the case of high $`\alpha `$, low $`\delta `$, and low $`\tau `$. This corresponds to the case of a high rate of accretion, a low rate of hydrogen desorption, and high rates for Reactions (2) and (3). This is the case in which there is a large population of X atoms on the surfaces of the grains. The inaccuracy is also high for high $`\alpha `$, high $`\delta `$, and high $`\tau `$, which corresponds to fast rates of accretion and hydrogen desorption, and a slow rate for Reaction (3). This results in a large population of Y atoms on the surfaces of the grains. The results given by the master equation method with low truncation values are therefore inaccurate when there are large numbers of atoms on the surfaces of grains, as should be expected; this can also be seen in Figs. 5j–l and 6j–l.

Fig. 7 shows the regions of $`N(\mathrm{X})`$$`N(\mathrm{Y})`$ space in which the standard rate equation approach, or the low-truncation master equation approach, is more accurate. Plot (a) is for X2, plot (b) for XY, and plot (c) for Y2. Dark regions indicate that the rate equation approach is more accurate; light regions are those in which the low-truncation master equation approach is more reliable. Regions of intermediate shading indicate that both approaches give results which are accurate to within 10%. As expected, when either the results given by one method or both methods are not accurate to within 10%, the low-truncation master equation approach is more accurate at low values of $`N(\mathrm{X})`$ and $`N(\mathrm{Y})`$, and the rate equation approch at higher values. The better of the two approaches gives results for $`x`$(X2), $`x`$(XY), and $`x`$(Y2) which are usually within 10 or 20% – and always within 25% – of those given by the exact method, except for the results given for $`x`$(Y2) in a small region of $`\alpha `$$`\delta `$$`\tau `$ space around $`\alpha =0.7`$, $`0.1<\delta <0.3`$, $`\tau >0.7`$. In these cases, the more accurate method is the rate equation approach, and the value of $`x`$(Y2) given by that method is around 40% less than the exact value.

Although in general the rate equation approach is more accurate than the low-truncation master equation approach for higher values of $`N(\mathrm{X})`$ and $`N(\mathrm{Y})`$, it can be seen in Fig. 7 that for $`N(\mathrm{X})1.21.4`$, $`N(\mathrm{Y})3`$, the low-truncation master equation approach is more accurate for X2. However, in most of these cases the results given by the two methods are very similar, and the discrepancies between them and the exact results are within about 20%.

## 4 Conclusions

We have studied grain surface chemistry with a variety of approaches with a range of parameters. We deliberatelty made our study as general as was reasonable given the amount of work involved in a multiparameter study. We did so in anticipation of revisions of rates pertaining to specific problems treated in earlier literature, and of future studies of surface astrochemistry in a very wide range of environments including some in which atomic hydrogen accretion is unimportant.

The modified rate equation method was found to be no more accurate than the standard rate equation approach under the conditions examined; indeed it was in many cases less accurate. The modified rate equation method that we used is closely related to that of Caselli et al. (2002). They studied a system in which reaction barriers are important, and the values of $`\alpha `$ approriate for their studies are large. The modified rate equation approach that we used gives reliable results for large $`\alpha `$ for some values of $`\tau `$. Hence, our findings are in harmony with those of Caselli et al. (2002). The modified rate equation approach that we adopted differs from that employed by Stantcheva et al. (2001) which they found to give reliable results for the specific $`\alpha 0.1`$ and large $`\delta `$ cases they examined. They, like the authors of a number of papers referenced here, were examining a region of parameter space they thought to be relevant when hydrogen accretion is important for the surface chemistry and the surface reactions proceed without barriers. Of the approximate methods we have examined, only the low-order truncated master equation approach is reliable for general small $`\alpha `$, large $`\delta `$ cases.

The approximate method of Green et al. (2001), which was devised specifically for the H,O system, was also found to give inaccurate results under certain conditions, but can be improved by considering the possibility that an atom of species Y may accrete onto the surface of a grain on which there are already two Y atoms.

The standard rate equation approach was found to work well except under conditions which lead to there being a small average number of X and Y atoms on the surface of a grain. Under these conditions, the master equation approach with low truncation values is accurate. Therefore, a combination of the two approaches should be enough for a reasonably accurate calculation of the X2, XY, and Y2 abundances in the parameter regime we considered – generally within about 20% of the exact values. Practical approaches to the use of stochastic models are under investigation (Stantcheva et al. 2001).

###### Acknowledgements.

JGLR was supported by grants from the Leverhulme Trust and PPARC. TT was supported by a grant from PPARC.


format: text

text:
# Entanglement constrained by superselection rules

(26 August 2003)

## Abstract

Bipartite entanglement may be reduced if there are restrictions on allowed local operations. We introduce the concept of a generalized superselection rule (SSR) to describe such restrictions, and quantify the entanglement constrained by it. We show that ensemble quantum information processing, where elements in the ensemble are not individually addressable, is subject to the SSR associated with the symmetric group (the group of permutations of elements). We prove that even for an ensemble comprising many pairs of qubits, each pair described by a pure Bell state, the entanglement per element constrained by this SSR goes to zero for a large number of elements.

Entanglement lies at the heart of quantum information processing (QIP) Nie00 , and quantifying entanglement as a physical resource is a primary goal of this field Hor00 . Recently, it has been shown that the existence of superselection rules (SSRs) Wic52  requires us to reassess traditional entanglement measures Wis02  and the allowed bipartite operations Ver03 : the SSRs enforce additional restrictions on what Alice and Bob can accomplish using only local operations and classical communication (LOCC).

In this Letter, we quantify entanglement constrained by a generalized SSR and show that this entanglement is typically less than the amount given by any standard measure. To accomplish this task, we first introduce the concept of a generalized SSR as a rule associated with some group of physical transformations of a system. The rule is defined operationally: it restricts the allowed operations on the system to those that are covariant with respect to that group. Our definition encompasses traditional SSRs such as charge and particle number as well as effective SSRs for quantities such as angular momentum or photon number (which may arise due to practical restrictions on operations, the lack of an appropriate shared reference frame, or through interaction with an environment). Our measure of entanglement constrained by SSRs is also operational in that it describes the accessible entanglement that Alice and Bob can distill into standard quantum registers through allowed LOCC.

As an explicit example of entanglement constrained by a SSR, we describe ensemble QIP where access to individual elements of the ensemble is not possible. The relevant SSR here restricts the allowed operations to be “collective” in that they act identically on all elements of the ensemble. We find that our operational measure of entanglement constrained by this SSR can be hugely smaller than that found from standard entanglement measures. In particular, we prove the remarkable result that, even if each element of the ensemble consists of two qubits described by a *pure* Bell state, the entanglement per element constrained by this SSR is zero in the limit of a large number of elements. We discuss how this result places a powerful constraint on QIP in liquid-state NMR Cor97  and spin-squeezing experiments Jul01 .

We begin by providing an operational definition of a SSR, and show that this definition is compatible with colloquial uses. *A SSR is a restriction on the allowed local operations on a system, and is associated with a group of physical transformations.* This restriction could be imposed by properties of the underlying theory (e.g., a SSR for charge required in a Lorentz-invariant quantum field theory Str74 ), but we also consider SSRs that arise due to practical restrictions. Consider a local quantum system with Hilbert space $``$. The set of physical operations on this quantum system is given by the semigroup of completely positive (CP) trace-preserving maps $`\{\}_{\mathrm{CP}}`$. These CP maps describe not only unitary (closed) operations but also open processes such as state preparation, dissipation and measurement. Let $`G`$ be a group of physical transformations acting on $``$ through a unitary representation $`T`$. We define an operation $`𝒪\{\}_{\mathrm{CP}}`$ to be *$`G`$-covariant* if

$$𝒪[T(g)\rho T^{}(g)]=T(g)𝒪[\rho ]T^{}(g),$$
(1)
for all group elements $`gG`$ and all density operators $`\rho `$. We then define the *SSR associated with $`G`$*, or $`G`$-SSR, to be to be a restriction on the allowed operations on the system to those CP maps $`\{𝒪\}_{G\text{-SSR}}\{\}_{\mathrm{CP}}`$ that are $`G`$-covariant. The following examples reveal how this definition is compatible with some traditional SSRs:

*Example 1: Charge.* Let $`G`$ be a one-dimensional Lie group U(1) generated by a Hermitian operator $`Q`$; i.e., $`T(\xi )=\mathrm{exp}(\text{i}\xi Q)`$. If $`Q`$ is a local charge operator then this U(1)-SSR is usually referred to as a SSR for charge. Similar SSRs can be developed for particle number. When such a SSR applies, one cannot, for instance, locally create superpositions of charge eigenstates because the required operations are not $`G`$-covariant. Note that this SSR does not forbid the creation of superpositions where, for example, one charge can be found at two different locations, as in the twin-slit experiment for electrons.

*Example 2: Angular momentum.* Let $`G=`$ SO(3) be the rotation group generated by the total angular momentum operators $`\{L_{x,y,z}\}`$. The associated SSR ensures that all allowed operations are rotationally invariant. This SSR may apply, for instance, when there is no reference frame for orientation and thus all observables commute with the total angular momentum. A reference frame would establish operators that specify a direction; such operators do not commute with total angular momentum and thus violate the SSR. In this example, the SSR is a practical rather than fundamental consideration: the lack of a reference frame leads to a SSR.

*Example 3: Environmentally-induced SSR.* Let $`\widehat{H}_{\mathrm{int}}`$ be a coupling Hamiltonian between the system and an environment, and let $`G=`$ U(1) be the group generated by this Hamiltonian. Einselection Zur03 , which is often expressed as the condition that the only allowed states of the system are those that commute with this Hamiltonian, has the form of a U(1)-SSR.

It should be noted that the existence of a SSR is not equivalent to a conservation law; in fact, the only interesting SSRs are those that apply to *non-conserved* quantities Wis03 . Also note that a SSR does not restrict the allowed states of the system. However, the restrictions imposed on the allowed operations by the $`G`$-SSR mean that a state $`\rho `$ is indistinguishable from the states $`T(g)\rho T^{}(g)`$ for all $`gG`$. Because of this indistinguishability, it is operationally appropriate to describe $`\rho `$ by the state

$$𝒢[\rho ]\{\begin{array}{cc}(\text{dim}G)^1_{gG}T(g)\rho T^{}(g),\hfill & \text{finite groups}\hfill \\ _G\text{d}v(g)T(g)\rho T^{}(g),\hfill & \text{Lie groups}\hfill \end{array}$$
(2)
where $`\text{d}v`$ is the group-invariant (Haar) measure Ful91 . The state $`𝒢[\rho ]`$ is invariant under the action of $`G`$,

$$T(g)𝒢[\rho ]T^{}(g)=𝒢[\rho ],gG,$$
(3)
so we call this state the *$`G`$-invariant state*.

Consider a SSR for charge as an example. States that are superpositions of charge eigenstates are not *a priori* prohibited. For a state that is a superposition of charge eigenstates $`|\psi =\alpha |q_1+\beta |q_2`$, with $`Q|q_i=q_i|q_i`$, the effect of the superoperator $`𝒢`$ on this state is

$$𝒢\left[|\psi \psi |\right]=|\alpha |^2|q_1q_1|+|\beta |^2|q_2q_2|.$$
(4)
Thus, in the presence of the SSR, a superposition of charge eigenstates is operationally equivalent to a *mixture* of charge eigenstates. The effect of $`𝒢`$ is to project onto eigenspaces of the group generator $`Q`$. SSRs associated with one-dimensional Lie groups are often defined this way (cfVer03 ). However, for general SSRs (including the example associated with the rotation group), there is not necessarily an equivalent expression.

We now consider imposing a SSR in a bipartite setting; that is, both parties (Alice and Bob) are restricted to local operations obeying Eq. (1). Consider a bipartite state $`\rho ^{ab}`$ shared by Alice and Bob. This state may have been prepared by a third party under conditions where no SSR applies. The $`G`$-invariant state constrained by these local SSRs is $`𝒢[\rho ^{ab}]=𝒢^a𝒢^b[\rho ^{ab}]`$. To quantify the entanglement of this state we assume that, in addition to this bipartite system, Alice and Bob each possess a quantum register with Hilbert space dimension equal to or greater than that of their respective systems. These registers are initially in the pure product state $`\varrho _0^{ab}`$ and are not subject to any SSR. (For example, these registers could be standard qubits over which Alice and Bob have complete control.) We quantify the entanglement $`E_{G\text{-SSR}}(\rho ^{ab})`$ constrained by the $`G`$-SSR as the maximum amount of entanglement that Alice and Bob can produce between their registers by LOCC Wis02 . The latter can be quantified by an appropriate standard measure $`E`$, e.g., the entanglement of distillation Nie00 . The following theorem quantifies the entanglement constrained by an arbitrary SSR for pure or mixed states, generalizing the result of Wis02 :

Theorem: The entanglement $`E_{G\text{-SSR}}(\rho ^{ab})`$ that Alice and Bob can produce between their registers from the state $`\rho ^{ab}`$ by LOCC constrained by a $`G`$-SSR is given by the entanglement $`E(𝒢[\rho ^{ab}])`$ that they can produce from the state $`𝒢[\rho ^{ab}]`$ by unconstrained LOCC, where $`E`$ is a standard measure of entanglement.

Proof: First, note that any CP map can be composed with $`𝒢`$ to yield a $`G`$-invariant operation, i.e.,

$$𝒢𝒢\{𝒪\}_{G\text{-SSR}}\{\}_{\mathrm{CP}},$$
(5)
which follows from the definitions (1) and (2). Let $`𝒪`$ be a $`G`$-invariant operation in LOCC acting on the initial state $`\rho ^{ab}\varrho _0^{ab}`$. The final state of the registers is given by $`\varrho _1^{ab}=\mathrm{Tr}_{\mathrm{sys}}\left(𝒪[\rho ^{ab}\varrho _0^{ab}]\right)`$, where the trace is over the shared system. The maximum entanglement produced between the registers is given by maximizing $`E(\varrho _1^{ab})`$ over all LOCC obeying the $`G`$-SSR. Thus, using (5),

$`E_{G\text{-SSR}}(\rho ^{ab})`$ $`=\underset{𝒪}{\mathrm{max}}E\left(\mathrm{Tr}_{\mathrm{sys}}\left(𝒪[\rho ^{ab}\varrho _0^{ab}]\right)\right)`$
$`=\underset{𝒪}{\mathrm{max}}E\left(\mathrm{Tr}_{\mathrm{sys}}\left((𝒢𝒪𝒢)[\rho ^{ab}\varrho _0^{ab}]\right)\right)`$
$`=\underset{}{\mathrm{max}}E\left(\mathrm{Tr}_{\mathrm{sys}}\left((𝒢𝒢)[\rho ^{ab}\varrho _0^{ab}]\right)\right)`$
$`=\underset{}{\mathrm{max}}E\left(\mathrm{Tr}_{\mathrm{sys}}\left(\left[𝒢[\rho ^{ab}]\varrho _0^{ab}\right]\right)\right),`$ (6)
where the second line follows from the properties of trace and the definition (2), and the last line follows from the properties of trace. The latter maximization is over all LOCC (not just operations in $`\{𝒪\}_{G\text{-SSR}}`$), and gives the entanglement $`E(𝒢[\rho ^{ab}])`$ that Alice and Bob can produce between their registers from the state $`𝒢[\rho ^{ab}]`$ by unconstrained LOCC. $`\mathrm{}`$

We now turn to a specific application of the above result that yields a striking difference between the amount of entanglement with and without the SSR. Ensemble QIP describes $`N`$ identical copies of a system of qubits, where $`N`$ is usually taken to be very large. We consider a situation where access to individual elements of the ensemble is not possible, and thus only *collective* transformations and measurements (i.e., operations which affect each element identically) are allowed. In the following, we formulate this restriction as a SSR, and show that it severely limits the entanglement in the system.

Consider an ensemble consisting of $`N`$ copies of a single qubit. (For convenience, we assume $`N`$ is even.) The Hilbert space $`_2^N`$ carries a collective tensor representation $`R`$ of SU(2), by which a rotation $`\mathrm{\Omega }`$ SU(2) acts identically on each of the $`N`$ qubits. The Hilbert space also carries a representation $`P`$ of the symmetric group $`S_N`$, which is the group of permutations of the $`N`$ qubits. The action of these two groups commute, and Schur-Weyl duality Ful91  states that the Hilbert space $`_2^N`$ carries a multiplicity-free direct sum of SU(2)$`\times S_N`$ irreducible representations (irreps), each of which can be labelled by the SU(2) total angular momentum quantum number $`j`$. Each of these irreps can be factored into a tensor product $`_{jR}_{jP}`$, such that SU(2) acts irreducibly on $`_{jR}`$ and trivially on $`_{jP}`$, and $`S_N`$ acts irreducibly on $`_{jP}`$ and trivially on $`_{jR}`$. Thus,

$$_2^N=\underset{j=0}{\overset{N/2}{}}_{jR}_{jP}.$$
(7)
The dimension of $`_{jR}`$ is $`2j+1`$, and that of $`_{jP}`$ is Bar03

$$c_j^{(N)}=\left(\genfrac{}{}{0pt}{}{N}{N/2j}\right)\frac{2j+1}{N/2+j+1}.$$
(8)
Consider a basis $`|j,m_R|j,r_P`$ for $`_{jR}_{jP}`$, with $`\{|j,m_R,m=j,\mathrm{},j\}`$ the standard angular momentum basis for $`_{jR}`$ and $`\{|j,r_P,r=1,\mathrm{},c_j^{(N)}\}`$ a basis for $`_{jP}`$. The group SU(2)$`\times S_N`$ acts on this basis as $`R(\mathrm{\Omega })|j,m_RP(p)|j,r_P`$ for $`\mathrm{\Omega }`$ SU(2) and $`pS_N`$.

In ensemble QIP without individual addressability, the only allowed operations $`𝒪`$ are those that are invariant under permutations of elements and thus must satisfy

$$𝒪[P(p)\rho P^{}(p)]=P(p)𝒪[\rho ]P^{}(p),$$
(9)
for all $`pS_N`$. (Note that these allowed operations include all transformations generated by Hamiltonians in the enveloping algebra of su(2), i.e., which are polynomials in $`J_x`$, $`J_y`$ and $`J_z`$. In liquid-NMR QIP the operations are more restricted because there are no controllable inter-molecular interactions. We will not consider that additional restriction here.) Thus, ensemble QIP with this restriction must respect the SSR associated with the symmetric group $`S_N`$. Unlike previous examples involving Lie groups, this SSR is associated with a finite group. We define the superoperator

$$𝒫[\rho ]=\frac{1}{N!}\underset{pS_N}{}P(p)\rho P^{}(p),$$
(10)
which can be extended to act on states of $`n`$ qubits on $`N`$ elements. The action of $`𝒫`$ is best seen in the decomposition of Eq. (7): it completely mixes states in $`_{jP}`$ while leaving states in $`_{jR}`$ invariant. The spaces $`_{jR}`$ are called noiseless subsystems (NSs) Kni00 , and are free from the decohering effect of $`𝒫`$. These NSs are dual to the collective NSs $`_{jP}`$, which have been explored in the context of quantum computation Kni00 ; Zan97  and quantum communication without shared orientation reference frames Bar03  and which are free from collective SU(2) decoherence.

We now quantify bipartite entanglement in ensemble QIP constrained by the $`S_N`$-SSR; specifically, we show that the standard (unconstrained) measure of entanglement can grossly overestimate the amount of entanglement accessible to Alice and Bob. Consider the following example, where each of $`N`$ elements possesses two qubits, $`a`$ and $`b`$. These qubits are separated such that all the qubits of type $`a`$ are given to Alice and $`b`$ to Bob. If the $`S_N`$-SSR is enforced, Alice and Bob are both restricted to local $`S_N`$-covariant operations, and any state $`\rho ^{ab}`$ is indistinguishable from the state $`𝒫[\rho ^{ab}]=𝒫^a𝒫^b[\rho ^{ab}]`$.

If the two qubits on every element are described by the Bell state $`|\mathrm{\Phi }^+=\frac{1}{\sqrt{2}}\left(|uu^{ab}+|dd^{ab}\right)`$, the state of the total ensemble is $`|\mathrm{\Phi }^{(N)}|\mathrm{\Phi }^+^N`$. A naive quantification of entanglement of this pure state gives $`N`$ ebits. However the constrained entanglement is much less. Expressing this state in terms of the decomposition of Eq. (7) yields

$`|\mathrm{\Phi }^{(N)}`$ $`={\displaystyle \frac{1}{\sqrt{2^N}}}{\displaystyle \underset{j=0}{\overset{N/2}{}}}{\displaystyle \underset{m=j}{\overset{j}{}}}{\displaystyle \underset{r}{}}|j,m_R^a|j,r_P^a|j,m_R^b|j,r_P^b`$
$`={\displaystyle \underset{j=0}{\overset{N/2}{}}}\sqrt{{\displaystyle \frac{(2j+1)c_j^{(N)}}{2^N}}}|\varphi _j^{ab}|\chi _j^{ab},`$ (11)
where

$`|\varphi _j^{ab}`$ $`={\displaystyle \frac{1}{\sqrt{2j+1}}}{\displaystyle \underset{m=j}{\overset{j}{}}}|j,m_R^a|j,m_R^b,`$ (12)
$`|\chi _j^{ab}`$ $`={\displaystyle \frac{1}{\sqrt{c_j^{(N)}}}}{\displaystyle \underset{r}{}}|j,r_P^a|j,r_P^b,`$ (13)
are (normalised) maximally entangled states in $`_{jR}^a_{jR}^b`$ and $`_{jP}^a_{jP}^b`$, respectively.

The action of $`𝒫`$ on the state (Entanglement constrained by superselection rules) is

$$𝒫\left[|\mathrm{\Phi }^{(N)}\mathrm{\Phi }^{(N)}|\right]=\underset{j=0}{\overset{N/2}{}}\frac{(2j+1)c_j^{(N)}}{2^N}|\varphi _j^{ab}\varphi _j|\sigma _j^{ab},$$
(14)
where $`\sigma _j^{ab}`$ is the (normalised) completely mixed state on $`_{jP}^a_{jP}^b`$. The resulting state is an incoherent sum of maximally-entangled states on each irrep $`_{jR}^a_{jR}^b`$. The entanglement of this state can be easily calculated because both Alice and Bob can *locally* perform a measurement of total $`J^2`$, which determines $`j`$ and yields a pure state in $`_{jR}^a_{jR}^b`$. Thus, the entanglement of this state constrained by the $`S_N`$-SSR is

$$E_{S_N\text{-SSR}}\left(|\mathrm{\Phi }^{(N)}\mathrm{\Phi }^{(N)}|\right)=\underset{j=0}{\overset{N/2}{}}\frac{(2j+1)c_j^{(N)}}{2^N}\mathrm{log}_2(2j+1),$$
(15)
which, for large $`N`$, behaves as $`\frac{1}{2}\mathrm{log}_2N`$. Thus, although the state $`|\mathrm{\Phi }^{(N)}`$ possesses $`N`$ ebits of unconstrained entanglement, its entanglement constrained by the SSR is only $`\frac{1}{2}\mathrm{log}_2N`$ ebits (asymptotically). This result is remarkable: for a pure state of the ensemble, each element consisting of two qubits in a Bell state, the constrained entanglement per element rapidly approaches zero for large $`N`$.

Note that the state $`|\mathrm{\Phi }^{(N)}`$, describing each element as a Bell state, is *not* a maximally entangled state under the $`S_N`$-SSR constraint; we now identify such a state. Observing the form of the decohering mechanism $`𝒫`$, this state is clearly a pure maximally entangled state in the NS $`_{jR}^a_{jR}^b`$ with the largest dimension, given by $`j_0=N/2`$. The entanglement per element of this state is $`N^1\mathrm{log}_2(N+1)`$, which approaches zero for large $`N`$. As this state is the maximally entangled state under the SSR constraint, we have proved that the maximum entanglement per element in the large $`N`$ limit is zero.

A remarkable duality is evident between the SSR associated with the symmetric group and that associated with the rotation group when one considers the maximum entanglement these SSRs allow. The latter describes a situation where Alice and Bob do not share an orientation reference frame for their qubits Bar03 . In the Hilbert space decomposition of Eq. (7), the SSR for the rotation group is described by a decohering superoperator on the SU(2) irreps, as opposed to the $`S_N`$ irreps described above. As proven in Bar03 , the maximum entanglement between $`N`$ pairs of qubits constrained by the SU(2)-SSR behaves asymptotically as $`N\mathrm{log}_2N`$; in this letter, we proved that the maximum entanglement between $`N`$ pairs of qubits constrained by the $`S_N`$-SSR behaves asymptotically as $`\mathrm{log}_2N`$. Note that these two values asymptotically sum to $`N`$, which is the maximum unconstrained entanglement for $`N`$ qubit pairs.

In summary, we have defined generalized SSRs, and quantified the constrained entanglement of a bipartite state as the amount of entanglement that can be distilled into quantum registers using only LOCC that obey the appropriate SSR. Our example of ensemble QIP reveals that systems with apparently large amounts of entanglement can in fact possess very little under the appropriate SSR constraint. We note that this result for ensemble QIP applies to liquid-state NMR Cor97 , where qubits are realized as nuclear spins on a molecule and a sample generally contains $`N10^{20}`$ molecules <sup>1</sup><sup>1</sup>1However, NMR QIP possesses additional constraints due to impure initial conditions, restrictions on the allowed operations, and inefficient read-out.. Our operational definition of entanglement constrained by a $`S_N`$-SSR is also applicable to spin-squeezed atomic gases Jul01 ; because the NS corresponding to $`j_0=N/2`$ is used in such experiments, our result shows that the present measures of entanglement used for this system Sto03  *are* appropriate.

Another question related to our operational definition of entanglement is: What constraints does a SSR impose on the entangled states that can be created (formed) from a set amount of entanglement in the quantum registers? As pointed out in Ver03 , it is not even possible to create certain *separable* states in the presence of a SSR. It is clear that SSRs place severe contraints on QIP, and our operational definitions of SSRs and entanglement constrained by them provide a new understanding and a valuable tool to quantum information science.

###### Acknowledgements.

We thank E. Knill, R. W. Spekkens, F. Verstraete and P. Zanardi for helpful comments on our manuscript, and thank M. A. Nielsen, T. Rudolph, B. C. Sanders, and R. W. Spekkens for valuable prior discussions.