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# Interface Motion and Pinning in Small World Networks

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## Abstract

We show that the nonequilibrium dynamics of systems with many interacting elements located on a small-world network can be much slower than on regular networks. As an example, we study the phase ordering dynamics of the Ising model on a Watts-Strogatz network, after a quench in the ferromagnetic phase at zero temperature. In one and two dimensions, small-world features produce dynamically frozen configurations, disordered at large length scales, analogous of random field models. This picture differs from the common knowledge (supported by equilibrium results) that ferromagnetic short-cuts connections favor order and uniformity. We briefly discuss some implications of these results regarding the dynamics of social changes.

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Small-world networks have received a great deal of attention in the past few years, in particular for their realistic description of the topology of the interactions that take place among populations in various biological, social or economical systems . An important feature of small worlds, that is not shared neither by regular lattices nor random networks, is the interplay that exists between local (or “physical”) interactions, e.g. between nearest-neighbors, and non-local ones, involving nodes (or agents) separated by large distances but connected through short-cuts. Among other outstanding topological properties, the effective space dimension of such networks grows linearly with their size , even if the fraction of sites with short cuts is very small.

The strong connectivity of small worlds usually enhances dramatically cooperative effects, as predicted by epidemic models of spreading of diseases , or of propagation of conventions or rumors in social systems . Naturally, many models of social dynamics have been inspired from the Ising model . The Ising model on a small world exhibits ferromagnetic order at low temperatures even in one dimension , while, in higher dimensions, the critical temperature is increased compared with that of the regular lattice . In addition, the fact that the transition is of mean-field nature agrees with the intuitive argument that each site is effectively close to a large number of sites due to the short-cuts of the lattice.

However, because of their inherent random topology, one may ask whether in some situations small-world networks would not rather exhibit features characteristic of disordered systems. In this work, we study as a basic example the nonequilibrium dynamics of the Ising model, as observed after a rapid quench from the high temperature phase to the ferromagnetic phase. We show that the random (all ferromagnetic) connections that enhance ordered states at thermodynamic equilibrium, are responsible in the present case for very slow dynamics and stabilize at large times configurations that, instead of being uniform, are spatially heterogeneous. At zero temperature, systems do not perform long range order dynamically, but remain asymptotically trapped in metastable states characterized by a finite domain size. These features are reminiscent of nonequilibrium processes in the random field Ising model (RFIM) , in binary mixtures with fixed impurities , as well as in a few social models on regular lattices like the voter model . This has to be contrasted with the much more efficient phase ordering kinetics of the Ising model on regular lattices (or Model A in the lexicon of Hohenberg and Halperin ), where the mean size of ordered domains grows with time as $`t^{1/2}`$ . Our present analysis focuses on the motion of domain walls between “up” and “down” domains, and shows evidence of competing effects between surface tension and pinning (or localizing) effects.

We use a standard model of small-world network  consisting of a regular square lattice (or a chain in 1D) composed of $`N`$ nodes connected to their nearest neighbors. For each site, we then establish with a probability $`p`$ an additional connection, or short-cut, linking the considered site to an other site chosen at random in the lattice. (We do not remove the nearest neighbors connections.) For $`p=0`$, the lattice is regular, while for $`p=1`$, the network is strongly disordered. Here, we will consider only the so-called “small world” limit, that corresponds to the case $`p1`$, where connections are mainly local and only long-ranged for a small fraction of nodes.

On a fixed network, we then assign to each node a spin-like variable $`S_i=\pm 1`$: it represents a social convention, initially chosen at random for each node. At each time step, each node updates its convention in order to reach a better consensus with the nodes it is connected to. In other words, the system follows a zero temperature Glauber dynamics with the Hamiltonian $`H=_{i,j}J_{ij}S_iS_j`$, where the sum is performed over all possible pairs of nodes. $`J_{ij}=1`$ if sites $`i`$ and $`j`$ are connected, $`J_{ij}=0`$ otherwise. At each step, a spin is thus chosen at random and flipped. If $`H`$ decreases, does not change, or increases, the new configuration is accepted with probability $`1`$, $`1/2`$ and $`0`$, respectively.

In regular networks ($`p=0`$), the system evolves toward a minimum of $`H`$ (all $`S_i`$’s equal to $`+1`$ or $`1`$). Transient configurations are characterized by the presence of growing and competing ordered domains of “up” and “down” spins. The large time dynamics is controlled by the motion and annihilation of interfaces (or domain walls) that separate these domains. As for many other systems ordering in phases with broken symmetries, its time evolution is self-similar: The two-point correlation function, $`C(r,t)=S_i(t)S_{i+r}(t)`$, obeys a scaling relation $`C(r,t)=f(r/\xi (t))`$, where $`f`$ is a scaling function, while $`\xi `$, the domain size, grows as $`t^{1/2}`$ .

On the contrary, in small-world networks ($`p0`$, $`p1`$) one observes after some time that the typical domain size of ordered spins saturates to a finite value, which decreases when the density of short-cuts ($`p`$) increases. For a one dimensional chain (of length $`L=10^5`$), we plot $`\xi (t=\mathrm{})`$ as a function of $`p`$ in Figure 1. The correlation length is determined from the half-width of $`C`$ averaged over 10 networks and initial conditions. A behavior $`\xi (t=\mathrm{})1/p`$ can be observed. $`1/p`$ represents the characteristic size of the one dimensional network, i.e. the average distance between two nodes that have long range connections (or “influent” nodes).

Influent sites strongly affect the motion of interfaces. At low $`p`$, most of these nodes are characterized by one additional connection. On Figure 2$`a`$, two nodes far apart, A and B, are connected, and $`S_A=S_B`$. Any interface $`I`$ passing through node A leftward can not jump back toward the right, since it is energetically unfavorable. Therefore, at large times, through interface motion, influent nodes will tend to be (irreversibly) connected to nodes that have the same spin (a situation analogous to assortative mixing, as observed in some real life networks ).

This argument can be extended to a succession of domains. Figure 2$`b`$ illustrates a typical large time configuration: In this example, interface $`I_1`$ stands between two influent nodes $`A`$ and $`B`$ with opposite spins: for the reason mentioned above, $`I_1`$ can not jump to the left of $`A`$, nor to the right of $`B`$. The interface is then localized, i.e. restricted to perform a random walk within the interval \[$`A`$,$`B`$\]. Interface $`I_1`$ is therefore unable to annihilate with interface $`I_2`$, that is localized between $`C`$ and $`D`$. Hence, the two disjoint black domains can not merge to form a bigger one, what would happen in the standard Ising model. The domain size, or correlation length $`\xi `$, does not exceed the distance, of order $`1/p`$, that separates influent unlike (antagonist) successive nodes.

We also find that the structure of frozen configurations obeys a scaling relation with $`p`$, i.e. that they are statistically independent of $`p`$ via proper length rescaling. The asymptotic correlation function $`C(r,t=\mathrm{})`$ is plotted in Figure 3 as a function of the reduced variable $`r/\xi _{\mathrm{}}(p)`$, for various values of $`p`$. Data collapse rather well on a single curve. At short times, the kinetics is not affected by the small world structure of the lattice, and that $`\xi (t)`$ starts growing as $`t^{1/2}`$. When interfaces become localized, the structure can be roughly seen as the one given by the standard Glauber dynamics of the 1D Ising model stopped at a time $`(1/p)^2`$. Since that problem obeys dynamical scaling, frozen configuration should scale with parameter $`p`$. However, this picture is not quantitatively correct, as the scaling functions in both problems slightly differ.

Finite, low temperature effects are quite subtle in one dimensional small-worlds since they do not destroy the ferromagnetic order observed at $`T=0`$, unlike in usual Ising chains. One can interpret here the order/disorder transition temperature $`T_c`$ as the temperature where ordering via interface jumps over localizing barriers (that enable further domain merging) no longer overcomes disordering happening within domains (subdomain creation). In Figure 2$`b`$, interface $`I_2`$ (or $`I_1`$) can jump in interval \[$`B`$,$`C`$\] at a rate $`r_a=\mathrm{exp}(2/T)`$. Besides, the rate at which any spin among the $`p^1`$ spins of interval \[$`D`$,$`E`$\] would flip is $`r_b=p^1\mathrm{exp}(4/T)`$: it is roughly the rate at which a white domain is created and can start to grow. Qualitatively, the order/disorder transition occurs when $`r_a=r_b`$. This gives: $`T_c2/\mathrm{ln}p`$, a expression derived (with a $``$ sign) in ref.  using the replica method. The above relation may be exact as $`p0`$ (as the numerical prefactors in the different rates become irrelevant). Simulation results (not shown) give $`T_c=2.3/\mathrm{ln}p`$ for $`p=0.03`$.

In two dimensions, one also observes that random initial configurations freeze at large times. Figure 1 displays as a function of $`p`$ the asymptotic correlation length (determined from $`C(r,t=\mathrm{})`$ averaged over 8 networks with $`1500^2`$ spins), as well as the length associated with interface density. The latter is defined as $`L^2/`$, where $`L`$ is the system linear extend and $``$ the total length of all boundaries. Both length scales remain proportional to each other when varying $`p`$, suggesting that frozen configurations can be characterized by one characteristic length scale, referred to as the “domain size”, $`R_{\mathrm{}}(p)`$. Numerical results suggest that $`R_{\mathrm{}}`$ varies as an inverse power-law of $`p`$, with an non-trivial exponent close to $`2/3`$ over nearly two decades. Surprisingly, $`R_{\mathrm{}}`$ does not scale as $`p^{1/2}`$, the characteristic length scale of the network . Once again, the spin-spin correlation function at $`t=\mathrm{}`$ scales rather well as $`C(r)=f(r/\xi _{\mathrm{}}(p))`$, see Figure 3.

Figure 4 shows a typical frozen pattern at $`p=0.05`$. The positions of the “influent” spins are marked by dots: in white, those which are connected to an other influent spin of same sign (“like” pairs, of number density $`n_l`$), in black those connected to a spin of opposite sign (“unlike” pairs, number density $`n_u`$). Initially, $`n_ln_u`$, but as coarsening proceeds, “unlike” dots turn more easily to “like” than the contrary, as in one dimension (Fig. 2$`a`$). Once again, mixing tends to be assortative ($`n_l>n_u`$), but with the increase of $`n_l`$, at some point, there are no more possible moves toward better consensus. We find numerically that coarsening stops and interfaces get pinned when $`n_l1.86n_u`$.

The finite domain size can be interpreted as the result of competing effects between surface tension (the driving force for domain growth) and energy barriers created by the multiplication of influent “like” sites. We picture the system as a collection of $`L^2/R^2`$ domains of radius $`R`$, and estimate its energy change when domains coarsen from $`R`$ to $`R+dR`$ ($`dR>0`$). The usual contribution from surface tension is $`\delta E_I2L^2dR/R^2`$. Meanwhile, the number of influent nodes that flip spin is proportional to $`2pRdR(L^2/R^2)`$. “Like” nodes turn to “unlike” (with an energy cost per spin of 2), and reversely (with an energy decrease of -2). The total energy difference thus reads

$$\delta E\left[\frac{2}{R^2}+\frac{n_ln_u}{n_l+n_u}\frac{4p}{R}\right]L^2dR.$$
(1)
The second term is positive and dominate at large $`R`$. Hence, coarsening is arrested when $`\delta E=0`$, or $`R_{\mathrm{}}p^1`$. This argument is somehow similar to the (equilibrium) Imry-Ma argument for the RFIM . Yet, an important difference is that here the average magnetic field felt on influent nodes (or “impurities”) is not zero, but has been biased ($`n_ln_u`$) due to previous spin flips.

The above continuous Imry-Ma-like argument qualitatively explains frozen states, but over-estimates $`R_{\mathrm{}}`$ ($`p^1`$ instead of $`p^{2/3}`$). The exponent $`2/3`$ can be explained as an effect of the square lattice. As shown on Figure 5$`a`$, a single influent “like” node located at a domain corner can disappear through the diffusive motion of a step. Figure 5$`b`$ represents then the simplest distribution of “like” nodes such that the hatched domain can not shrink. It is composed of two right-angle corners $`\{A,A_1,A_2\}`$ and $`\{B,B_1,B_2\}`$ defining a square $`r\times r`$. If the other white nodes $`\{D_1,..D_n\}`$ contained in the square do not form any right-angle corners, then this region encloses the smallest (or “critical”) pinned domain: any bubble of hatched region comprised in the square and that does not contain both corners $`\{A,A_1,A_2\}`$ and $`\{B,B_1,B_2\}`$ will shrink. Any larger bubble will not. We now calculate the probability $`P_{\mathrm{freeze}}(r)`$ that a configuration such as represented in Fig. 5$`b`$ has a size $`r`$, and then identify $`r^{}`$ such that $`P_{\mathrm{freeze}}(r^{})`$ is maximal with the asymptotic domain size $`R_{\mathrm{}}`$ in the disordered medium.

Given the node $`A`$ located at the origin, the probability that there is at least one white dot ($`A_1`$) on the same line within a distance $`r`$ is $`P_1(r)=1(1p_l)^r`$, with $`p_l/p=n_l/(n_l+n_u)`$ the fraction of influent nodes that are “like” (here, the numerical value of this ratio $``$ close to 0.65 $``$ is unimportant and could be set to 1). Therefore, $`P_{\mathrm{freeze}}(r)=p_l[P_1(r)]^4P_2(r)`$, with $`P_2`$ the probability that the $`D_n`$’s do not form right-angle corners, i.e. that each node $`D_i`$ is at least located on a line or a column not occupied by an other $`D_j`$ (see the dotted lines in Fig. 5b). $`P_2`$ can be approximated as

$$P_2(r)\underset{n=0}{\overset{(r2)^2}{}}(1p_l)^{(r2)^2n}p_l^nC_{(r2)^2}^n[1P_1(r)]^n,$$
(2)
or $`P_2(r)(1p_lP_1(r))^{(r2)^2}`$. In the sum (2) we have multiplied the probability of having $`n`$ white dots inside the square by the probability $`[1P_1(r)]^n`$ that $`n`$ independent dots have no neighbors on the same line within $`r`$. For $`n`$ small, no or few corners can be formed anyway, so that relation (2) slightly under-estimated $`P_2`$, since a small fraction of empty sites are counted twice ($`[1P_1(r)]^n1`$). For $`n`$ large, on the contrary, relation (2) over-estimates $`P_2`$, since it is impossible to locate many dots without forming corners (while $`[1P_1(r)]^n`$ is small but $`0`$). We suppose that both errors compensate. This factorization enable us to compute the most probable square size $`r^{}`$ analytically. $`P_1(r)`$ increases with $`r`$, $`P_2(r)`$ decreases with $`r`$, and $`P_{\mathrm{freeze}}(r)`$ has one single maximum. Assuming $`p1`$, $`r1`$, $`rp1`$, we find that $`r^{}=p_l^{2/3}p^{2/3}`$, in agreement with the numerical results.

To summarize, we have shown on an example that assortative mixing in small world networks can dynamically generate frozen metastable states : At large times, some influent nodes have simply no immediate interest to evolve. These results suggest that long term dynamics in highly connected social systems can produce spatial heterogeneities (or segregation), despite that these configurations are not the most desired ones by individual agents. A similar picture, in agreement with some empirical observations, was drawn recently from antiferromagnetic models on scale-free networks . Right after strong political changes (in Eastern European countries in 1989, in Mexico in 2000) the evolution of reforms can be fast, but rapidly social inertia takes over and renders further adjustments difficult or null. Physically speaking, the response of social systems to external forcings (i.e. large-scale policies) is susceptible to exhibit some of the interesting features known for disordered systems .

While revising the manuscript, we became aware of a similar study on the voter model on small-worlds . We acknowledge fruitful discussions with G. Cocho, J. Viñals and R. Boyer.


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# Quantum cellular automata quantum computing with endohedral fullerenes

## I Introduction

Quantum information processing (QIP), relies on the ability to perform a selection of unitary operations on a multi-partite system. More precise criteria that must be met by any physical implementation of a quantum information processor have been proposed in DiVen1 . In particular, in a spin-based quantum computer architecture the spin sites (i) should be easy to physically manipulate, (ii) easy to replicate in numbers, (iii) they should possess some type of inter-site interaction and (iv) they also should be somewhat isolated from their environment. Meeting such ideals in practice is very demanding. It is believed by some that a solid-state implementation could prove highly advantageous in terms of the scaling up of the number of spin sites and many solid-state proposals for a quantum information processor are currently under study Kane98 ; Spiller01 ; review . However, to achieve (iv), usually requires the spin-sites to be located within a near-perfect crystal lattice and this leads to great difficulties in satisfying (i) and (ii) above. If the interaction between spin sites is mediated by a predominantly electronic interaction, as is the case in ion-trap quantum computers and Kane98 , the quantum computer operation will be very sensitive to stray electric charges. Such systematic charge noise can be source of heating and may be very difficult to eliminate. Additionally the use of local qubit addressing is ubiquitous in very many quantum computer designs. However the use of such local qubit addressing comes with a potentially very large overhead such as the building of nanoscopic metal gates as in Kane98 , or the greatly increased bandwidth required in NMR quantum computing in order to frequency address a large number of spins in a molecule Jones01 . For small numbers of qubits, this overhead may be acceptable but the decoherence effects of imperfect local addressing in a device containing many tens of qubits may be much more serious. Finally, the use of nuclear spins alone in a spin-based quantum computer design leads to a serious difficulty in achieving a sufficiently high initial spin polarization with which to initialise the quantum computer. This is a primary obstacle in liquid state NMR quantum computing and the problem remains in solid-state designs even when the nuclei are cooled to milli-Kelvin temperatures.

Faced with all these challenges, a number of us QIPDDF ; Harneit00 ; LimandSuter , following ideas put forward by the author in QIPDDF , have considered a molecular-based quantum computer which may offer a potentially more robust packaging of the qubit. The central idea is to encode a qubit into the spin system contained within an endohedrally doped fullerene.

In earlier publications Harneit00 , we outlined the unusual properties of Group V C60 endohedral fullerenes and indicated their potential use in a solid-state implementation. We, however, did not there give a detailed description of a concrete quantum computing architecture for use with this material.

In LimandSuter , a locally-addressed quantum computer design using endohedral fullerenes was proposed. Briefly this design stored the qubit on the nuclear spin of the endohedral atom and used the endohedral electron spins as a local bus. The interaction between neighboring qubits is mediated by the magnetic dipole force between neighboring endohedral electrons. By constructing a linear chain of molecules and subjecting the chain to a large magnetic field gradient one can frequency address the electronic spin of an individual molecule and through this perform universal quantum computation.

This type of design has a number of serious drawbacks: (a) to achieve fast local addressing the resonant frequencies of neighboring endohedral electrons must be well separated. Thus the microwave bandwidth required to frequency address many frequency separated spins grows with the number of qubits and may become technically quite challenging to achieve beyond a few hundred MHz (which corresponds to a few tens of qubits). In addition, (b) to be scalable one must perform quantum error correction and to do so will require the simultaneous performance of various quantum gates within the device. Thus the number of independent spectrometer frequency channels required to produce such multi-frequency microwave pulses will grow with the device. To engineer such a spectrometer may be not be ultimately scalable. Finally, (c) to achieve local addressing in LimandSuter  requires the generation of a magnetic field which is highly stable in time and possesses a very large, and preferably very homogeneous, spatial gradient. Currently spectrometers are engineered to yield highly homogeneous, ultra-stable constant magnetic fields (zero spatial gradients), and the engineering of magnetic fields desired in LimandSuter , on a microscopic scale, though possible, will require further development.

The purpose of this work is to show that a quantum cellular automata quantum computing architecture (QCAQCA), can successfully be applied to operate with Group V C60 endohedrals. Further, the resulting design does not exhibit the above mentioned drawbacks seen in LimandSuter . The QCAQCA design only requires an homogeneous constant magnetic field. More importantly, in the QCAQCA, full scale universal quantum computation with quantum error correction only requires frequency addressing at a fixed, small number of frequencies, independent of the size of the device. These two advantages mean that a quantum cellular automata based device may be far easier to develop in hardware than any locally addressed architecture.

For the design developed below we exhibit the specific pulse primitives necessary for quantum cellular automata quantum computation. We are also able to estimate rough figures of merit, or number of quantum gates that can be executed in a decoherence time. The estimated figure of merit obtained below compares well with other proposed quantum computer designs.

In section II below we review the properties of $`𝒳\mathrm{@}`$C60 ($`𝒳={}_{}{}^{15}N,{}_{}{}^{31}P)`$, pertinent for quantum information processing. In section III we briefly outline the essential ingredients of QCAQCA. In section IV we develop a number of tools (pulse sequences), for manipulating the Hamiltonian of an alternating linear chain, $`𝒜𝒜𝒜`$, of these endohedrals where $`𝒜=`$15N@C60 and $`=`$31P@C60. In section V we examine the possibility of an all-electronic QCAQCA and find that universal quantum computation seems not possible using the electrons alone. In section VI we consider an architecture which also includes the nuclear spins and show, by developing new gate pulse sequences, that universal quantum computation can be achieved via a quantum cellular automata design. We finally, in section VII, propose a number of readout techniques that might be applicable to the proposed ensemble (a Type-II quantum computer design Yepez ), and single-issue (or a Type-I quantum computer design Yepez ), quantum computer design.

## II Group V Endohedrals

The endohedrals 15N@C60, 31P@C60 and N@C70 all exhibit very sharp ESR spectra Weidinger98 ; Knapp98 . This indicates the presence of free electrons within these molecules. It has been further shown, both theoretically and experimentally Greer00 ; Dinse00 ; Smith01 , that the trapped atom ($`N`$ or $`P`$), sits at the geometric center of the fullerene cage and that the electrons are in a $`S=3/2`$ quartet ground state. The trapped atoms are extreme examples of compressed atoms Buchachenko01 ; Greer00 , where the electronic wavefunction of the trapped atom is repulsed away from the encompassing carbon cage and suffers a spatial compression. This unique type of “bonding” leads to significantly higher nuclear-electron wavefunction overlap and thus larger Hyperfine coupling constants than what is found in “free” atoms. For the case of C60 Group V endohedrals, the large symmetry renders this hyperfine coupling highly isotropic. Another consequence of this compression is the virtual lack of any electronic interaction between the trapped atom and the carbon cage. The trapped atom is motionally confined by a harmonic-like potential to the center of the cage. In almost all respects, the trapped atom behaves as a “free” (unbonded) atom, though spatially restricted to be within the fullerene cage. All of the above findings imply that such endohedrals behave as nanoscopic molecular neutral atom traps.

The distributed $`\pi `$ bonding electrons on the C60 also act as an almost perfect Faraday cage, strongly isolating the electrons of the trapped atom from external electric fields Pietzak97 . This latter observation implies that it would require the application intense local electric field gradients $`1V/nm`$, in order to alter the Hyperfine coupling constant of the trapped atom. Such an electrostatic addressing scheme has been proposed to address nuclear spin qubits in the Phosphorus donors of the Kane design Kane98 , but with far lower field gradients. Such a scheme would prove very difficult to execute here due to the requirement of such intense electric field gradients. One very significant advantage of containing the spin site inside a relatively large C60 molecule (diameter $`1nm`$), is that such endohedrals can be nano-positioned using current scanning tunneling microscope techniques Beton00 , and moreover neighboring C60 molecules can be nano-positioned on the Silicon(100)-2x surface to be as close as $`1.1nm`$. The C60 molecules, on the Silicon(100)-2x surface, are fixed translationally at room temperature and also rotationally at lower temperatures. More speculatively, due to the electronic-wavefunction spatial compression experienced by these molecules, the chemistry of the doped Group V fullerene material is practically identical to undoped fullerene. It may then be possible to self-assemble large organised spin structures using existing well-studied synthetic supra-chemistry techniques Harneit00 .

The very sharp ESR spectra from these molecules indicates very long relaxation times and more recent measurements have shown the electronic relaxation times are $`T_11s`$ at $`T7^{}K`$, while $`T_220\mu s,T`$ Knor00 . No nuclear relaxation times have yet been recorded but they are expected to be several orders of magnitude longer than the electronic relaxation times. The measured $`T_2`$ time contains contributions from several sources, e.g. unresolved dipolar couplings. The theoretical maximum of $`T_2`$, in the complete absence of the unwanted interactions with other paramagnetic impurities, is the relaxation time $`T_1`$. Indeed, for the case of Phosphorus defects in isotopically ultra-pure 28Si, the phase relaxation time of the loosely bound Phosphorus electrons can be as long as $`T_2>.1`$ msec with $`T_1>1`$ hour Phase . There $`T_2`$ is limited by Hyperfine interactions with residual 29Si nuceli Kane00 . The indicated increase of $`T_2`$ towards $`T_1`$ in the situation of vanishing spin density is crucial for all current spin-based quantum computer proposals Kane98 ; review ; Spiller01 ; QIPDDF ; Harneit00 ; LimandSuter ; Phase1 . Achieving such limits will be very challenging. Making these assumptions for the endohedral electrons we expect $`T_2T_11`$sec, at $`T7^{}K`$, with perhaps longer times at lower temperatures. Such Electronic $`T_1`$ relaxation times ($`1`$sec), in such complicated molecules is highly unusual and may be unique in all non-crystal hosted spin-sites. Long relaxation times also add to the usefulness of such material as hosts for storing and manipulating quantum information.

An essential ingredient for any quantum information processing is an inter-qubit interaction which can generate entanglement. For Group V C60 endohedrals this cannot be a direct electronic exchange type interaction as the electronic wavefunctions are tightly compressed to be within the C60 cage. The C60’s Faraday cage does not restrict magnetic interactions and neighboring endohedrals experience a significant magnetic dipole coupling, $`H_D\stackrel{~}{J}(13\mathrm{cos}^2\theta )[3\widehat{I}_z\widehat{S}_z\widehat{𝐈}\widehat{𝐒}]J_D\widehat{I}_z\widehat{S}_z`$, in the weak coupling limit. The strength of this dipolar coupling has been estimated to be $`J_D50`$MHz$`(1/r^3)`$, where $`r`$ is the separation between the neighboring trapped atoms in the endohedrals measured in nanometers Waiblinger00 , and $`\theta `$ is the angle between $`\stackrel{}{r}`$ and the external $`\stackrel{}{B}`$ field. The Hyperfine coupling constants for 15N@C60, 31P@C60 have been measured Waiblinger , and are given in Table 1.

From the above, to a first approximation, the full spin Hamiltonian for the pair $`𝒜`$, ($`𝒜=`$15N@C60, $`=`$31P@C60), can be given as

$`\widehat{H}/h`$ $`=`$ $`g_e\mu _eB_z\widehat{S}_z^𝒜g_N^𝒜\mu _NB_z\widehat{I}_z^𝒜+A^𝒜\widehat{S}_z^𝒜\widehat{I}_z^𝒜`$ (1)
$`+`$ $`g_e\mu _eB_z\widehat{S}_z^{}g_N^{}\mu _NB_z\widehat{I}_z^{}+A^{}\widehat{S}_z^{}\widehat{I}_z^{}`$
$`+`$ $`J_D\widehat{S}_z^𝒜\widehat{S}_z^{}`$
where $`I(S)`$, labels nuclear(electronic) spin, and we have made the secular approximation dropping terms which do not commute with the electronic Zeeman Hamiltonian since $`\omega _{Larmour}^Sg_e\mu _eB_z(J_D,\omega _{Larmour}^Ig_N\mu _NB_z,A)`$. The individual ESR and NMR spectra of these molecules are simulated in Figure 1, and have been measured in Knapp98 .

## III Quantum Cellular Automata

Typical quantum computer architectures assume the capability of locally addressing every qubit. Such a requirement is highly challenging to engineer and the achievement of this level of individual quantum control is a major goal in almost every current implementation. The use of such local control methods forces an interaction of the quantum information with very many “classical” control gates, each possibly providing a decohering effect on the quantum information. It is also important that the effects of such control gates on the computer’s Hamiltonian remain as “classical” as possible in that they effect a change in the parameters appearing in the system Hamiltonian and do not themselves become entangled with the quantum computer. This criteria of classical gating becomes non-trivial as the length scales of the quantum computer architecture reduces to nanometers.

An alternative architecture is to utilize a small number of identifiable spins, placed in a regular spatial pattern, and to manipulate the quantum information encoded in this spin chain via global addressing techniques. This first of such globally addressed architectures was invented by Lloyd in 1993 Lloyd93 , and utilized three types of addressable spin arranged in the linear pattern $`𝒜𝒞𝒜𝒞𝒜𝒞`$, and where each spin site encodes one logical qubit. In fact this cellular automata design was one of the very earliest quantum computer architectures proposed in the literature. Lloyd showed that such a quantum computer architecture was universal. Benjamin Benjamin99 , found a similar architecture which used only two types of identifiable spin species arranged in the alternating linear pattern $`𝒜𝒜𝒜`$. This reduction in spin resources came with an increase in logical encoding: a logical qubit is now encoded into four spin sites with a buffer space of at least four empty spin sites between each logical qubit.

The operation of Benjamin’s architecture centers on the ability to implement the global unitary operator, $`\widehat{𝒜}_f^U`$. Denoting the spin up(down) state as $`1(0)`$, $`\widehat{𝒜}_f^U`$ is the conditional application of the unitary $`U`$ to the $`𝒜`$ spins in the alternating spin chain $`𝒜𝒜𝒜`$, depending on the state of $`𝒜`$’s neighboring $``$ spins. In particular, letting $`f`$ be the sum of the states of the neighboring $``$ spins, we have $`f[0,1,2]`$. Thus, for example, $`\widehat{𝒜}_1^U`$ is the conditioned application of $`U`$ to all $`𝒜`$ spins in the alternating chain which have neighboring $``$ spins that are different from each other, i.e. $`f=1`$. One has a similar definition for for $`\widehat{}_f^U`$, for the application of $`U`$ on all $``$ spins conditioned on their neighboring $`𝒜`$ spins. The case when $`U\mathrm{NOT}`$, in $`\widehat{𝒜}_f^U`$ (or $`\widehat{}_f^U`$), occurs quite frequently in Benjamin’s architecture and is shortened to $`\widehat{𝒜}_f`$ (or $`\widehat{}_f`$).

Benjamin shows in Benjamin99 , that through a judicious sequence of applications of $`\widehat{𝒜}_f^U`$ and $`\widehat{}_f^U`$, one can implement single qubit operations and two-qubit CNOT operations and thus the architecture is universal. In particular, to move qubits through the spin chain one applies an alternating pulse sequence of $`\widehat{𝒜}_1`$ followed by $`\widehat{}_1`$, while the generation of a control-U between two neighboring logical qubits requires $`30`$ global pulses Hovland00 . One can translate all the standard circuit-based quantum algorithms to run with this quantum cellular automata architecture Hovland00 . This programming architecture, though somewhat expensive in terms of spatial and temporal resources, is ideal for use in systems where the individual control of qubits is difficult and it could provide a interim test-bed for various implementations while the more long term goal of local gating is developed.

Since Lloyd’s and Benjamin’s pioneering work little has appeared in the literature with regard to quantum cellular automata designs for quantum computers Benjamin\_recent . In this paper we will consider a quantum cellular automata architecture consisting of an alternating linear array of Group V endohedrals, $`𝒜𝒜𝒜`$, with the $`𝒜`$ Hamiltonian given by (1) (schematically depicted in Figure 2). Essentially this task reduces to developing a “quantum algorithm” for generating Benjamin’s global operation $`\widehat{𝒜}_f^U`$ (similarly for $`\widehat{}_f^U`$). We first investigate the possibility of implementing $`\widehat{𝒜}_f^U`$, using the $`S`$ (electron), spins alone.

## IV The global operation

In this section we consider an alternating spin 1/2 chain of electronic spins $`S^𝒜S^{}S^𝒜S^{}`$. We begin by considering the $`𝒮^𝒜𝒮^{}`$ unit alone where $`𝒜`$ spin has only one neighboring $``$ spin. We assume that we know how to perform the controlled operation of applying $`U`$ to $`S^𝒜`$, with $`S^{}`$ controlling, an operation we denote by $`C(,𝒜;U)`$. We shall describe below the details regarding the sequence of pulses required to execute $`C(,𝒜;U)`$. We next consider the case when $`𝒜`$ has two neighbors, e.g. $`S^{}S^𝒜S^{}`$. Remembering that one cannot separately address an individual neighboring $``$ spin one can show that instead of performing $`C(,𝒜;U)`$, the above mentioned sequence of pulses now performs

$$\mathrm{\Xi }(,𝒜;U)C(,𝒜;U)C(,𝒜;U)=C(,𝒜;U)^2,$$
(2)
where Eq. (2), defines the function $`\mathrm{\Xi }`$. One can observe that the case when the desired global operation is $`\widehat{𝒜}_1\widehat{𝒜}_1^{\mathrm{NOT}}`$, we have $`\widehat{𝒜}_1=\mathrm{\Xi }(,𝒜;\mathrm{NOT})`$.

We now indicate the procedure for implementing $`\widehat{𝒜}_2^U`$, when the desired $`U\mathrm{exp}(i\theta S_x^𝒜)`$. For ease of notation we define the standard NMR/ESR symbol for $`\pi /2`$ pulses ESRPauli ; Linden99 ; Schulte00 ,

$$[+S_y^{}]\mathrm{exp}(i\frac{\pi }{2}S_y^{}),$$
(3)
and the more general rotation through the angle $`\gamma `$ about the $`z`$axis, for example, by the symbol

$$\{Z_\gamma ^𝒜\}\mathrm{exp}(i\gamma S_z^𝒜).$$
(4)
We find that we can execute $`\widehat{𝒜}_2^U`$, when $`U\mathrm{exp}(i\theta S_x^𝒜)`$ through the following pulse sequence (read right to left),

$`\widehat{𝒜}_2^U`$ $`=`$ $`\mathrm{\Xi }(,A;\{X_\delta ^𝒜\})\{X_{\pi /2\delta }^𝒜\}\{Z_{\pi /2}^𝒜\}\mathrm{\Xi }(,𝒜;\{X_\pi ^𝒜\})`$ (5)
$`\{Z_{\pi /2}^𝒜\}\{X_{\pi /2\delta }^𝒜\}\mathrm{\Xi }(B,A;\{X_\delta ^𝒜\}).`$
where $`2\delta =\theta `$. To implement $`\widehat{𝒜}_1^U`$ one sets $`\delta =\theta `$ and replaces the left most term in (5), $`\mathrm{\Xi }(,𝒜;\{X_\delta ^𝒜\})`$, by $`\{Z_\pi ^𝒜\}`$, while to implement $`\widehat{𝒜}_0^U`$, one applies $`\{X_\pi ^{}\}`$ to all the $``$ spins, then $`\widehat{𝒜}_2^U`$, and finally flip the $``$ spins back with $`\{X_\pi ^{}\}`$. The above pulse sequence (5), can be easily modified to suit other forms of $`U`$ besides $`\mathrm{exp}(i\theta S_x^𝒜)`$, however we will find below that the most useful case is when $`\theta =\pi `$ and $`U=\mathrm{exp}(i\pi S_x^𝒜)NOT`$ on the $`𝒜`$ spin.

## V All Electronic Quantum Cellular Automata Quantum Computer

From Figure 1, we can separately address the electronic spins $`S^𝒜`$ and $`S^{}`$ with a multifrequency selective soft pulse of length $`>20ns`$. If we first consider both $`S^𝒜`$ and $`S^{}`$ to both be spin-$`1/2`$, then one can use standard pulse encodings of the CNOT Linden99 ; Schulte00 ,

$`C(𝒜,,NOT)`$ $`=`$ $`[S_y^{}][S_z^𝒜S_z^{}][\pm 2S_z^𝒜S_z^{}][+S_y^{}]e^{\pm i\pi /4},`$ (6)
$`C(,𝒜;NOT)`$ $`=`$ $`[S_y^𝒜][S_z^𝒜S_z^{}][\pm 2S_z^𝒜S_z^{}][+S_y^𝒜]e^{\pm i\pi /4},`$ (7)
to generate the operation $`\widehat{𝒜}_1`$ and $`\widehat{}_1`$ of the previous section. To perform universal quantum computation one must be at least capable of implementing a two-qubit CNOT and a minimal set of one-qubit operations such as the phase gate, the $`\pi /8`$ gate, and the Hadamard gate. In the quantum cellular automata architecture of Benjamin this means that one must at least be able to implement the global operation $`\widehat{𝒜}_f^U`$, where $`U`$ is taken from this minimal set of one qubit gates and the case where $`UNOT`$. NMR and ESR pulses effectively generate terms in the Hamiltonian which are linear in the spin operators, $`I_{x,y,z}`$, and $`S_{x,y,z}`$. In particular, the spin operators when commuted close to form the Pauli algebra. In the case of spin-1/2, the Pauli algebra generates the group SU(2), or all possible spin-1/2 unitaries. Thus one can generate any desired spin-1/2 unitary through a sequence of pulses when acting on an isolated spin. Furthermore, in the case of the alternating chain $`𝒜𝒜𝒜`$, one can find suitable alterations of (7), when used in (2) and (5), to generate any given unitary $`U`$ in $`\widehat{𝒜}_f^U`$ and similarly for $`\widehat{}_f^U`$. Thus an all electronic quantum cellular automata quantum computer architecture (QCAQCA), using a spin-$`1/2`$ $`𝒜𝒜𝒜`$ chain is possible.

The endohedrals 15N@C60 and 31P@C60, however posses electron spin $`S=3/2`$ and the application of Benjamin’s QCAQCA is not as straightforward. One possibility is to consider the four electronic levels of the electron spin with $`S=3/2`$ to constitute a qu-dit with $`d=4`$. Multi-level quantum computation has been proposed elsewhere multiqdit , but to extend Benjamin’s formulation of the spin-1/2 QCAQCA to operate with qu-dits is far beyond the scope of this article. Indeed, as shown below there are reasons to believe that that such an extension may not be possible within the confines of NMR and ESR.

Remaining with qubits we instead propose to encode a qubit into the four levels of a spin $`3/2`$ in two ways: an “inner qubit” $`\{|m_s=\pm 1/2\}`$, and an “outer qubit” $`\{|m_s=\pm 3/2\}`$. By a small alteration of (7), one can obtain

$`C_{inner}(S^𝒜,S^{};NOT)=C_{outer}(\overline{S_𝒜},S^{};NOT)`$ $`=`$ $`[S_y^{}][S_z^𝒜S_z^{}][+2S_z^𝒜S_z^{}][S_y^{}]e^{+i\pi /4},`$ (8)
$`C_{inner}(S^{},S^𝒜;NOT)=C_{outer}(\overline{S_{}},S^𝒜;NOT)`$ $`=`$ $`[S_y^𝒜][S_z^𝒜S_z^{}][+2S_z^𝒜S_z^{}][S_y^𝒜]e^{\pm i\pi /4},`$ (9)
where $`C_{inner}`$ is a $`CNOT`$ on the Hilbert space spanned by the inner qubits, and similarly for $`C_{outer}`$, $`\overline{S^A}=NOT(S^A)`$, and we have used the spin-$`3/2`$ representations of the $`SU(2)`$ group. Armed with this one can easily construct the Benjamin global operations $`\widehat{A}_1`$ and $`\widehat{B}_1`$ on the inner qubit subspace. One can further construct (see section VI.3), the global operations $`\widehat{A}_f^{NOT}`$, (and similarly $`\widehat{B}_f^{NOT}`$), for $`f=0,\mathrm{\hspace{0.17em}1}`$ and $`f=2`$, the operations most frequently used in the quantum cellular automata quantum computation.

However one finds that one cannot generate all the one-qubit gates required for universal quantum computation. As above, ESR pulses essentially generate terms in the Hamiltonian that are linear in the spin operators and again these terms commute to form a Pauli algebra. Evolution under such terms lead to dynamics that resides in the group generated by this Pauli algebra (or $`SU(2)`$). However, since now we have $`S=3/2`$, this $`SU(2)`$ is merely a subgroup of the full group of unitaries that can act on a spin-3/2, but as long as the system Hamiltonian is linear in the spin operators we need only to consider the dynamics within the $`SU(2)`$ subgroup. Normally a unitary operation $`USU(2)SU(4)`$ will not factor into unitary operations on the inner and outer qubit subspaces. However if $`U`$ is diagonal in the $`|m_s`$ basis it can so factor and with this one can find pulse sequences to implement $`\widehat{A}_f^U`$ where $`U`$ is a phase gate, and the $`\pi /8`$ gate but crucially not the Hadamard gate. Thus an all electronic-QCAQCA with a system Hamiltonian which is linear in the spin operators and where $`S>1/2`$ seems not possible.

One way of implementing $`SU(2)`$ operations on the qubit subspaces and one which is well known in NMR and ESR is to introduce terms in the system Hamiltonian which are not linear in the spin operators. Such terms lie in the full spin-3/2 algebra and the generated unitaries no longer lie in the $`SU(2)`$ subgroup but in the much larger $`SU(4)`$ group. One effect of such nonlinear terms, for example Zero-Field-Splitting terms: $`H_{ZFS}S_z^2`$, can be to lift the degeneracy of the microwave transition frequencies between the $`|m_s|m_s+1`$. This allows one to frequency address the transition $`|m_s=1/2|m_s=+1/2`$, or the inner qubit subspace, and directly implement $`SU(2)`$ operations on this subspace. This allows the generation of arbitrary one-qubit unitaries $`U`$ Wokaun77 . However, this solution frustrates the coherence transfer portion, $`[+2S_z^𝒜S_z^{}]`$, of the pulse sequence (8), and (9), and thus the construction of the global QCAQCA operator $`\widehat{𝒜}_f^U`$. This can be seen by realising that to obtain a $`[+2S_z^𝒜S_z^{}]`$ pulse one must effectively cancel out all the terms in the system Hamiltonian bar the term $`S_z^𝒜S_z^{}`$. As standard in NMR and ESR one does this cancellation through “average Hamiltonian” theory average , via the application of various $`SU(2)`$ unitaries by RF or MW pulses. As long as the system evolution remains within the $`SU(2)`$ subspace such an averaging out can be achieved. However when terms nonlinear in the spin operators are introduced into the system Hamiltonian no application of $`SU(2)`$ unitaries can, in general, average out the resulting “nonlinear” evolution (i.e. in the average Hamiltonian theory nonlinear terms in the Hamiltonian will almost always average to other nonlinear terms), and thus the generation of $`[+2S_z^𝒜S_z^{}]`$, and from this $`\widehat{A}_f^U`$, is not possible.

Thus we have found that when operating on an $`𝒜𝒜𝒜`$, spin-$`3/2`$ chain with ESR pulses one cannot generate all of the necessary global operations required for universal quantum computation. We next find that the combination of nuclear and electronic spins within the chain can improve matters.

## VI Nuclear-electron quantum cellular automata

15N@C60 and 31P@C60 both have nuclear spin-$`1/2`$. In this section we assume that the quantum information is stored in the nuclear spins of the dopant atoms in the $`𝒜𝒜𝒜`$ chain. This has the significant advantage that the nuclear spin relaxation times are typically longer than the electronic spins by several orders of magnitude. As the nuclei only are coupled via the Hyperfine interaction to the electrons, one can, via a suitable RF and MW pulse sequence, cancel out this Hyperfine interaction with high precision. This allows the nuclei to act as a quantum memory and store the quantum information for very long periods of time in between processing.

To execute the Benjamin global operation $`\widehat{𝒜}_f^U`$ we essentially use the inner electronic qubits as a local “bus” for the quantum information stored in the nuclei. The procedure can be thought of as a quantum algorithm for the generation of the global operation and consists of several steps which are pictorially represented in Figure 3.

The algorithm starts with the inner electronic qubit bus in the ground state ($`|m_s=|1/2`$ for all molecules), and this bus is returned to the ground state after implementing the global operation $`\widehat{𝒜}_f^U`$. We first (a) assume that we have an arbitrary pattern of quantum information written onto the nuclear spins of the $`𝒜`$ and $``$ molecules with the electrons set as above. We then, (b) swap the quantum information of all the $``$ molecules from their nuclei to their inner electronic qubits. We then (c) tag those $`𝒜`$ molecules which will receive the unitary operation $`U`$ in $`\widehat{𝒜}_f^U`$ by flipping the state of the electronic qubit of all the $`𝒜`$ molecules conditioned on the state of it’s neighboring $``$ electronic qubits. We then (d) undo (b) by swapping the quantum information back into the $``$ nuclei from their electrons.

At this point all the inner electronic qubits are back in their ground states except for the “tagged” $`𝒜`$ molecules. We then, (e) perform a controlled-$`U`$ operation on the nuclear qubits of all the molecules using their inner electronic qubits as the control. Finally (f), we undo the operations (d), (c) and (b). The system is then ready for the execution of the next global operation.

One restriction we make in the following is that we rule out the use of selective pulses on the nuclear spins of the Nitrogen and Phosphorus. From Figure 1, to execute such selective pulses would require RF pulses of very long duration to frequency differentiate between the NMR transitions of the Nitrogen and Phosphorus. Such slow nuclear pulse sequences would lead to very long gates times. We will therefore not allow ourselves to use such selective nuclear pulse sequences and instead make use of fast “hard” nuclear pulse sequences hard . We do allow selective addressing of the electronic transitions of the Nitrogen and Phosphorus as these pulse sequences are much shorter in duration. With this restriction however we are still able to design all the pulse sequences that are required to carry out the steps (b)-(e), above. The resulting combined total pulse sequence is somewhat lengthy but could be substantially shortened by applying the principles of optimal control theory glasser02 .

We now expand on the above steps (a)-(e), in detail. In section (A) below we describe the initialization of the spin-chain. In section (B) we design the $`SWAP`$ pulse sequence required for step (b). In section (C) we design the electronic pulse sequence to implement the conditional operation required in step (c), and finally in section (D) we outline the execution of the controlled-$`U`$ needed in step (d). In section (E) we discuss the undoing of the previous steps (b)-(d), while in section (F) we provide some estimates of the pulse durations and logical QCA gate times.

### VI.1 Initialization

The QCA architecture may be implemented on an ensemble (Type-II) or single-issue (Type-I), quantum computer. The achievement of high nuclear polarizations has proved to be a major obstacle in NMR quantum computation. It remains a source of difficulty here as well. Polarizing the electrons is far easier, and one can achieve a difference in the ground to excited electronic populations of $`ϵ0.999`$, at a temperature of $`1^{}K`$ and $`B10`$T. Even when multiple spins are tensored to produce a pseudo-pure state, with such high individual polarizations one can still achieve a pseudo-pure state with a purity on the order of $`ϵ.998`$, with $`1000`$ spins at these temperatures and magnetic fields. This polarization can be transferred to the nuclei via an INEPT pulse sequence Levit . To repump the electronic polarization and achieve a subset of completely spin (nuclear and electron), polarized molecules one could consider two chains of equal length: an $`𝒜𝒜\mathrm{}`$ chain and a $`𝒞𝒟𝒞𝒟\mathrm{}`$ chain where all $`𝒜`$, $``$, $`𝒞`$, and $`𝒟`$ are globally addressable. Since at $`1^{}`$K and $`B=10`$T, half of the spins (the electrons), are completely polarised, one can consider an $`𝒜𝒜\mathrm{}𝒜𝒜𝒳𝒞𝒟𝒞𝒟\mathrm{}𝒞𝒟𝒞𝒟`$ super-chain where $`𝒳`$ has a different resonant frequency yet again. One can then use a spin cooling quantum algorithm Schulman99 , to efficiently spin cool all the nuclear and electronic spins on one side of $`𝒳`$ (ie. $`𝒳`$ acts as a spin gate). One would then switch off the interaction between the two sub-chains at $`𝒳`$ and use the spin polarised half chain to perform the quantum computation. Such a design would be suitable for a Type-II (ensemble), quantum computer. Alternatively, in the case of a Type-I quantum computer one can replace the $`𝒞𝒟𝒞𝒟`$ chain with an $`𝒜𝒜`$ chain and place the readouts on the polarised half chain. More practically any Type-I quantum computer will require a single-spin readout of the electronic spins of the endohedral atoms. Such a readout may also serve to initialize the electronic qubits. We discuss possibilities for a single-spin readout further below.

### VI.2 Nuclear-Electronic $`SWAP`$

A crucial ingredient in the above mentioned quantum algorithm to generate $`\widehat{𝒜}_f^U`$ is the Hyperfine $`SWAP`$. This operation performs a logical swap between a qubit stored in the nuclear spin and a qubit stored in the electron spin. Below we find two types of Hyperfine $`SWAP`$, one that performs the swap using the inner electronic qubit and one that uses the outer electronic qubit. For the most part we will use the former type of swap but we will find later that the latter swap, which incorporates the outer electronic qubit, may be of significant use in the problem of qubit readout and we discuss this below.

To develop the pulse sequence for the Hyperfine $`SWAP`$ it is useful to break down the $`SWAP`$ operation into three $`CNOT`$ operations. Denoting $`SWAP(I:S)`$, we have, $`SWAP(I:S)=CNOT(I;S)CNOT(S;I)CNOT(I;S)`$, where $`CNOT(I;S)`$ is the controlled $`NOT`$ for $`I`$ controlling $`S`$. In our case $`I=1/2`$ while $`S=3/2`$. Substituting the spin-$`3/2`$ representations for $`S`$ into the standard spin-$`1/2`$ $`CNOT`$ pulse sequence (7), fails to yield a proper $`CNOT`$ operation. One instead must make reference to the two cases of a $`CNOT`$ with respect to the inner and outer qubits of $`S`$. With this one can find:

$`CNOT_{outer}(I;S)`$ $`=`$ $`[S_y][S_zI_z][\pm 2S_zI_z][S_y]e^{\pm i\pi /4},`$
$`CNOT_{outer}(S;I)`$ $`=`$ $`[I_y][\pm S_z\pm I_z][\pm 2S_zI_z][I_y]e^{\pm i\pi /4},`$ (10)
while

$`CNOT_{inner}(I;S)`$ $`=`$ $`[S_y][S_zI_z][\pm 2S_zI_z][S_y]e^{\pm i\pi /4},`$
$`CNOT_{inner}(S;I)`$ $`=`$ $`[I_y][S_zI_z][\pm 2S_zI_z][I_y]e^{\pm i\pi /4}.`$ (11)
With these one can derive

$`SWAP_{inner}(I:S)`$ $`=`$ $`[I_y][+2I_zS_z][S_yI_y][S_xI_x][+2I_zS_z][I_xS_x][+2I_zS_z][I_y]e^{i\pi /4};,`$ (12)
$`SWAP_{outer}(I:S)`$ $`=`$ $`[I_y][+2I_zS_z][I_yS_y][I_xS_x][+2I_zS_z][S_x+I_x][+2I_zS_z][I_y]e^{+3i\pi /4},`$ (13)
and the related pulse sequences are graphically shown in Figure 4. We note for later the curious case of (13), where we have in some sense “amplified” the magnetic signature of the qubit from a $`\mathrm{\Delta }m_I=\pm 1`$, transition to a $`\mathrm{\Delta }m_S=\pm 3`$, transition. In the following we will restrict ourselves to the inner electronic qubit subspace and thus (12).

Having found a $`SWAP`$ operation between the nuclear and inner electronic qubits of either molecule we now must show how one can adapt the sequence (12), to swap out only the $``$ qubits while leaving the $`𝒜`$ nuclear qubits alone. We now consider the case of two coupled $`𝒜`$ molecules with the Hamiltonian (1). The desired selective swap action can be achieved by replacing the $`[+2I_zS_z]`$ terms in (12), with the pulse sequence shown in Figure 5. This new pulse sequence effectively averages out the Hyperfine coupling interaction in the $`𝒜`$ molecules thus turning off the action of the Hyperfine $`CNOT`$ and $`SWAP`$ gates for these molecules. The Hyperfine interaction for the $``$ molecules is left intact by the pulse sequence but is reduced in magnitude thus lengthening their Hyperfine gate durations.

This particular pulse sequence has a number of advantages, the most important of which is that we do not selectively address the nuclear spins and thus can apply fast hard pulses to $`I^𝒜`$ and $`I^{}`$ simultaneously. We only take advantage of the selective addressing of the electronic spins of $`𝒜`$ and $``$ as outlined at the beginning of section V. Alternatively, one can use soft multi-frequency nuclear pulses in the following to approximate the hard nuclear pulse. In more detail, from Guenter01 ; Beth01 , the action of this pulse sequence is to remove to all orders (within the secular approximation made in II), all interactions between $`S^𝒜S^{}`$ and $`S^𝒜I^𝒜`$. This sequence also removes all the Zeeman terms in the $`𝒜`$ Hamiltonian and one is thus left with $`\widehat{H}/hA^{}\widehat{S}_z^{}\widehat{I}_z^{}`$. When inserted into (12), the effect is to swap the qubit that was stored in $`I^{}`$, into the inner electronic qubit of $`S^{}`$. As mentioned above, the quantum information stored in $`I^𝒜`$ is not swapped into $`S^𝒜`$, but these spins do receive the local unitary transformation, $`[S_y^𝒜][I_y^𝒜]`$. The local unitary $`[S_y^𝒜]`$ is removed with a spin selective electronic pulse $`[S_y^𝒜]`$, however we cannot remove the $`[I_y^𝒜]`$ without performing a spin selective nuclear pulse, an operation we wish to avoid. We will see however, that this extraneous local operation on $`I^𝒜`$ is not important for the tagging of the $`𝒜`$ molecules and furthermore the operation will be “undone” in step (d) (c.f. Figure 3).

### VI.3 Electronic tagging of $`f`$

Summarizing the previous steps: we have now swapped out the nuclear qubits of the $``$ molecules in the $`𝒜𝒜𝒜𝒜`$ chain into their inner electronic qubits. Additionally, all the inner electronic qubits of the $`A`$ molecules are in their ground states $`|m_s=|1/2`$, i.e. we are at step (b) in Figure 3. We will now electronically “tag” those $`𝒜`$ molecules targeted by the global operation $`\widehat{𝒜}_f^U`$. More precisely, we wish to flip the state of the $`𝒜`$ inner electronic qubit subject to the function $`f`$, with the control being $`𝒜`$’s nearest neighbor $``$’s inner electronic qubits. We noted at the end of section V, that many inter-molecular electronic unitaries cannot be achieved with $`SU(2)`$ pulses. However, the case of $`f=1`$ is simply the operation $`\mathrm{\Xi }(,𝒜;NOT)`$, (see section IV), where one uses (8) for the $`CNOT`$ in the inner electronic qubit subspace. The case $`f=2`$ is more difficult and one must make full use of the construction given in (5), to obtain the following pulse sequence

$`\mathrm{\Xi }(,𝒜;\sqrt{NOT})\{Z_{\pi /2}^𝒜\}\mathrm{\Xi }(,𝒜;\sqrt{NOT})`$
$`\{Z_{\pi /2}^𝒜\}\mathrm{\Xi }(,𝒜;\sqrt{NOT})e^{3i\pi /4}.`$ (14)
where $`\mathrm{\Xi }(,𝒜;\sqrt{NOT})C(S^{},S^𝒜;\mathrm{\Sigma })^2`$, (see (2)), and

$$C(S^{},S^𝒜;\mathrm{\Sigma })e^{i\frac{1}{2}\pi S_Y^𝒜}e^{i\frac{1}{4}\pi (S_Z^𝒜+S_Z^{}2S_Z^𝒜S_Z^{})}e^{i\frac{1}{2}\pi S_Y^𝒜}e^{i\pi /4}.$$
(15)
With this pulse sequence one achieves the required spin flip of the $`𝒜`$ molecule’s inner electronic qubit up to a phase. This global phase is unimportant as it will be removed in step (e), when we undo the unitaries. Finally the case $`f=0`$ is dealt with by first flipping all $``$ inner electronic qubits, then using the $`f=2`$ operation above, and then flipping back. In the case of Figure 3, we have chosen to implement the tag $`f=1`$ operation in step (c). Once we have set the electronic tag on the appropriate $`𝒜`$ molecules we “undo” the $`SWAP`$, returning $``$’s quantum information back into its nuclei and $``$’s inner electronic qubits to the ground state, arriving at step (d) in Figure 3.

### VI.4 Implementing $`U`$

We now can implement any desired unitary on the flagged $`𝒜`$ qubits. The construction of this operation is well known Chuangandnielsen , and consists of applying hard pulses hard , to all of the $`𝒜`$ and $``$ and nuclei interspersed by CNOT gates between the inner electronic qubits and nuclear qubits of all the molecules. More precisely, the controlled execution of any given unitary operation on the nuclear spin $`I`$ controlled by the inner electronic qubit $`S`$ on all the molecules may be written as

$`C(S,I;U)`$ $`=`$ $`DC(I,S;X)EC(I,S;X)F,`$ (16)
$`U`$ $``$ $`e^{i\alpha }R_z(\beta )R_y(\gamma )R_z(\delta )`$ (17)
$`=`$ $`e^{i\alpha }DXEXF.`$
In (16), $`\beta ,\gamma `$, and $`\delta `$ are the Euler angles of the desired nuclear $`SU(2)`$ operation, $`C(I,S;X)`$ is the Hyperfine control-NOT given in (11), the nuclear rotation operators are given by $`R_\delta (\theta )\mathrm{exp}(i\theta \delta /2)`$, where $`\delta =x,y,z`$ and standard pulse sequences for these spin rotations can be found in Levit . Further $`DR_z(\beta )R_y(\gamma /2)`$, $`E=R_y(\gamma /2)R_z((\delta +\beta )/2)`$, $`F=R_z((\delta \beta )/2)`$, $`XNOT`$, and $`\alpha `$ is a phase. Crucially one can show that $`DEF=I`$. From this one can see that the action of the sequence (16), on the nuclear spin is unity when the inner electronic qubit is not set. When the inner electronic qubit is set however, the action of (16) is to execute $`U`$ from (17) on the nuclear spin up to the phase $`\alpha `$. One then finally applies the local unitary $`\mathrm{exp}(i\alpha (S_z^𝒜+S_z^{}))`$, to all molecules to yield the final phase factor $`\alpha `$ in (17). With this one has the very powerful capability of applying any desired single-qubit unitary to the nuclear qubits of the tagged $`𝒜`$ molecules. However, the typical operation in the QCAQCA is $`\widehat{𝒜}_f`$, and this can be executed more simply by a Hyperfine $`CNOT`$ between the electronic and nuclear qubits of all the molecules. In Figure 3, we illustrate the application of $`\widehat{𝒜}_1`$ in subfigure (e).

### VI.5 Undoing the unitaries

Following the arguments made in section VI above, we execute step (e), that is: once we have implemented the desired unitary on the $`𝒜`$ nuclear qubits we “undo” steps (b), (c) and (d). We $`SWAP`$ the nuclear qubit into the electrons on all $``$ molecules, undo the tagging of the $`𝒜`$ molecules, and then $`SWAP`$ the quantum information back into the nuclei of the $``$ molecules. The system is left with all the inner electronic qubits in their ground states while the nuclear qubits have received the global operation $`\widehat{𝒜}_f^U`$.

### VI.6 Gate duration

As we noted above, the resulting pulse sequence is quite lengthy. However it may be possible to compress many of the above operations. Also all nuclear pulses are fast hard pulses of little duration caveat , while the primary slowdown arises from the nuclear-electronic $`SWAP`$ whose duration is limited by the value of the Hyperfine coupling constant of 15N@C60 ( $`20`$MHz), and the separation of the spectral lines of the $`𝒜`$ and $``$ molecules in the ESR spectrum of Fig. 1 ($`50`$MHz). The typical QCAQCA global operation, $`\widehat{𝒜}_f`$, entails a pulse sequence in which the terms $`[+a_zb_z]`$, occurs 15 times, each with an average duration of $`50ns`$, thus roughly bringing the cycle time of the global operation down to $`1\mu s`$. As noted above, the simplest quantum logic gate in the QCAQCA scheme requires $`30`$ global operations. This finally brings the cycle time for logical gates in the resulting QCAQCA to be roughly $`30\mu s`$.

We noted in section II, one has $`T_11s`$ at $`T=7^{}K`$, and $`T_220\mu `$s for concentrated samples of 15N@C60 Group-V endohedral material. As mentioned above, recent experiments have indicated a dependence on concentration for $`T_2`$ and it is commonly expected in all current spin-based quantum computer implementations that $`T_2`$ will rise towards the value of $`T_1`$ in the limit of zero spin concentration. If $`T_21`$s then one can expect on average $`10,00030,000`$, logical operations within this dephasing time (figure of merit). Indeed, at temperatures lower than $`7^{}`$K one might be able to achieve far greater figures of merit as the decoherence and dephasing times increase. A figure of merit of $`10^4`$ compares very favorably with most alternative proposed implementations for quantum information processors.

## VII Readout

One of the most challenging aspects of any solid-state implementation is that of readout. We first discuss the possibilities for an ensemble readout for the QCAQCA and later a single-spin readout for a Type-I implementation.

In the original scheme of Lloyd Lloyd93 , the only spin sites which could be individually addressed were those at either end of the chain as these spins were frequency differentiated by having a single neighbor. This is also the situation here. However, if these two sites were the only readout sites on the chain then the architecture would not be scalable in the presence of noise. One ensemble readout possibility would be to attach an electrically isolated paramagnetic adduct to every $``$ molecule, ( Gd@C82 may be a possibility). Such readout sites would typically possess short relaxation times and one would have to isolate such sites from the operation of the primary processor using ESR pulses. It should be possible within the cellular automata architecture to selectively readout the state of a single qubit, that is, to transfer the state of a given logical qubit into the readout site. This can be done by adapting the single-qubit unitary operator $`U`$, pulse scheme in Benjamin99 . This pulse sequence is arranged so that a logical qubit (which is usually encoded in four spins, $`𝒜𝒜`$), gets driven into the state of a single spin which is then subject to a unitary operation, $`U`$, through the application of the global operation (say $`\widehat{}_f^U`$, when the qubit has been forced into the spin state of a $``$ molecule). The spin neighborhood of this target $``$ spin is arranged so that this global operation only effects the state of that spin alone with an appropriate choice for $`f`$. For readout one could instead apply an operation $`\widehat{}_f^{SWAP}`$, which swaps out the state of the spin into the readout site. This would be read and then $`SWAP`$ed back.

For a Type-I quantum information processor based on the $`𝒜𝒜`$ chain of 15N@C60 and 31P@C60 one must be capable of performing a single electron spin readout. We suggest a number of possible technologies that may be capable of performing such a readout below. Before mentioning these we return to section VI.2 and Equation (13). There we noticed that this pulse sequence was able to $`SWAP`$ the qubit between the highest and lowest weight subspaces of the nuclear and electronic spins, $`I=1/2`$ and $`S=3/2`$, and in the process increase the detectable magnetic signature by a factor $`1000`$.

We will now further enquire whether there exists similar pulse sequences which could further $`SWAP`$ out the quantum information now stored in the outer electronic qubit into a separate coupled electronic system of larger spin. This could be very advantageous, for example, for the purposes of coupling into the spin-chain, a nano-molecular magnet with a spin of $`1030`$ as a potential readout site sessoli . As the $`SWAP`$ gate is built from $`CNOT`$ gates we can focus on the latter. Further, the pulse sequences must only consist of higher spin representations of the Pauli group. There may be many such pulse sequences and we here present one set of sequences. The ones given below perform a $`CNOT`$ between the highest and lowest weight subspaces of spins $`I`$ and $`S`$. We set $`I=a/2`$ and $`S=b/2`$, where $`ba`$ and both $`a`$ and $`b`$ are odd integers. Letting $`\alpha =[a/2]`$ and $`\beta =[b/2]`$, where $`[]`$ is the integer part of the fraction, we can find $`CNOT`$ pulses for the following four cases:

$`\alpha \mathrm{even},`$ $`\beta \mathrm{even}:`$ $`C_(I,S;NOT)=[S_y][S_zI_z][+2S_zI_z][S_y]e^{+i\pi /4},`$ (19)
$`C_(S,I;NOT)=[I_y][S_zI_z][+2S_zI_z][I_y]e^{+i\pi /4},`$
$`\alpha \mathrm{odd},`$ $`\beta \mathrm{odd}:`$ $`C_(I,S;NOT)=[S_y][+S_z+I_z][+2S_zI_z][S_y]e^{+i\pi /4},`$ (21)
$`C_(S,I;NOT)=[I_y][+S_z+I_z][+2S_zI_z][+I_y]e^{+i\pi /4},`$
$`\alpha \mathrm{odd},`$ $`\beta \mathrm{even}:`$ $`C_(I,S;NOT)=[S_y][+S_z+I_z][+2S_zI_z][S_y]e^{+i\pi /4},`$ (23)
$`C_(S,I;NOT)=[I_y][S_zI_z][+2S_zI_z][I_y]e^{+i\pi /4},`$
$`\alpha \mathrm{even},`$ $`\beta \mathrm{odd}:`$ $`C_(I,S;NOT)=[S_y][S_zI_z][+2S_zI_z][S_y]e^{+i\pi /4},`$ (25)
$`C_(S,I;NOT)=[I_y][+S_z+I_z][+2S_zI_z][I_y]e^{+i\pi /4}.`$
A Type-I quantum computer design will require the capability of single qubit readout and this translates in our case to the capability of reading out the spin state of the endohedral electrons. One can classify the various readout methods into the general categories (i) force, (ii) electric, and (iii) optical, measurement techniques. As was mentioned before, since the electronic wavefunction of the trapped atom is totally confined within the C60 cage, spin measurement techniques that involve the physical transport of this spin outside the molecule are not possible here. Some techniques, such as ODMR (optically detected magnetic resonance), have so far not proved possible with 15N@C60 and 31P@C60, and thus the addition of separate readout sites which can be dynamically coupled and decoupled from the primary processor via NMR/ESR pulses are warranted.

Possible techniques in the above mentioned categories include (i) Magnetic Resonance Force Microscopy (MRFM) MRFM ; (iia) Micro-Squids, a technology which is already capable of discriminating a $`\mathrm{\Delta }m_S=30`$ Pakes ; (iib) Scanning-Tunneling-Microscope ESR, a technique which, though not well understood, has yielded single molecule ESR spectroscopy of iron impurities in Silicon STMESR , and in single BDPA molecules on Silicon Durkan . (iic) A single molecule endohedral fullerene single electron transistor mcewen . This is a very challenging technology which has yielded a single electron tunneling current through a C60 molecule with an electro-mechanical coupling to the quantized motion of the entire molecule. Performing such an experiment with 15N@C60 may yield endohedral spin information; (iiia) Magnetic coupling of the endohedral electronic spin to a solid-state paramagnetic optical dipole such as a nanocrystaline N-V center in diamond. The optical paramagnetic center can then be probed via optical shelving techniques NV ; (iiib) ODMR via a magnetic coupling to a paramagnetic endohedral adduct which is chemically bonded to the 15N@C60 molecule. For use with ODMR the adduct endohedral should ideally possesses an optical transition in the visible spectrum such as $`\mathrm{Er}_x\mathrm{Sc}_{3x}`$N@C80 Dorn  .

The techniques suggested above are, in some cases, already at the single electron detection level (though not capable of detecting the spin orientation), while the out-coupling of the quantum information into a large-spin system may allow the techniques of micro-Squids and MRFM as they presently stand to act as a readout of a single endohedral electronic spin.

## VIII Conclusion

The philosophy taken in this work with regard to the construction of a quantum information processor is to follow as closely as possible the system Hamiltonian that nature provides. The globally addressed approach has very significant advantages over the local gating approach. Global addressing avoids the buildup of numerous decoherence pathways associated with the effects of the local gates on the processor. Global addressing also avoids the very significant problem of the scaling up of the external resources required to execute local gating, eg. numerous metallic contacts or multi-frequency MW/RF generators with increasing bandwidths. Although it may be true that for local gating, the external resources required increase polynomially with the number of qubits in the processor, such an overhead may not be experimentally feasible as the size of the processor grows large.

In some sense the technical complexities involved in the construction and operation of local gating are transferred into the quantum cellular automata “software”. As shown above, the detailed operation of a quantum cellular automata quantum computer architecture does not follow the standard quantum circuit model. This should not be seen as a disadvantage as all quantum circuit algorithms can be “compiled” to run on a QCAQCA with a polynomial overhead Benjamin99 . Indeed the QCAQCA may be able to run programs that do not follow the quantum circuit model (see Raussendorf  for an example of a non-circuit quantum program in another architecture). Furthermore, as the fundamental quantum operations are implemented via the very well developed methods of NMR and ESR, the fidelity of software execution is heightened. The QCAQCA also has the very important property that it can execute quantum computations in parallel, a characteristic necessary for the ultimate scalability of the architecture.

In this work we considered the endohedral fullerene material 15N@C60 and 31P@C60 and argued that the system Hamiltonians and interactions present are sufficient to implement universal quantum computation via a quantum cellular automata architecture. Following the DiVincenzo criteria: (i) we argued that the Group-V endohedral materials behave as essentially electrostatically isolated nanoscopic molecular neutral atom traps that can be physically manipulated with relative ease using STM techniques and perhaps may be self-assembled using fullerene supra-chemistry. (ii) the electronic decoherence times are perhaps the longest seen in any molecular system, of the order of seconds at temperatures of $`7^{}`$K, which is also an upper limit for the electronic dephasing time. The nuclear decoherence times have not yet been measured but they are expected to be several orders of magnitude longer than the electronic decoherence times. (iii) The complete polarization of both the nuclear and electronic computational spins is feasible as half of the spins (electrons), within the entire system are completely polarised at moderate conditions of temperature and magnetic field strength. There are efficient cooling schemes exist to shuffle the unpolarized spins away from the computational spins. (iv) entanglement can be generated via the inter-molecule magnetic dipole interaction, the strength of which has been measured to be $`50`$MHz. Armed with the two species 15N@C60 and 31P@C60, we showed that one has sufficient control to implement a two-component quantum cellular automata quantum computing architecture storing the quantum information in the nuclear spins while using the electrons as a local bus. We further found that the expected “figure of merit” compares very well with other proposed solid-state quantum computer designs. We also discovered pulse sequences that $`SWAP`$ed the quantum information between the highest and lowest weight spaces of two spins of different size, e.g. $`S=1/2S=11/2`$. These sequences could prove useful for out-coupling the quantum information into a spin readout system with large spin.

DiVincenzo’s final criterion: (v) an efficient single qubit readout, is perhaps the most difficult challenge for any solid-state based quantum computer design. We have proposed various possible ensemble and single-issue (Type-I), readout technologies many of which are themselves the subjects of intense study. The ideas presented here combine the tremendous power of NMR and ESR science together with the very “clean”, and almost atomic, systems presented by the endohedrals 15N@C60 and 31P@C60. These, married with supra-molecular chemistry, may provide a very real possibility for a physical implementation of a quantum information processor.

## Acknowledgments

The author thankfully acknowledges useful discussions with Dieter Suter and Wolfgang Harneit. This work was supported by the EU IST FET QIPC project QIPD-DF (http://planck.thphys.may.ie/QIPDDF).