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# Stability of quantum Fourier transformation on Ising quantum computer

## I Introduction

Quantum information theory Bennett  is a rapidly evolving field. It uses quantum systems to process information and by doing so can achieve things that are not possible with classical resources. Quantum secure communication for instance is already commercially available. Quantum computation on the other hand is still far from being useful outside of the academic community. Two serious obstacles to overcome in building quantum computers are: (i) one must be able to control the evolution in order to precisely implement quantum gates, (ii) one must suppress all external influences. Errors in both cases are caused by the perturbation of an ideal quantum computer, either due to the internal imperfections in the first case or due to coupling with the “environment” in the second case. In the present paper we study both kind of errors in QFT algorithm and try to minimize them.

In order to be closer to the experimental situation we choose a concrete model of a quantum computer, namely the Ising quantum computer (IQC) Ising1st . IQC is one of the simplest models still having enough complexity to allow universal quantum computation. Quantum gates on this computer can be realized by the application of electromagnetic pulses. For the algorithm we choose to discuss QFT. The first reason to choose QFT is that it is one of the most useful quantum algorithms, giving exponential speedup over the best classical procedure known, and is also one of the ingredients of some other important algorithms, e.g. Shor’s factoring algorithm Shor . The second reason is that it is a complex algorithm, where by complex we mean it has more than $`𝒪(n)`$ number of quantum gates as opposed to previously studied more simple algorithms where the number of gates scales only linearly with the size of the computer (e.g. entanglement protocol DynFid ). Previous study of Shor’s algorithm in IQC IsingShor  did not use recently introduced generalized $`2\pi k`$ method carlos  which is the best known procedure for inducing transitions on IQC. It is easy to imagine that in most useful quantum algorithms the size of the program will grow faster than linearly with the number of qubits $`n`$ and therefore it is important to see how errors accumulate in such algorithms. This importance is confirmed by our results showing that errors due to unwanted transitions for QFT grow with the square of the number of pulses and not linearly as in algorithms with linear $`𝒪(n)`$ number of gates, for a typical state.

For QFT algorithm running on IQC we analyze errors due to spurious transitions caused by pulses, these we call intrinsic errors, and errors due to the coupling with an external “environment”, called external errors, modeled by a random hermitian matrix from a gaussian unitary ensemble (GUE) Guhr . We minimize intrinsic errors by applying some additional pulses to correct most probable errors carlos  and by doing this, we are able to suppress intrinsic errors by several orders of magnitude. To suppress external errors due to GUE perturbation we use previously proposed improved quantum Fourier transformation (IQFT) IQFT  which is more stable against GUE perturbations in a certain range of parameters. By using correlation function approach Corr  we analyze in detail the dependence of errors on all relevant parameters and on the number of qubits $`n`$. By doing this we can set the limits between which parameters of IQC should lay in order to preserve the stability of computation. In our approach to decrease errors we do not use error correcting codes for the following reasons: we want to remove as many errors as we can on the lowest possible level and second, the intrinsic and external errors are not easily handled by error correcting codes (see Ref.Andrew  and references therein).

The outline of the paper is as follows. In section II we repeat the definition of IQC and in section III we summarize linear response formalism which is the main theoretical tool for studying fidelity. In section IV we study intrinsic and external errors, first separately and then the case of both errors present at the same time. In the appendix we present the pulse sequences used to implement QFT and IQFT algorithms.

## II Ising quantum computer

IQC consists of a 1-dimensional chain of $`n`$ equally spaced identical spin $`1/2`$ particles coupled by nearest neighbor Ising interaction of strength $`J`$, so that parallel spins are favored over anti-parallel ones by an energy difference of $`J`$ (we set $`\mathrm{}=1`$ throughout the paper). The quantum computer is operated via an external magnetic field having two components. The first one is a permanent magnetic field oriented in the $`z`$ direction with a constant gradient which allows for the selective excitation of individual spins, while the second one is a sequence of $`T`$ circular polarized fields in the $`x`$-$`y`$ plane (which are called pulses) with different frequencies $`\nu ^{(m)}`$, amplitudes (proportional to the Rabi frequencies $`\mathrm{\Omega }^{(m)}`$), phases $`\phi ^{(m)}`$ and durations $`\tau ^{(m)}`$ for the $`m`$th pulse, in which is encoded the protocol. A particular orientation of the register allows to suppress the dipole-dipole interaction between spins magicangle1 ; magicangle2 .

The Hamiltonian of the system is

$$\widehat{H}=\frac{1}{2}\underset{l=0}{\overset{n1}{}}\omega _l\widehat{\sigma }_l^z\frac{J}{2}\underset{l=0}{\overset{n2}{}}\widehat{\sigma }_l^z\widehat{\sigma }_{l+1}^z\underset{m=1}{\overset{T}{}}\widehat{V}^{(m)}(t)\mathrm{\Theta }^{(m)}(t)$$
(1)
with

$$\widehat{V}^{(m)}(t)=\frac{\mathrm{\Omega }^{(m)}}{4}\underset{l=0}{\overset{n1}{}}(\widehat{\sigma }_l^{}\mathrm{exp}\{\mathrm{i}(\nu ^{(m)}t+\phi ^{(m)})\}+\text{h.c.}),$$
(2)
$`\mathrm{\Theta }^{(m)}(t)`$ equal to one during the $`m`$th pulse and zero otherwise, $`\widehat{\sigma }_l^{x,y,z}`$ the usual Pauli operators for spin $`l`$ and $`\widehat{\sigma }_l^\pm =\widehat{\sigma }_l^x\pm \mathrm{i}\widehat{\sigma }_l^y`$. Due to the constant gradient of the permanent magnetic field, the Larmor frequencies depend linearly on $`l`$, $`\omega _l=(l+1)a`$. By appropriately choosing the energy units we fix $`J=1`$ throughout the paper so that the only relevant energy scales are $`\mathrm{\Omega }^{(m)}`$ and $`a`$. The basis states are chosen so that $`\widehat{\sigma }_l^z|0_l=|0_l`$.

We will introduce the following notation for further discussion. Let the pulse $`P_i^{ac}`$ indicate a pulse with frequency $`\nu _i^{ac}`$ resonant with the flip of the $`i`$-th spin if its neighbors are in states “$`a`$” and “$`c`$”. This will induce the resonant transition $`|\mathrm{}a_{i+1}b_ic_{i1}\mathrm{}|\mathrm{}a_{i+1}\overline{b}_ic_{i1}\mathrm{}`$, named $`T_i^{ac}`$, if the pulse is a $`\pi `$ pulse ($`a,b,c\{0,1\}`$). Note that for edge qubits, i.e. $`i\{0,n1\}`$, only one superscript is needed.

Operating IQC in the selective excitation regime, $`\mathrm{\Omega }^{(m)}Ja`$, allows one to separate transitions induced by pulses into three sets: resonant, near-resonant and non-resonant according to the detuning $`\mathrm{\Delta }`$ of the transition which is the difference between the frequency of the pulse and the energy difference of the states involved in the transition. If $`\mathrm{\Delta }`$ is exactly equal to zero, the transition is called resonant ($`T_i^{ac}`$ induced by the pulse $`P_i^{ac}`$), if $`\mathrm{\Delta }`$ is of the order of $`J`$ it is called near-resonant ($`T_i^{a^{}c^{}}`$ induced by the pulse $`P_i^{ac}`$ with $`\{a^{},c^{}\}\{a,c\}`$), and if $`\mathrm{\Delta }`$ is of the order of $`a`$ it is called non-resonant ($`T_i^{}^{a^{}c^{}}`$ induced by the pulse $`P_i^{ac}`$ with $`i^{}i`$). In the implementation of a protocol resonant transitions are the ones wanted, while near-resonant and non-resonant transitions are a source of error.

In the two level approximation magicangle1 , a given unwanted transition with detuning $`\mathrm{\Delta }`$ is induced with probability

$$p=\frac{\mathrm{\Omega }^2}{\mathrm{\Omega }^2+\mathrm{\Delta }^2}\mathrm{sin}^2\left(\rho \frac{\pi }{2}\sqrt{1+\frac{\mathrm{\Delta }^2}{\mathrm{\Omega }^2}}\right),$$
(3)
where $`\rho `$ is a dimensionless duration of the pulse (for a $`\pi `$ pulse $`\rho =1`$ and for $`\pi /2`$ pulse it is $`1/2`$). The most probable transitions are the near-resonant ones and these can be suppressed as briefly described in the next paragraph.

For $`P_i^{10}(=P_i^{01})`$ pulses all near-resonant transitions have the same detuning so setting $`\mathrm{\Omega }`$ to $`\mathrm{\Delta }/\sqrt{4k^21}`$ with $`k`$ an integer suppresses these transitions. Since for near-resonant transitions $`\mathrm{\Delta }=𝒪(J)`$, Rabi frequency is for all pulses of the order of $`\mathrm{\Omega }J/k`$. On the other hand, for $`P_i^{00}`$ and $`P_i^{11}`$ pulses near-resonant transitions have two different detunings therefore it is impossible to suppress both with a single pulse. This problem can be overcome adding an additional correcting $`P_i^{10}`$ pulse. The combination of these pulses in order to suppress all near-resonant transitions is called $`Q`$-pulse denoted by $`Q_{i\rho }^{ac}`$ when doing a $`\rho \pi `$ rotation of the $`i\text{th}`$ qubit if neighbors are in states “$`a`$” and “$`c`$”. This method to eliminate near-resonant transitions is called generalized $`2\pi k`$ method. We refer the interested reader to Ref. carlos  for further details. $`Q`$-pulses are the basic building blocks of gates, which in turn are the building blocks of algorithms such as QFT and IQFT.

QFT for $`n=4`$ qubits can be written as

$$U_{\text{QFT}}=\text{T}\text{A}_0\text{B}_{01}\text{B}_{02}\text{B}_{03}\text{A}_1\text{B}_{12}\text{B}_{13}\text{A}_2\text{B}_{23}\text{A}_3.$$
(4)
There are in total $`n`$ Hadamard A gates , $`n(n1)/2`$ two-qubit B gates, $`\text{B}_{jk}=\text{diag}\{1,1,1,\mathrm{exp}(\mathrm{i}\theta _{jk})\}`$, with $`\theta _{jk}=\pi /2^{kj}`$ and one transposition gate T which reverses the order of qubits (e.g. $`\text{T}|001=|100`$). In total there are $`n(n+1)/2+1`$ gates. IQFT algorithm IQFT  for $`n=4`$ qubits is given by

$`U_{\text{IQFT}}`$ $`=`$ $`\text{T}\text{A}_0\text{R}_{01}\text{R}_{02}\text{R}_{03}\text{G}_{01}\text{G}_{02}\text{G}_{03}`$ (5)
$`\times \text{A}_1\text{R}_{12}\text{R}_{13}\text{G}_{12}\text{G}_{13}\text{A}_2\text{R}_{23}\text{G}_{23}\text{A}_3,`$
where $`\text{G}_{ij}:=\text{R}_{ij}^{}\text{B}_{ij}`$. The R gate is defined by $`\text{R}_{ij}|\mathrm{}a_i\mathrm{}b_j\mathrm{}:=(1)^{b_j}|\mathrm{}a_i\mathrm{}(\overline{a_i}b_j)\mathrm{}`$. In total there are $`n^2+1`$ gates in IQFT, i.e. roughly two times as many as for QFT.

Recall that the implementation of quantum gates on IQC is easier in the interaction frame. Therefore, pulse sequences used in the paper implement the intended gates in the interaction frame. Each gate for QFT or IQFT (Eqs. (4) and (5)) must in turn be implemented by several pulses (see appendix). The number of pulses for QFT grows as $`18n^3`$ whereas it grows as $`54n^3`$ for IQFT. Note that this number can become very large, e.g. for IQFT and $`n=10`$ one has $`44541`$ pulses. Throughout the paper our basic unit of time will be either a gate (as written for instance in Eqs. (4) and (5)) or a pulse. A single exception will be the paragraph discussing correlation function of intrinsic errors, where the basic unit is a $`Q`$-pulse, which is composed of one or two pulses. The reason is that $`Q`$-pulses are the smallest near-resonant corrected unit of generalized $`2\pi k`$ method.

## III Linear Response theory

As a criteria for stability we will use the fidelity $`F(t)`$, defined as an overlap between a state $`\psi (t)`$ obtained by an evolution with an ideal algorithm and the perturbed $`\psi _\delta (t)`$ obtained by the perturbed evolution:

$$F(t)=|\psi _\delta (t)|\psi (t)|^2,$$
(6)
where $`|\psi (t)=U(t)|\psi (0)`$ and $`|\psi _\delta (t)=U_\delta (t)|\psi (0)`$. To simplify matters we will assume time $`t`$ to be a discrete integer variable, denoting some basic time unit of an algorithm, like a gate or a pulse. The quantity measuring the success of the whole algorithm is the fidelity $`F(t)`$ at $`t=T`$ where $`T`$ denotes the number of gates (pulses). One of the most useful approaches to studying fidelity is using linear response formalism in terms of correlation function of the perturbation, for a review see Ref. Pregledni . This approach has several advantages. First it rewrites the complicated quantity fidelity in terms of a simpler one, namely the correlation function, simplifying the understanding of the fidelity. Second, the scaling of errors with the perturbation strength, Planck’s constant and with the number of qubits is easily deduced. Furthermore, as in practice one is usually interested in the regime of high fidelity, linear response is enough.

First we will shortly repeat linear response formulas as they will be useful for our discussion later. Let us write an ideal algorithm up to gate $`t`$ as $`U(t)`$

$$U(t)=U_tU_{t1}\mathrm{}U_1,$$
(7)
where $`U_i`$ is the $`i`$-th gate (pulse). If $`t=T`$ we have a decomposition of a whole algorithm.

The perturbed algorithm can be similarly decomposed into gates

$$U^\delta (t)=U_t^\delta U_{t1}^\delta \mathrm{}U_1^\delta .$$
(8)
Each perturbed gate $`U_j^\delta `$ is now written as

$$U_j^\delta =\mathrm{exp}(\mathrm{i}\delta V_j)U_j,$$
(9)
where $`V_j`$ is the perturbation of $`j`$-th gate and $`\delta `$ is a dimensionless perturbation strength. For any perturbed gate one can find a perturbation generator $`V`$, such that the relation (9) will hold. Observe that the distinction into perturbation strength $`\delta `$ and the perturbation generator $`V`$ in Eq. (9) is somehow arbitrary. If one is given an ideal gate $`U`$ and a perturbed one $`U^\delta `$ one is able to calculate only a product $`\delta V`$. This arbitrariness can always be fixed by demanding for instance that the second moment of the perturbation $`V`$ in a given state equals to $`1`$, $`V^2V^2=1`$.

To the lowest order in the perturbation strength fidelity can be written as Corr

$$F(t)=1\delta ^2\underset{t_1,t_2=1}{\overset{t}{}}C(t_1,t_2),$$
(10)
where the correlation function of the perturbation is

$$C(t_1,t_2)=V_{t_1}(t_1)V_{t_2}(t_2)V_{t_1}(t_1)V_{t_2}(t_2)$$
(11)
with $`V_j(t)=U^{}(t)V_jU(t)`$ being the perturbation of $`j`$-th gate propagated by an ideal algorithm up to time $`t`$, i.e. in the Heisenberg picture. The brackets $``$ denote the expectation value in the initial state. Throughout the paper we use random gaussian initial states and average over many of them to reduce statistical fluctuations. Note that the time dependence of the correlation function (11) is due to two reasons: one is time dependence due to the Heisenberg picture (time index in brackets) and the second one is due to the time dependence of the perturbation itself (time index as a subscript), i.e. one has different perturbations $`V_jV_k`$ for different gates $`j,k`$. The expression for the fidelity Eq. (10) is the main result of the linear response theory of the fidelity. From this one can see that decreasing the correlation sum (or even making it zero, see Ref. Freeze ) will increase the fidelity. In Ref. IQFT  stability of QFT algorithm was considered with respect to static GUE perturbation. Analyzing the correlation function they were able to design an improved QFT algorithm (IQFT) which increases fidelity.

We are mainly interested in the fidelity $`F(T)`$ at the end of an algorithm. The final time $`T`$ in useful quantum algorithms depends on the number of qubits in a polynomial way, say as $`Tn^p`$. The power $`p`$ depends on the algorithm considered and of course also on our decomposition of an algorithm into gates (pulses). For QFT and IQFT algorithms with decomposition into gates, Eqs. (4) and (5), one has $`p=2`$. On the other hand, for the implementation of QFT on IQC one needs $`Tn^3`$ ($`p=3`$) basic electromagnetic pulses, as one is not able to directly perform $`\text{B}_{jk}`$ gates on distant qubits but has to instead use a number of pulses proportional to the distance between the qubits $`|jk|`$. Now if the correlation function decays sufficiently fast, the fidelity will decay like $`F=1\delta ^2\sigma n^p`$ whereas in the case of slow correlation decay the fidelity will decay as $`F=1\delta ^2cn^{2p}`$. In the extreme case of perturbations at different gates being statistically uncorrelated (very fast decay of correlations) $`V_jV_k\delta _{jk}`$ one obtains the exact formula $`F=\mathrm{exp}(\delta ^2n^p)`$ IQFT . In the limit of large quantum computer (large $`n`$) strongly correlated static errors, giving slow decay of correlations, will therefore be dominant due to fast $`n^{2p}`$ growth. When we will discuss errors caused by perturbations due to the coupling with the environment we will focus on static perturbations, meaning the same perturbation on all gates, $`V_k=V_j=V`$, as this component will dominate large $`n`$ behavior.

## IV Errors in QFT

Errors in an experimental implementation of QFT algorithm on an IQC can be of three kinds: (i) due to unwanted transitions caused by electromagnetic pulses (ii) due to coupling with external degrees of freedom and (iii) due to variation of system parameters in the course of algorithm execution. In the present paper we will discuss only the first two errors. Errors due to electromagnetic pulses are inherent to all algorithms on an IQC as we are presently unable to design pulse sequences for quantum gates without generating some unwanted transitions albeit with small probabilities. This errors can be in principle decreased by going sufficiently deep into selective excitation regime but one must of course keep in mind the limitations of real experiments111A new method for dealing with intrinsic errors have been proposed recently in Ref. lidar . Coupling with the “environmental” degrees of freedom is endemic in all implementations of quantum computers. As the environment will usually have many degrees of freedom we will model its influence on the quantum computer by some effective perturbation $`V_{\text{eff}}`$ given by a random matrix from a Gaussian unitary ensemble (GUE) Guhr . Note that coupling with the environment will generally cause non-unitary evolution of the central system. We expect quantum computation to be stable only on a time scale where evolution is approximately unitary, i.e. for times smaller than the non-unitarity time scale. Therefore we limit ourselves to unitary external perturbations. The third kind of errors due to the variation of system parameters, like e.g. variation of Larmor frequencies due to the variation of the magnetic field is not considered in this paper. This does not mean they are not important. Let us consider a systematic error in the gradient of the magnetic field throughout the protocol ($`aa+\delta a`$). Demanding that the error in the largest eigenphase at the end of the algorithm is much smaller than $`1`$, one gets the condition $`a/\delta aan^{p+2}/\mathrm{\Omega }`$. If one is in the selective excitation regime, this ratio can become very large and this puts a severe demand on the experiments.

To ease up understanding we will first discuss intrinsic errors only, then we will discuss external errors only and finally we will combine both errors.

### IV.1 Intrinsic Errors

Let us consider probabilities of non and near-resonant transitions. For near-resonant and non-resonant transitions we have $`\mathrm{\Delta }\mathrm{\Omega }`$ and the probability given by the perturbation theory is $`p(\mathrm{\Omega }/\mathrm{\Delta })^2`$. In the $`2\pi k`$ method Rabi frequency $`\mathrm{\Omega }`$ is given as $`\mathrm{\Omega }J/k`$ so the probabilities for near-resonant and non-resonant transitions are

$`p^{\text{near}}`$ $``$ $`\left({\displaystyle \frac{1}{k}}\right)^2`$
$`p_{jl}^{\text{non}}`$ $``$ $`\left({\displaystyle \frac{J}{ka(jl)}}\right)^2,`$ (12)
where $`p_{jl}^{\text{non}}`$ denotes probability of a non-resonant transition with $`\mathrm{\Delta }a|jl|`$ involving $`j`$-th and $`l`$-th spin, one of which is a resonant one. The dependence of near and non-resonant errors on system parameters is therefore different.

For pulse sequences used to generate QFT or IQFT we always used a generalized $`2\pi k`$ method by which one can get rid of all near-resonant transitions. Therefore the only errors that remain are non-resonant ones. We first checked numerically that this is indeed the case by studying dependence of errors on system parameters by which one is able to distinguish near and non-resonant errors, Eq. (12).

As one can observe from Fig. 1 the agreement with the theoretical $`p^{\text{non}}`$ (Eq. (12)) is excellent thereby confirming that the only errors left are non-resonant ones. By using generalized $`2\pi k`$ method we therefore decreased intrinsic errors by a factor of $`(a/J)^2`$ as compared to ordinary $`2\pi k`$ method where there are still some near-resonant errors present. In order to have complete understanding of fidelity decay due to intrinsic errors we have to understand scaling of these with the number of qubits. As we already discussed in section III this depends on two things: how strong the errors are correlated, giving possible scalings from $`n^p`$ to $`n^{2p}`$ and on the increase of the perturbation strength with the number of qubits. Let us first discuss the later. Under the assumption that the average transition probability (i.e. perturbation strength) for a non-resonant transition is the sum of all possible non-resonant transitions averaged over all possible resonant qubits, we can estimate

$$\delta \frac{1}{n}\underset{jl=0}{\overset{n1}{}}p_{jl}^{\text{non}}\underset{}{n\mathrm{}}\left[\frac{J}{ka}\right]^2\left(\frac{\pi ^2}{3}\alpha \frac{\mathrm{log}n}{n}\right),$$
(13)
with $`\alpha `$ some $`n`$ independent constant. We can see that the perturbation strength does not grow with $`n`$ asymptotically, but the convergence to its limit is logarithmically slow. For small $`n`$ the perturbation strength therefore will grow with $`n`$ whereas it will saturate for large $`n`$. The second contribution to the $`n`$-dependence of the fidelity comes from the dynamical correlations between errors given by the correlation function (11) of the perturbation generator for non-resonant errors. We numerically calculated this correlation function in order to understand how the correlation sum and therefore fidelity, Eq. (10), behaves as a function of $`n`$.

In Fig. 2 we show $`C(t_1,t_2)`$ averaged over all Hilbert space. One can see that there are large 2-dimensional regions of high correlations in all parts of the picture. This means there are strong correlations between errors at different pulses and therefore the correlation sum will likely grow as $`n^6`$ as the number of pulses scales as $`n^3`$ for our implementation of QFT. Similar results are obtained also for IQFT as can be inferred from Fig. 4. One interesting thing to note is that during the application of the transposition gate at the end of the protocol the correlation sum starts to decrease at some point, nicely seen in Fig. 3 and also visible in the correlation picture in Fig. 2 as there are more negative than positive areas towards the end of the algorithm. This very interesting phenomena means that applying transposition at the end is advantageous (as compared to doing it classically for instance) as it will decrease non-resonant errors. We checked that this principle can not be exploited further by repeating transposition many times and by this decreasing correlation sum even more. Still, this surprising behavior suggests that it might be possible to decrease non-resonant errors in a systematic way.

To furthermore confirm predicted $`n^6`$ growth of the correlation sum we calculated the dependence of intrinsic errors on $`n`$. This can be seen in Fig. 4, where we plot $`1F(T)`$ as a function of $`n`$ for QFT and IQFT and for two different sets of parameters, one for $`k=128`$, $`a=100`$ giving large errors and one for $`k=1024`$, $`a=1000`$. One can see that asymptotically for large $`n`$ the dependence is indeed $`n^6`$ but the convergence to this behavior is fairly slow, one needs of the order of $`n=7`$ or more qubits. This slow convergence we believe is due to the logarithmic convergence of the perturbation strength (Eq. (13)). To get exact coefficients in front of $`n^6`$ dependence we fitted dependences of errors in Fig. 4 with a polynomial in $`n`$ using at most two nonzero terms. Defining polynomials in the linear response regime as $`s^{\text{in}}=(1F)(ka/J)^2`$ one gets for QFT and IQFT

$`s_{\text{QFT}}^{\text{in}}(n)`$ $`=`$ $`280n^6660n^5`$
$`s_{\text{IQFT}}^{\text{in}}(n)`$ $`=`$ $`1300n^62100n^5.`$ (14)
Both expressions are good for $`n5`$ and superscript “in” denotes intrinsic errors. Beyond the linear response the exponential dependence is frequently justified Corr  and one has

$$F=\mathrm{exp}\left(\left[\frac{J}{ka}\right]^2s^{\text{in}}(n)\right).$$
(15)
Large coefficients of polynomials in Eqs. (14) are due to large number of pulses. The maximum possible dependence in the case of no decay of correlation function (see discussion at the end of section III) could be $`T^2`$ and therefore the leading terms in polynomials (14) expressed by the number of pulses are $`s_{\text{QFT}}^{\text{in}}0.8T_{\text{QFT}}^2`$ and $`s_{\text{IQFT}}^{\text{in}}0.5T_{\text{IQFT}}^2`$. Therefore relative to the number of pulses IQFT slightly decreases non-resonant errors but in the absolute sense QFT is better simply because it has only one third as many pulses as IQFT and the coefficient in front of $`n^6`$ (Eq. (14)) is thereby smaller. If only intrinsic errors in the generalized $`2\pi k`$ method are concerned QFT is always more stable than IQFT. Note that the intrinsic errors due to non-resonant transitions for QFT grow as $`T^2`$ ($`n^6`$) whereas in previously studied “simple” algorithms, for instance entanglement protocol DynFid , they grow only as the first power of the number of gates $`T`$. This means that QFT is much more sensitive to intrinsic errors.

### IV.2 External Errors

In order to study only external errors we set throughout this section parameters to $`k=1024`$ and $`a=1000`$, for which intrinsic errors are much smaller than external ones.

External error will be modeled by the perturbation $`V`$ (Eq. (9)) chosen to be a random hermitian matrix from a GUE ensemble. To facilitate comparison with previous results on IQFT IQFT  we will make perturbation after each quantum gate, except for the last transposition gate T, Eq. (4), after which we do not make perturbation. So for QFT we make $`n(n+1)/2`$ perturbations, while for IQFT we make $`n^2`$ perturbations. One other possible choice would be to make perturbations after each pulse. We will discuss this possibility at the end of this section. For now let us just say that qualitatively the results are the same as if doing perturbation after each gate, one just has to rescale perturbation strength like $`\delta _{\text{gate}}n\delta _{\text{pulse}}`$ as there are effectively $`𝒪(n)`$ perturbations (pulses) per gate.

The implementation of QFT on IQC is written in the interaction picture. As the static perturbation is the worst, meaning it will asymptotically in large $`n`$ limit be dominant, we will concentrate only on static perturbation, i.e. the same perturbation for all gates (pulses) $`V_j=V_k=V`$. There are still two possibilities, either making static perturbation in the interaction frame or making it static in the laboratory frame. Let us first discuss the later case. If we make static perturbation in the laboratory frame, we can of course transform it to the interaction frame by a unitary transformation $`W(t)=\mathrm{exp}(\mathrm{i}H_0t)`$ given by the time independent part $`H_0`$ of the Hamiltonian Eq. (1). This transformation

$$\mathrm{exp}(\mathrm{i}\delta V_{\text{int}}(t)):=W^{}(t)\mathrm{exp}(\mathrm{i}\delta V_{\text{lab}})W(t),$$
(16)
will result in the perturbation in the interaction frame $`V_{\text{int}}(t)`$ being time dependent. As the transformation to the laboratory frame $`W(t)`$ in the selective excitation regime involves large phases, perturbations at different gates will tend to be uncorrelated due to averaging out of widely oscillating factors in the correlation function (11). Therefore in the first approximation one can assume $`C(t_1,t_2)=\delta _{t_1,t_2}`$ and the fidelity will in this extreme case of uncorrelated errors decay as $`F(T)=\mathrm{exp}(\delta ^2T)`$ IQFT . On the other hand, if we make perturbation to be static in the interaction frame and the correlation function is not Kronecker delta in time, the fidelity will decay faster with the number of qubits (or $`T`$). To numerically confirm these arguments, we show in Fig. 5 dependence of fidelity with the number of qubits $`n`$ for the two cases discussed, static perturbation in the interaction frame and static perturbation in the laboratory frame. Polynomial fitting of $`n`$ dependence for QFT gives

$`s_{\text{lab}}^{\text{gue}}(n)`$ $`=`$ $`0.47n^2+1.41n2.42`$
$`s_{\text{int}}^{\text{gue}}(n)`$ $`=`$ $`0.45n^30.42n^2+0.58n.`$ (17)
The fidelity due to external GUE errors is given as

$$F=\mathrm{exp}(\delta ^2s^{\text{gue}}(n)),$$
(18)
with the appropriate $`s^{\text{gue}}(n)`$ from Eq. (17). Note that $`s_{\text{int}}^{\text{gue}}(n)`$ grows faster than $`s_{\text{lab}}^{\text{gue}}(n)`$ as argued. Observe also that for the static perturbation in the laboratory frame using the assumption of uncorrelated errors in the interaction frame we predicted $`s_{\text{lab}}^{\text{gue}}Tn^2/2`$ for QFT which is remarkably close to the numerically observed value Eq. (17). For IQFT and the application of GUE perturbation in the laboratory frame one gets a similar result with the leading term $`s_{\text{lab}}^{\text{gue}}(n)1.12n^2`$. One can write an arbitrary time dependent perturbation in the interaction frame as a Fourier series and for large $`n`$ the static component will always prevail. Therefore, from now on we will exclusively discuss only static perturbations in the interaction frame.

The dependence of errors due to GUE perturbation in the case of QFT and IQFT has already been derived 222Taking into account different definition of fidelity in Ref. IQFT , polynomials are almost the same with the slight difference due to the different number of applied perturbations.. For IQFT numerical fitting in our case gives dependence

$$s_{\text{IQFT}}^{\text{gue}}(n)=1.31n^2+0.86n3.73.$$
(19)
Here the perturbation is again static in the interaction frame as is the case throughout the paper with a single exception being the previous paragraph. Dependence of fidelity in both cases for QFT and IQFT can be seen in Fig. 6, together with the theory (Eq. (18)) using polynomials (19) and (17).

Observe that IQFT for $`n>n_{\text{crit}}=3`$ is better than QFT despite having more gates and therefore applying perturbation on it more times (for $`n3`$ QFT is slightly better). What is important is that the dependence of errors on $`n`$ is also different, $`n^3`$ for QFT, but only $`n^2`$ for IQFT. This means that asymptotically IQFT is much more stable against GUE perturbations than ordinary QFT.

Finally, let us discuss what happens if we make static GUE perturbations in the interaction frame after each pulse, and not after each gate as done so far. The product of two operators $`\mathrm{exp}(\mathrm{i}\delta V)U`$ can be written as $`\mathrm{exp}(\mathrm{i}\delta V)U=U\mathrm{exp}(\mathrm{i}\delta V(1))`$, with $`V(1):=U^{}VU`$. Using this expression for all errors within a single gate and bringing them all to the beginning of the gate we get

$`\mathrm{exp}(\mathrm{i}\delta V)U_r\mathrm{}\mathrm{exp}(\mathrm{i}\delta V)U_1`$
$`U_r\mathrm{}U_1\mathrm{exp}(\mathrm{i}\delta [V(1)+\mathrm{}+V(r)]),`$ (20)
where $`r`$ is number of pulses constituting a gate. This means that the application of the perturbation after each pulse is to the lowest order in $`\delta `$ equivalent to the application of the effective perturbation $`\delta _j^rV(j)`$ after the gate. Of course now the perturbation is explicitly time dependent. But for a GUE matrix acting on a whole Hilbert space individual pulses will do transformations on an exponentially small subspace (i.e. on one qubit) and therefore one might expect that effectively one can write $`\delta _j^rV(j)rV_{\text{eff}}`$, where $`V_{\text{eff}}`$ is some effective random matrix independent of the gate. As in our case of QFT on IQC we have on average $`n`$ pulses for a single gate we can predict that doing perturbation with strength $`\delta _{\text{pulse}}`$ after each pulse is approximately equal as doing perturbation of strength $`\delta _{\text{gate}}n\delta _{\text{pulse}}`$ after each gate. In order to confirm these expectations we did numerical experiments with the results shown in Fig. 7.

Fitting polynomial in the dependence of fidelity, Eq. (18), for QFT and IQFT gives in this case

$`s_{\text{QFT}}^{\text{gue}}(n)`$ $`=`$ $`4.86n^5+35.8n^4`$
$`s_{\text{IQFT}}^{\text{gue}}(n)`$ $`=`$ $`25.6n^4+606n^3.`$ (21)
The leading dependence of $`n^5`$ for QFT and $`n^4`$ for IQFT nicely agrees with our rescaling prediction $`\delta _{\text{gate}}n\delta _{\text{pulse}}`$. IQFT is asymptotically again better than QFT as the errors grow slower with the number of qubits. The crossing point between the two in this case happens at $`n_{\text{crit}}=10`$, whereas in the case of perturbation after each gate we had $`n_{\text{crit}}=3`$. This confirms that doing GUE perturbation after each pulse is qualitatively the same as doing it after each gate, only the crossing point between QFT and IQFT changes and of course also the dependence of errors on $`n`$ changes, simply due to the different number of applied perturbations. If perturbation strength $`\delta `$ is properly rescaled, the $`n`$ dependence is the same in both cases.

Up to now we discussed intrinsic errors and external errors separately. The next question is of course, what happens if both errors are present at the same time and are of similar strength?

### IV.3 Intrinsic and External Errors combined

If both kinds of errors are present, a first naive guess would be that they just add,

$$F^{\text{both}}=F^{\text{in}}F^{\text{gue}}=\mathrm{exp}\left(\left[\frac{J}{ka}\right]^2s^{\text{in}}(n)\delta ^2s^{\text{gue}}(n)\right),$$
(22)
with the appropriate polynomials $`s^{\text{in}}(n)`$ and $`s^{\text{gue}}(n)`$ given in previous Eqs. (14), (17) and (19). In the linear response regime this formula means that both errors are uncorrelated, i.e. their cross-correlations are zero. This is easy to proof using properties of GUE matrices. Let us calculate cross-correlation function between $`V^{\text{in}}(t_1)`$ and $`V^{\text{gue}}(t_2)`$ averaged over GUE ensemble. Written explicitly one has to average products of the form $`V_{ij}^{\text{in}}V_{jk}^{\text{gue}}`$, where $`V^{\text{gue}}`$ is a GUE matrix. As this expression is linear in $`V^{\text{gue}}`$ it averages to zero, $`V_{ij}^{\text{in}}V_{jk}^{\text{gue}}_{\text{gue}}=0`$, thereby explicitly confirming a simple additions of both errors. Of course in real experiments we are not averaging over GUE ensemble but are taking one definite representative member of it. But for large Hilbert space the expectation value of a typical random state and one particular GUE matrix is “self-averaging” and will be equal to the ensemble average.

Let us check the theoretical prediction for fidelity Eq. (22) with a numerical experiment. We again apply GUE perturbation after each gate. The results together with the theoretical prediction Eq. (22) are in Fig. 8. The agreement between the theory and the experiment is good also beyond the linear response regime. Please note that we deliberately choose parameters so that both QFT and IQFT give similar fidelity in order to also see the crossing of the two curves within the shown range of $`n`$. Given fixed $`\delta `$ and $`ka`$, QFT is always better for large $`n`$ because intrinsic errors will prevail over external ones, due to their fast $`n^6`$ growth. But still, for intermediate $`n`$’s IQFT can be better that QFT as seen in Fig. 8.

Now we are equipped with understanding of errors in QFT and IQFT due to external GUE perturbation and intrinsic errors so we can make some predictions regarding ranges of experimental parameters $`ka`$, $`\delta `$, $`n`$ for which the fidelity will be high enough. Interesting question for instance is, when is IQFT better than QFT? To find that, we set $`F_{\text{QFT}}=F_{\text{IQFT}}`$ with $`F`$’s given by Eq. (22). This results in the condition

$$\delta _{\text{crit}}=\frac{J}{ka}\sqrt{\frac{s_{\text{QFT}}^{\text{in}}s_{\text{IQFT}}^{\text{in}}}{s_{\text{QFT}}^{\text{gue}}s_{\text{IQFT}}^{\text{gue}}}}.$$
(23)
For $`\delta >\delta _{\text{crit}}`$ IQFT is better than QFT.

In Fig. 9 we show curves of constant fidelity for $`n=5`$. They are composed of two parts, above the line for $`\delta _{\text{crit}}`$ IQFT is better than QFT, and below vice versa. Two characteristic features are also vertical and horizontal asymptotes of the curves of constant fidelity. The vertical asymptote means that for fixed $`n`$, even if $`\delta =0`$, we must have $`ka`$ larger than some critical value determined just by intrinsic errors, in order to have given fidelity. Horizontal asymptote for high $`ka`$ means that if $`\delta `$ is larger than some critical value, increasing $`ka`$ will not help to improve fidelity.

In Figs. 10 and 11 we show similar plots, only these time one of the axes is dependence on $`n`$. For instance, from Fig. 10 on can see that having $`ka=10^5`$, the maximum number of qubits is $`n12`$ if we want to have fidelity larger than $`0.9`$ (even if $`\delta =0`$). This unfavorable growth of required $`kan^3`$ in order to have a fixed fidelity is due to $`n^6`$ growth of intrinsic errors. It would therefore be advantageous to find a way to suppress errors due to non-resonant transitions kamenev .

## V Conclusions

We analyzed two possible errors in the implementation of QFT on IQC working in the selective excitation regime. We consider: (i) intrinsic errors due to unwanted transitions caused by pulses, (ii) external errors due to coupling with the external degrees of freedom. We carefully analyze their dependence on system parameters and on the number of qubits. To diminish intrinsic errors we use the generalized $`2\pi k`$ method by which we are able to suppress all near-resonant transitions, with only much smaller non-resonant transitions remaining. We then study these non-resonant errors in QFT algorithm and by using correlation function formalism explain their growth with time as $`T^2`$, in contrast to so far studied “simple” algorithms (having $`𝒪(n)`$ gates), where the growth is linear in time. The immediate question is whether this behavior is general for algorithms having more than $`𝒪(n)`$ gates. This very fast growth with $`n`$ is a consequence of strong correlations between errors at different pulses and puts a severe demand on experimental requirements. Therefore it would certainly be desirable to find a way to suppress also non-resonant errors. We also consider perturbations due to coupling with external degrees of freedom modeled by a random GUE matrix. To suppress this kind of errors we show that it is advantageous to use an improved QFT algorithm, for which the errors grow only as $`n^2`$, whereas they grow as $`n^3`$ for ordinary QFT. By a combination of both techniques, the generalized $`2\pi k`$ method and improved QFT algorithm, we are able to make implementation of QFT stable in a much wider range of parameters.

###### Acknowledgements.

Useful discussions with T. Prosen, T. H. Seligman, G. Berman, B. Borgonovi and R. Bonifacio, are gratefully acknowledged. The work of C.P. was supported by Dirección General de Estudios de Posgrado (DGEP). C.P. is thankful to the University of Ljubljana and the Universita Cattolica at Brescia for hospitality. The work of M. Ž. has been financially supported by the Ministry of Science, Education and Sport of Slovenia.

*

## Appendix A QFT and IQFT implementation on the Ising Quantum Computer

To implement the protocol with high fidelity we use $`Q_{i\rho }^{ab}`$ pulses derived in Ref. carlos , which completely suppress all near-resonant errors. Phases of $`Q`$-pulses composing a gate must be chosen correctly so that the gate works on an arbitrary state. The protocols implementing $`\text{CN}_{ij}`$ (control not gate) and $`\text{N}_j`$ (not gate) can be found in sections 7.1-7.3 of Ref. carlos .

In order to complete QFT and IQFT we still need to implement the $`\text{R}^{}`$, R, A, B and T gates. We can decompose R, $`\text{R}^{}`$ and T gates into simpler pieces:

$`\text{R}_{ij}`$ $`=`$ $`\text{N}_i\text{CN}_{ij}\text{N}_i\text{Z}_j,`$ (24)
$`\text{R}_{ij}^{}`$ $`=`$ $`\text{N}_i\text{Z}_j\text{CN}_{ij}\text{N}_i,\text{ and}`$ (25)
T $`=`$ $`{\displaystyle \underset{i=1}{\overset{q}{}}}{\displaystyle \underset{j=1}{\overset{qi}{}}}\text{S}_{qj,qj1}`$ (26)
with $`\text{S}_{ij}=\text{CN}_{ij}\text{CN}_{ji}\text{CN}_{ij}`$ the swap gate, $`\text{Z}=\text{diag}\{1,1\}`$ the $`\sigma _z`$ gate and each term in the product in Eq. (26) is placed at the left of the sub-product (e.g. $`_{i=0}^2D_i=D_2D_1D_0`$). Therefore, the only gates left to design are A, B and Z.

The phases of $`Q`$-pulses can be expressed in terms of angles $`\theta _\rho `$, $`\alpha _\rho `$, $`\mathrm{\Theta }_\rho `$, $`\beta _\rho `$ and $`\gamma _\rho `$ carlos  which are given by

$`\theta _\rho `$ $`=`$ $`\pi \sqrt{k_\rho ^2\rho ^2/4},`$ (27)
$`\alpha _\rho `$ $`=`$ $`{\displaystyle \frac{\pi }{2}}\sqrt{k_\rho ^2+3\rho ^2/4},`$ (28)
$`\mathrm{tan}\mathrm{\Theta }_\rho `$ $`=`$ $`{\displaystyle \frac{\theta _\rho }{2\alpha _\rho }}\mathrm{tan}\alpha _\rho ,`$ (29)
$`\mathrm{tan}\beta _\rho `$ $`=`$ $`{\displaystyle \frac{\pi }{2\alpha _\rho }}\mathrm{tan}\alpha _\rho \mathrm{cos}\mathrm{\Theta }_\rho ,`$ (30)
$`\gamma _\rho `$ $`=`$ $`\sqrt{(\pi k_\rho )^2(\pi +\beta _\rho )^2}.`$ (31)
We use notation of angles without subscripts denoting angles for $`\pi `$ pulses i.e. $`\theta \theta _1`$ and set $`k_{1/2}=2k`$.

The Hadamard gate can now be expressed as

$`\text{A}_j`$ $`=`$ $`Q_j^{00}(\phi _1)Q_j^{10}(\phi _2)Q_j^{11}(\phi _3)Q_{j\frac{1}{2}}^{00}(\phi _4)`$ (32)
$`Q_{j\frac{1}{2}}^{10}(\phi _5)Q_{j\frac{1}{2}}^{11}(\pi /2),`$
for intermediate qubits and

$$\text{A}_j=Q_j^0(\phi _6)Q_j^1(\phi _7)Q_{j\frac{1}{2}}^0(\phi _8)Q_{j\frac{1}{2}}^1(\pi /2),$$
(33)
for edge qubits, with

$$\begin{array}{cccccc}\hfill \phi _1& =& 2\left(\theta +\gamma _{\frac{1}{2}}+\theta _{\frac{1}{2}}\right),\hfill & \hfill \phi _2& =& \theta 2\mathrm{\Theta },\hfill \\ \hfill \phi _3& =& 2\left(\theta +\gamma \gamma _{\frac{1}{2}}\theta _{\frac{1}{2}}\right),\hfill & \hfill \phi _4& =& \pi /22\gamma 4\theta _{\frac{1}{2}},\hfill \\ \hfill \phi _5& =& \pi /2\theta _{\frac{1}{2}}2\mathrm{\Theta }_{\frac{1}{2}},\hfill & \hfill \phi _6& =& \theta \theta _{\frac{1}{2}},\hfill \\ \hfill \phi _7& =& \theta +\theta _{\frac{1}{2}},\hfill & \hfill \phi _8& =& \pi /22\theta _{\frac{1}{2}}.\hfill \end{array}$$
(34)
For neighboring qubits ($`|ij|=1`$) the B gate can be written as,

$`\text{B}_{ij}`$ $`=`$ $`Q_i^{11}(0)Q_i^{10}(0)Q_i^{00}(0)Q_j^{10}(0)Q_j^{10}(\phi _1)Q_j^{00}(0)`$ (35)
$`Q_j^{00}(\phi _2)Q_i^{11}(\phi _3)Q_i^{10}(\phi _3)Q_i^{00}(\phi _3)Q_j^{10}(0)`$
$`Q_j^{10}(\phi _4)Q_j^{11}(0)Q_j^{11}(\phi _5),`$
for intermediate qubits and for edge qubits ($`i`$ or $`j\{0,n1\}`$) it is

$`\text{B}_{ij}`$ $`=`$ $`Q_i^1(0)Q_i^0(0)Q_j^{10}(0)Q_j^{10}(0)Q_j^{00}(0)`$ (36)
$`Q_j^{00}(\phi _6)Q_i^1(\phi _7)Q_i^0(\phi _8)Q_j^{10}(0)`$
$`Q_j^{10}(\phi _9)Q_j^{11}(0)Q_j^{11}(\phi _{10}).`$
Angles for B gates are

$$\begin{array}{cccccc}\hfill \phi _1& =& 2\gamma 3\theta +2\mathrm{\Theta },\hfill & \hfill \phi _2& =& \varphi /22\gamma 6\theta ,\hfill \\ \hfill \phi _3& =& \varphi /4\pi /2,\hfill & \hfill \phi _4& =& \phi _1,\hfill \\ \hfill \phi _5& =& \varphi /2+2\gamma +6\theta ,\hfill & \hfill \phi _6& =& \varphi /26\gamma 12\theta +4\mathrm{\Theta },\hfill \\ \hfill \phi _7& =& \phi _3\phi _1,\hfill & \hfill \phi _8& =& \phi _3+\phi _1,\hfill \\ \hfill \phi _9& =& 2\phi _1,\hfill & \hfill \phi _{10}& =& \varphi /22\gamma +4\mathrm{\Theta },\hfill \end{array}$$
(37)
and $`\varphi =\pi /2`$. For distant qubits ($`|ij|>1`$) it is necessary to use swap gates to bring $`i`$-th and $`j`$-th qubits to neighboring positions, then apply B protocol for neighbor qubits and finally take them back to their original positions using swap gates. The angle $`\varphi `$ in Eq. (37) is in this case $`\varphi =\pi /2^{|ji|}`$. Finally the Z gate is expressed as

$$\text{Z}_j=Q_j^{11}(0)Q_j^{10}(0)Q_j^{00}(0)Q_j^{11}(\pi /2)Q_j^{10}(\pi /2)Q_j^{00}(\pi /2)$$
(38)
for intermediate qubits and

$$\text{Z}_j=Q_j^1(0)Q_j^0(0)Q_j^1(\pi /2)Q_j^0(\pi /2)$$
(39)
for edge qubits. Counting the number of all pulses for QFT and IQFT one gets

$`T_{\text{QFT}}`$ $`=`$ $`18n^316n^249n+57`$ (40)
$`T_{\text{IQFT}}`$ $`=`$ $`54n^386n^2105n+191.`$ (41)


text:
# A cluster mode–coupling approach to weak gelation in attractive colloids

## Abstract

Mode–coupling theory (MCT) predicts arrest of colloids in terms of their volume fraction, and the range and depth of the interparticle attraction. We discuss how effective values of these parameters evolve under cluster aggregation. We argue that weak gelation in colloids can be idealized as a two–stage ergodicity breaking: first at short scales (approximated by the bare MCT) and then at larger scales (governed by MCT applied to clusters). The competition between arrest and phase separation is considered in relation to recent experiments. We predict a long–lived ‘semi–ergodic’ phase of mobile clusters, showing logarithmic relaxation close to the gel line.

Hard–sphere colloids with short–range attractions can undergo several types of arrest. At high densities they show two distinct glass transitions (repulsion–driven and attraction–driven), with a re–entrant dependence on attraction strength Pham et al. (2002). This scenario was first predicted by mode coupling theory (MCT) Bergenholtz and Fuchs (1999); Fabbian et al. (1999); Dawson et al. (2001), and depends on both the attraction range $`\delta `$ (in units of particle diameter) and well–depth $`\epsilon `$ (in units of $`k_BT`$). MCT is remarkably successful, at least for large volume fractions $`\varphi 0.4`$.

At lower volume fractions, however, there is no comparable theoretical framework. Yet ‘weak gelation’, in which bonding is strong but not so strong as to be irreversible, can lead to nonergodic soft solids, of nonzero static elastic modulus, at volume fractions of just a few percent Poon and Haw (1997). It might be argued that a finite modulus requires a percolating network of bonds whose lifetime exceeds that of the experiment. However this is simplistic: as shown by the case of repulsive glasses, a finite modulus can arise with no bonding at all. We argue here that the rigidity of weak gels arises not from bond percolation but from kinetic ergodicity breaking Bergenholtz et al. (2000), just as it does in glass formation. This suggests that an MCT–like approach to weak gelation could be fruitful.

MCT takes its structural input from equilibrium liquid state theory; it cannot address states of arrest where this structure is strongly perturbed foot1 . This matters relatively little at $`\varphi 0.4`$, where each particle interacts with many others, and not much room is left for structural development upon a quench. But more severe consequences must be expected at low volume fractions where strongly nonuniform, ramified gels arise. Here the pathway to complete nonergodicity (starting from a homogenized fluid sample, say) must involve a nontrivial episode of structure formation, akin to irreversible cluster aggregation (ICA). Such kinetics certainly dominates for irreversible (“strong”) gelation ($`\epsilon ^1=0`$), where particles aggregate on contact into clusters, with various kinetic universality classes Vicsek (1992). Relative simplicity is restored at low $`\varphi `$ thanks to the invariance of this aggregation process under coarse graining in the (ordered) limit $`\delta `$, $`\epsilon ^10`$ and $`\varphi 0`$. This scaling limit is controlled by an ICA ‘fixed point’, where details of the short–ranged attraction are irrelevant. The resulting fractal clusters grow indefinitely only if $`\varphi =0`$; for $`\varphi >0`$ they eventually form a percolating gel of locally ICA–like structure Hasmy and Jullien (1996).

In this Letter, we explore how ICA might connect to weak gelation through a unified (albeit speculative) MCT–based scenario of colloidal arrest. We consider the changes in the system parameters ($`\varphi ,\delta ,\epsilon ^1`$) upon coarse graining in the vicinity of the ICA fixed point. This leads to a schematic description of the suspension in terms of an effective theory for a dense liquid of ‘renormalized particles’ or coarse–grained clusters, for which recent simulations Del Gado et al. (2003) seem to provide some direct evidence. Applying MCT to this theory, we obtain a new condition for arrest of the clusters, and identify the arrested state with the weak gel phase. If this condition is not met, one has instead a fluid of clusters (or ‘cluster phase’ Segrè et al. (2001)) that is ergodic at large scales. We allow for bond–breaking and reconnection at the scale of entire clusters, but not reconstruction at shorter scales. We return to this later, where we also address the potentially complex interplay between weak gelation and phase separation.

Within our scenario, weak colloidal gelation emerges as a double ergodicity breaking: once when the original suspension becomes kinetically unstable against aggregation, and a second time when the fluid of clusters arrests. We suppose that the criterion for the initial instability is given by bare MCT Bergenholtz et al. (2000). We assume $`1\epsilon <\mathrm{}`$: bonds can break with a small but finite probability. Initially this has almost no effect on the aggregation, which flows towards the ICA fixed point. But as clusters grow, the chances of fragmentation increase. The ICA fixed point is unstable and the sytem eventually flows away from it. The flow takes place in a parameter space comprising effective system variables $`(\stackrel{~}{\varphi },\stackrel{~}{\delta },\stackrel{~}{\epsilon }^1)`$ (Fig. 1).

These coarse–grained parameters describe the density and interaction of aggregated clusters. We write:

$`\stackrel{~}{\varphi }`$ $`=\varphi N^{3/d_c1}`$ (1)
$`\stackrel{~}{\delta }`$ $`=\delta N^\nu `$ (2)
$`\stackrel{~}{\epsilon }`$ $`=\epsilon \chi \mathrm{ln}Nf(N)`$ (3)
and call the combination of MCT with Eqs.(13) ‘cluster mode–coupling theory’ (CMCT). $`N`$ is the number of particles in a typical cluster, which is a parametric label along flow trajectories, each of which is indexed by values of $`(\varphi ,\delta ,\epsilon ^1)`$ in the initial state after the quench. In Eqs.(1,2), evolution of the effective volume fraction of clusters (viewed as quasi–spherical, smooth objects) involves a scaling index $`d_c`$, and that of the effective relative range $`\delta `$ of their attraction another positive exponent $`\nu `$.

More subtle is the evolution of the bond energy $`\epsilon `$ in Eq.(3). Since the ICA fixed point leads only to singly–connected bonding, there is no power of $`N`$ multiplying the short–range attractive part of the bond energy. However, Eq.(3) accounts for bond breaking through a renormalization of the cluster–cluster attraction $`\epsilon `$ by a breaking entropy, which we write as the logarithm of a breaking degeneracy $`N^\chi N`$. This acknowledges that a ramified cluster falls apart when any of the $`N^\chi `$ bonds along its backbone is broken (with probability $`e^\epsilon `$). Eq.(3) also includes a term $`f(N)`$ arising from additional interactions. For purely short range attractions this term should vanish, but it allows us to address also the case of a weak long range repulsion, such as has recently been shown to arise from poorly screened dissociated surface charges even for supposedly neutral colloids in organic solvents Yethiraj and van Blaaderen (2003). Depending on the strength and range of the repulsion, the resulting $`f(N)`$ may dominate the logarithmic term in Eq.(3) without having much effect on the equilibrium phase diagram barrier .

Initially, all three exponents introduced in the CMCT equations are properties of the ICA fixed point (typically $`d_c2`$, $`\nu \chi 1/d_c`$, in three dimensions Vicsek (1992)). However, they will start evolving once the flow moves away from it, as the internal structure of clusters evolves. An explicit treatment of this drift is not attempted here: we treat $`d_c,\nu ,\chi `$ as negotiable constants.

The resulting CMCT flow within the renormalized parameter space $`(\stackrel{~}{\varphi },\stackrel{~}{\delta },\stackrel{~}{\epsilon }^1)`$ is sketched in Fig. 1. The flow is bounded by the MCT transition surface in this space, which divides ergodic (upper left) from nonergodic regions. This surface Bergenholtz and Fuchs (1999); Fabbian et al. (1999); Dawson et al. (2001) comprises a dome joined to a sheet. Below the dome lie attractive glasses and to the right of the sheet, repulsive ones. Note the presence of a seam $`\stackrel{~}{\varphi }_c`$, on the transition surface, along the line where the sheet meets the dome. Consider a trajectory of increasing $`N`$ which rises up through the dome, left of the seam ($`\stackrel{~}{\varphi }<\stackrel{~}{\varphi }_c`$). At this point, aggregation ceases, because the clusters’ effective parameter values now correspond to an ergodic phase. A semi–ergodic fluid of finite clusters can be expected whenever the initial parameter values belong to such a trajectory. (This requires small $`\delta `$.) If a series of such cluster fluids is now created by increasing $`\varphi `$ at fixed $`\epsilon `$ (or vice versa), then the last of these to enter an ergodic phase will do so just beside the seam ($`\stackrel{~}{\varphi }\stackrel{~}{\varphi }_c^{}`$). Accordingly the first fully nonergodic phase formed has a trajectory that just meets this seam; beyond lies a repulsive glass, so that aggregation ceases. Unlike the cluster fluid, the resulting marginal gel has finite modulus — as do the non–marginal gels arising at larger $`\varphi `$ or $`\epsilon `$. This not because of percolation, which for reversible bonding is not relevant, but because the CMCT flow has led to a “cluster glass” which we identify with the weak gel phase. A typical phase diagram predicted by this approach is shown in Fig. 2.

Note that for moderate $`\stackrel{~}{\delta }`$, the seam is not too far from the line of $`A_3`$ singularities, which is associated with a distinctive arrest scenario including a large exponent for the divergence of the structural relaxation time, and strongly stretched exponential or even logarithmic decay of the density correlations Dawson et al. (2001); Götze and Sperl (2002); Sciortino et al. . Marginal gels could thus be influenced by these singularities even at low volume fractions, although the details of this depend on the initial range $`\delta `$ and on the exponent $`\nu `$.

CMCT clearly offers nontrivial predictions for cluster phases, weak gels and relaxation anomalies. But it neglects two important pieces of physics which may complicate the experimental situation considerably. Firstly, we allowed clusters to dissociate by bond breaking, but neglected any internal restructuring within the clusters. By allowing these to coarsen into globules, this could cause both the cluster fluid and weak gel phases to have finite lifetime. Moreover, for $`f(N)=0`$ the breaking and rebonding of the $`𝒪(N)`$ dangling ends within a cluster may cause local restructuring even before the flow reaches the MCT surface. This issue is less important in the presence of a weak, long–range repulsion $`f(N)>0`$ (e.g. Yethiraj and van Blaaderen (2003)), which, like bond–breaking, drives an upward flow in Fig. 1. In favorable cases this could dominate the bond–breaking term at large $`\epsilon `$, and allow the CMCT scenario to establish on a timescale during which local reconstruction remains negligible.

The second, closely related, omission from the CMCT predictions of Fig. 2 is the interplay of cluster formation with liquid–gas type phase separation Miller and Frenkel (2003). To be confident of observing the CMCT line directly at small $`\varphi `$, it must lie outside the binodal. When that condition is not satisfied, we expect results that depend on quench rates. For a very slow quench, the system first demixes locally and then coarsens, until the denser coexisting phase, whose properties continue to evolve, arrests by a CMCT–like mechanism (merging with bare MCT at high enough density). Slow quenches have recently been examined experimentally, and these ideas may account for a surprising “bead phase” seen at low $`\varphi `$ Sedgwick et al. .

For faster quench rates, local arrest can precede coarsening so that at small $`\varphi `$, large fractal clusters will at first evolve, regardless of the underlying phase behavior. The resulting scenario is explored, within an indicative model, in Fig. 3. We follow Keller Frank, Keller (1988) in arguing that the densest phase capable of formation by demixing arises where the glass line intersects the binodal (point B). The nonergodicity line should depart from the CMCT prediction at this point, and track to lower densities along the tie line BA. This describes a locally demixed state in which only the denser (gel–like) B–component is nonergodic. At high $`\varphi `$ the B–phase percolates giving a finite modulus gel; but at lower $`\varphi `$ one expects a cluster fluid, now made of disconnected gel–like fragments. The ‘gel line’, separating states of finite modulus from those without, corresponds to the geometric percolation threshold of the arrested phase. Deeper quenches should behave similarly, with local coexistence between a dilute fluid C and an arrested state D whose density lies on the CMCT line. This is governed by a modified common tangent Frank, Keller (1988) in which inaccessible densities (beyond point D) are prohibited (Fig. 3, inset) shifting the binodals inward. Along the tieline CD, the gel line again corresponds to percolation of the arrested phase. At still deeper quenches the CMCT line lies within a (renormalized) spinodal curve; this local instability complicates matters further, and is ignored in the indicative model of Fig. 3. But a transition from percolating gel to a cluster phase of gel fragments should remain. Finally, at infinite $`\epsilon `$ the CMCT line, the gel line, the equilibrium spinodal, and the binodal all meet the ICA fixed point at the origin. Notably, this scenario allows the ‘marginal gel’ behavior to extend inside the gel phase: indeed a range of compositions, including the AB tieline and a region below it, now have local phase separation involving a marginal gel (Fig. 3).

We now confront the implications of our work with experimental data. The most direct consequence of our hypothesis of a double ergodicity breaking, a fractal gel structure, is a very common observation. It has inspired successful phenomenological gel models, e.g. Shih et al. (1990); Krall and Weitz (1998); Trappe and Weitz (2000), for which CMCT could provide a more rational (albeit still speculative) basis. Experiments Dinsmore and Weitz (2002) demonstrate that even for moderate attractions the assumed closeness to the ICA limit is well justified at low volume fractions in some cases, while in others the measured fractal dimension lies higher than for the appropriate ICA model Rojas et al. (2003). The latter could well be a consequence of a partial phase separation followed by arrest, as discussed above.

Secondly, CMCT predicts dynamic anomalies along and near much of the gel line (including the part that lies along AB tieline of Fig. 3). In this context, the observation in Ref.Segrè et al. (2001) of a large exponent ($`5.5\pm 1`$ at $`\varphi 0.1`$) for the divergence of the terminal time, and of slow, possibly logarithmic, structural relaxation close to the gel line at low $`\varphi `$ are both suggestive of CMCT.

A final comparison involves the nonequilibrium phase diagram, where a striking feature at low concentrations (e.g. Poon et al. (1999); Trappe and Weitz (2000); Segrè et al. (2001)) is indeed the existence of a phase of large mobile aggregates, lying between the ordinary fluid phase and the gel. In fact, the phase diagrams in Fig. 5 of Ref.Segrè et al. (2001) and Fig. 2 of Ref.Verduin and Dhont (1995) are very similar to our Figs. 23, respectively. As mentioned above, an interplay of CMCT with phase separation is expected for most colloidal parameters, including those of Ref.Segrè et al. (2001). Fig. 2 therefore shows also the phase boundaries adjusted to allow for phase separation according to the indicative model of Fig. 3. In this representation the cluster/gel boundary remains nearly straight, although shifted downward somewhat. The results remain qualitatively consistent with Ref.Segrè et al. (2001); given the indicative character of the model, this is encouraging. Since the system is among those for which a long range Coulomb repulsion might be present Yethiraj and van Blaaderen (2003), it is possible that $`f(N)>0`$. Qualitatively, this would move the calculated gel line upward, stabilizing the cluster phase.

In summary, we have proposed a new framework to describe weak gelation based on mode–coupling theory applied to clusters (CMCT). This certainly contains speculative elements but gives nontrivial predictions, several of which compare well to existing experimental data. Underlying our picture of a double ergodicity breaking is the premise of a time scale separation. Our “cluster glass” view of weak gels is a meaningful concept on time scales longer than the time for cluster formation, but short compared to typical times over which a cluster reconstructs as it evolves towards equilibrium. This condition is more easily satisfied in systems where a repulsion between clusters builds up as they grow (e.g. weakly charged particles), limiting their final size. When the size is limited by bond–breaking, the required time scale separation is less likely. But even if the resulting weak gels are not true examples of broken ergodicity and are only temporary structures, CMCT may offer valuable insights into their behavior. Further experimentally relevant consequences of the scheme will be the subject of future work.

We thank Mark Haw, Daan Frenkel, Matthias Fuchs, Helen Sedgwick, Matthias Sperl and Dave Weitz for valuable discussions, and the EC for financial support.


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# Mie-resonances, infrared emission and band gap of InN

## Abstract

Mie resonances due to scattering/absorption of light in InN containing clusters of metallic In may have been erroneously interpreted as the infrared band gap absorption in tens of papers. Here we show by direct thermally detected optical absorption measurements that the true band gap of InN is markedly wider than currently accepted 0.7 eV. Micro-cathodoluminescence studies complemented by imaging of metallic In have shown that bright infrared emission at 0.7-0.8 eV arises from In aggregates, and is likely associated with surface states at the metal/InN interfaces.

preprint: APS/123-QED

InN is one of the most mysterious semiconductor materials studied up to now. While it has been carefully investigated since the 1980s using all the modern spectroscopic techniques, the band parameters of InN (gap energy, effective masses) are still under debate. This uncertainty is particularly embarrassing since InN-containing heterostructures have a huge potentiality for lasers, white-light diodes, and other devices.

In this Letter we show that dramatic deviations in presently available experimental data on the band gap of InN from 0.7 to 2 eV 1 (1)-5 (5) have a fundamental physical reason. They are linked to the precipitation of indium in the metallic phase that leads to additional optical losses associated with Mie resonances.

Resonant light scattering and absorption by dispersed small particles, described by Mie almost 100 years ago 6 (6), have been thoroughly investigated in different objects in nature - cosmic dust, comets, atmosphere clouds $`\mathrm{𝑒𝑡𝑐}.`$ (see, e.g., Ref. 7 (7)). They have also been repeatedly observed in various dielectrics and semiconductors with clusters of different metals 8 (8),9 (9). These phenomena arise from interaction of an incident electromagnetic wave with multipolar excitations of electrons in the clusters. Radiative processes associated with metallic inclusions have been continuously reported as well 10 (10).

Such effects have been neglected in studies of InN, although it is well known that the poor thermal stability of InN and low In vapor pressure over the metal phase result in formation of In clusters at temperatures higher than 500C, commonly used to obtain high quality InN 5 (5). A good correlation between the recently registered infrared (IR) photoluminescence (PL) and the optical absorption edge has been considered as a doubtless evidence of the narrow gap 3 (3)-5 (5). An attempt has been made to verify the failure of the band gap-common-cation rule 11 (11), accordingly to which $`E_g`$ of InN has to be wider than that of InP (1.42 eV).

We have examined two representative sets of InN epilayers grown by both plasma-assisted molecular beam epitaxy (MBE) and metalorganic chemical vapor deposition (MOCVD) on sapphire and other substrates. The maximum of the IR emission in these samples has been registered in the 0.7-0.8 eV range independently of the growth technique and the way of excitation, i.e., optically, by different laser lines, or by an electron beam in the cathodoluminescence (CL) study (Fig. 1). The latter has been performed in a LEO 1550 Gemini analytical scanning electron microscope (SEM) equipped with a liquid-helium high-resolution CL system.

The electron concentration in the samples, as determined by IR ellipsometry measurements, varies from 2.1 up to 8.4$`\times `$1019 cm-3, assuming an effective electron mass of $`m_e^{}`$ = 0.11$`m_0`$ 12 (12). No noticeable correlation between the IR emission energy and the carrier concentration was observed. A shift of the PL with a temperature rise is very small (Fig. 1 (b)), similar to previous reports 13 (13).

The samples under study may be divided into three groups with (A) bright, (B) weak and (C) negligible IR emission (Fig. 2 (a-c)). Among ten MBE layers only one, grown with exceeding of 500C, belongs to group A. The most of the samples either does not emit light at all or show a very weak signal, in spite of reasonable structural quality. A similar picture has been observed in the MOCVD set, where two samples of eight, possessing bright IR emission, were grown directly on sapphire in the 500-550C temperature range.

All the samples exhibiting the IR PL contain inclusions of a tetragonal In phase in hexagonal InN, as revealed by x-ray diffraction (XRD) measurements, performed using a sensitive triple-crystal diffractometer. As can be seen in Fig. 2, the PL correlates with the (101) In peak; both are most intense in sample A and disappears completely in the MBE samples C. Note that the In precipitates have been directly observed in a transmission electron microscopy (TEM) image as well (Fig. 1, the inset).

We have studied whether there is any spatial correlation between the IR emission and the distribution of metallic In. This has been done in the same analytical microscope using a detector of backscattered electrons (BSE), sensitive to atomic weight, and an energy dispersive x-ray (EDX) analyzer. Figure 3 (a-d) summarizes results of the studies for the MBE sample A. It turns out that the IR CL arises within the In-enriched regions, visible as bright areas in both BSE image and mapping of In x-ray fluorescence. The IR emission is dotty, while emission from sapphire (not presented here), penetrating between the In-enriched regions at $``$8 kV, is homogeneous. Moreover, the spots of the IR emission coincide most frequently with specific defects, well resolved in the secondary electron (SE2) images. Such defects are, in fact, dips in the InN films above the contacts with the metal particles. The locally increased growth temperature induces dissociation of InN there and, hence, a reduction of the growth rate.

In samples B, with the smaller In content, the distribution of IR emitting spots in the CL images is more homogeneous. Their density and average size ($``$100 nm) are smaller than in the sample A. These spots appear on the In agglomerations which have almost circular shapes in the BSE images. In the samples C, we failed to register the IR emission at all. The BSE images of such layers do not exhibit any noticeable amount of the metallic In either, and accordingly the dips are absent in the respective SE2 images (Fig. 3 (e, f)).

In the MOCVD samples, the metallic In tends to agglomerate at the boundaries of hexagonal grains, as can be seen in both SE2 and BSE images (Fig. 4 (a, b)). Accordingly, the IR CL looks like a fine net along the grain boundaries (Fig. 4 (c, d)). With an increase of the electron beam energy, the net becomes brighter, but no noticeable emission appears inside the hexagons. The MOCVD samples demonstrate a similar disappearance of the IR PL in films without metallic In. Obviously, the bright IR (0.7-0.8 eV) emission in both sets of the InN samples is associated with the In aggregates.

Total optical extinction losses in a semiconductor matrix with metallic clusters, besides the interband absorption in the matrix, contain two additional components: i) true (bipolar) absorption or transformation of radiation energy into heat in small particles, and ii) resonant scattering on plasmon excitations, which is important for larger particles 8 (8). Characteristic features of both components are observed in our optical spectra.

The PL spectra often contain an additional ”S” band above the main one, in the 0.8-1.4 eV range (Fig. 1 (a)). Our study has shown that this is the contribution of an abnormally strong scattered background signal (non-monochromatic spontaneous emission of the semiconductor laser and/or fluorescence of all optical components at high excitation power). Apparently, the scattered signal is absent in the CL spectra due to the electron beam excitation without such a background. At the normal incidence, the signal may be so strong that it masks the real IR emission. This scattering can falsify the results of conventional optical absorption measurements as well, since less optical energy reaches the detector.

To distinguish between such optical losses and true absorption we have used the thermally detected optical absorption (TDOA) technique. This method, performed at 0.35 K, is based on the detection of a small increase in the sample temperature, which is proportional to true absorption 14 (14). In our case, the increase arises from the creation of phonons at nonradiative recombination activated by the initial interband optical absorption and from the bipolar absorption of light in the metallic particles.

The difference between the TDOA and the conventional absorption is illustrated by spectra in Fig. 2 (b). The optical absorption extends to lower energies and completely saturates at higher energies. In contrast, the TDOA features a complicated spectrum with a pronounced additional peak below a principal absorption edge. This peak shifts to the higher energy in the spectra of the samples B and disappears totally in the samples C, where In clusters are not detected. Therefore, we consider the peak to be associated with the absorption within the In particles.

In the classical Mie theory, the extinction losses of a metallic sphere embedded in a matrix are expressed through an imaginary part of its polarizability. This quantity depends on the complex dielectric functions of both matrix material ($`ϵ`$) and metal ($`ϵ_m`$). As shown by qualitative EDX analysis, there is excess of In of a few percents in our samples. Such a filling factor $`f`$ should significantly change the complex dielectric function of any semiconductor. Besides, the shape of In inclusions is far from spherical. To estimate the resonant absorption energies, we have used the model, based on the Maxwell-Garnett approximation for an effective medium, developed for non-spherical metal particles 15 (15),9 (9). In this model, the absorption is given as

$$\alpha \mathrm{Im}[ϵ(w)G(w)],$$

where

$$G(w)=(1+f\frac{(ϵ_mϵ)(1L_m)}{L_mϵ_m+(1L_m)ϵ})/(1f\frac{(ϵ_mϵ)L_m}{L_mϵ_m+(1L_m)ϵ}).$$

Here $`L_m`$ denotes the depolarization factor, which equals $`1/3`$ for spheres. The dielectric function for In is approximated by the Drude model. We take the material parameters of In from Refs. 16 (16), 17 (17), and the complex dielectric function of InN from Ref. 18 (18).

Figure 5 demonstrates that this model enables one to describe the TDOA data on absorption in InN. Reasonable agreement between the experimental peak and the calculated Mie resonance for the MBE sample A is obtained with $`f=2\%`$ and $`L_m=0.066`$ (Fig. 5 (a)). The blue shift with the decrease of the In content from 4 to 0.5$`\%`$ is 0.4 eV. Deviation from the spherical shape provides an even more crucial effect, as can be seen in Fig. 5 (b), where only the normalized Mie resonances are presented for the sake of demonstrativeness (interband transitions cause the damping of the resonances above 2 eV).

One should clarify that the band gap energy in a TDOA spectrum corresponds to the position of the kink between the constant and slope parts of the spectrum. The kink position in the spectra of InN samples, having no detectable metallic inclusions, is near 1.4-1.5 eV. Therefore, it is tempting to conclude that the true band edge of InN is in this range, with possible correction on the Burstein shift 19 (19). However, it is difficult to separate the interband absorption in InN from the Mie absorption in ultra small In nanoclusters. Thorough high-resolution TEM studies are needed to determine finally this fundamental characteristic.

The IR emission is situated significantly below the principal edge in TDOA spectra and below the Mie resonances. It arises on an interface of InN with a large enough In particle ($`>`$100 nm). Among the possible mechanisms, recombination involving surface states at an interface metal/semiconductor seems to us the most reasonable. Optical emission in several III-V compounds with thin metal coverage had been observed $``$0.7 eV below the respective band edge 20 (20). In perfect crystals, like the InN hexagons, the Tamm surface states can appear due to the change in the periodic crystal potential at an interface 21 (21). The potential change is essential, if a metal inclusion is ”bulk-like”, i.e., with a size much larger than the exciton Bohr radius. The energy of such states, governed by the Schottky-barrier height and the Fermi level stabilized by the metal inclusions, is weakly sensitive to the band energy variation with temperature, in agreement with our observation.

In conclusion, the presence of In precipitates could explain a lot of experimental data: the huge band edge shift, variation of the sample coloration from red to metallic, and the IR emission and scattering. The Mie resonances are important for InGaN epilayers as well, because of the observed activation of In segregation phenomena in the alloys at high growth temperatures. We resume that InN of high optical quality, grown at $`T>500^{}`$C, absorbs and emits light far below its bandgap due to Mie resonances and Tamm states, respectively.

We thank for help in structural characterization Dr. V. V. Ratnikov, V. M. Busov, and A.A. Sitnikova. This work was partly supported by RFBR (grants 03-02-17563 and 03-02-17567) and the cooperative Grant between Russia and France N04509PB. A. Kasic acknowledges support from The Wenner-Gren Foundation, Sweden.