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# The 2-local Hamiltonian problem encompasses NP

## 1 Introduction

The field of complexity theory has long been studied in terms of classical physics. One of the most important complexity categories is the NP complexity class \[GJ79\]. With the beginning of quantum computing there emerged quantum extensions of these complexity categories. For instance, Kitaev introduced the quantum complexity class BQNP as the quantum analog of NP, and showed that the $`5`$-local Hamiltonian problem is BQNP complete \[KSV02, AN02\]. It is not known whether the $`s`$-local Hamiltonian problem is BQNP-complete for $`s=2,3,4`$.

In this paper we study the complexity of the $`2`$-local Hamiltonian problem in classical terms. We prove that NP problems are polynomially reducible to the $`2`$-local Hamiltonian problem. This reduction is shown by formulating the NP-complete problems MAX CUT and INDEPENDENT SET as a $`2`$-local Hamiltonian problem.

The ideas of our proof are motived by results of statistical physics on the complexity of computing the energy of ground states of spin glasses. It is known that the problem of computing the energy of ground states of (1) spin glasses with no exterior magnetic field and of (2) planar spin glasses within a magnetic field are NP-complete. These results are established by showing that the problem of finding the energy of ground states is equivalent to solving the NP-complete problem MAX CUT in (1) and INDEPENDENT SET in (2) \[Bar82\].

## 2 Local Hamiltonian problem

We repeat the necessary definitions concerning the local Hamiltonian problem. For the general context we refer the reader to \[KSV02, AN02\].

Let $`:=^2`$ denote the Hilbert space of a single qubit and $`^n`$ the joint Hilbert space of $`n`$ qubits. $`𝐋(^s)`$ denotes the set of linear operators from $`^s`$ to $`^s`$. Let $`A𝐋(^s)`$ be an arbitrary operator and $`S\{1,\mathrm{},n\}`$ with $`|S|=s`$. We denote by $`A[S]𝐋(^n)`$ the embedding of the operator $`A`$ into the Hilbert space $`^n`$, i.e., the operator that acts as $`A`$ on the qubits specified by $`S`$.

###### Definition 1 (Local Hamiltonian)

An operator $`H:^n^n`$ is called an $`s`$-local Hamiltonian if it is expressible in the form

$$H=\underset{j}{}H_j[S_j],$$
(1)
where each term $`H_j𝐋(^{|S_j|})`$ is a positive semidefinite operator of bounded norm $`H_j1`$ acting on a set $`S_j`$, $`|S_j|s`$.

###### Definition 2 (The local Hamiltonian problem)

Let $`H`$ be an $`s`$-local Hamiltonian and $`a,b`$ be nonnegative real numbers, where $`s`$ is a constant and $`ba>n^\alpha `$ ($`\alpha >0`$ is a constant). The $`s`$-local Hamiltonian problem is to determine if either

1. $`H`$ has an eigenvalue not exceeding $`a`$, or
2. all eigenvalues of $`H`$ are greater than $`b`$.

The defined problem is a promise problem: we know that one of the two situations occurs.

## 3 Max cut

We show that the MAX CUT problem may be formulated as the $`2`$-local Hamiltonian problem defined by Kitaev.

The MAX CUT problem is defined as follows \[Kar72, GJ79\]:

* INSTANCE: Weighted graph $`G=(V,E)`$, weight $`w(e)`$ for each $`eE`$, positive integer $`w`$.
* QUESTION: Is there a partition or cut $`C=(V_0,V_1)`$ of $`V`$ into disjoint $`V_0`$ and $`V_1`$ such that the sum of the weights of the edges that have one end point in $`V_0`$ and one endpoint in $`V_1`$ is at least $`w`$?

This problem remains NP-complete if $`w(e)=1`$ for all $`eE`$ (the SIMPLE MAX CUT problem) \[GJS76\].

In the following we consider the SIMPLE MAX CUT problem. Let $`G=(V,E)`$ a graph. To have a unique representation we denote edges as ordered pairs $`(k,l)`$ with $`k<l`$. Following the idea of \[Bar82\] we associate a binary variable $`X_k\{0,1\}`$ to each vertex $`kV`$. For an assignment $`X_1,\mathrm{},X_n`$ let us define $`V_0:=\{kX_k=0\}`$, and $`V_1:=\{kX_k=1\}`$. This defines the cut $`C=(V_0,V_1)`$ of $`G`$. Let us also define $`E_{00}`$, and $`E_{11}`$ as the set of edges with both end points in $`V_0`$ and $`V_1`$, respectively. The cut refers to the set of edges that cross between “zero” vertices, i.e. $`kV_0`$, to the “one” vertices, i.e. $`kV_1`$. Let $`E_{01}`$ be the set of edges in the cut, i.e., all edges with the first vertex in $`V_0`$ and the second in $`V_1`$. $`E_{10}`$ is defined analogously. The weight of the cut is $`w(C)=|E_{01}|+|E_{10}|`$.

Clearly, as $`X_1,\mathrm{},X_n`$ varies over all assignments, the corresponding cut $`C`$ varies over all cuts of $`G`$. Especially, there is a one-to-one correspondence between assignments and cuts.

There is a cut whose weight is at least $`w`$ if and only if there is an assignment to the variables $`X_1,\mathrm{},X_n`$ such that

$$w(C)=|E_{01}|+|E_{10}|=\underset{(k,l)E}{}(1X_k)X_l+X_k(1X_l)w.$$
(2)
To define our $`2`$-local Hamiltonian encoding the MAX CUT problem we start from the inequality

$`{\displaystyle \underset{(k,l)E}{}}X_kX_l+(1X_k)(1X_l)`$ $`=`$ (3)
$`{\displaystyle \underset{(k,l)E}{}}\left(1(1X_k)X_lX_k(1X_l)\right)`$ $``$ $`|E|w`$ (4)
that is obtained from inequality (2) by multiplying with $`1`$, and adding $`|E|`$ on both sides. We use the $`2`$-local projection

$$P_{even}=\left(\begin{array}{cccc}1& 0& 0& 0\\ 0& 0& 0& 0\\ 0& 0& 0& 0\\ 0& 0& 0& 1\end{array}\right)=|0000|+|1111|$$

to define our $`2`$-local Hamiltonian such that its eigenvalues are given by (3). The Hamiltonian is defined as

$$H=\underset{(k,l)E}{}P_{even}[k,l].$$
(5)
Clearly, the eigenstates of $`H`$ are given by the computational basis states. We denote them by $`|X_1\mathrm{}|X_n`$. The energy of the state $`|X_1\mathrm{}|X_n`$ is given by (3).

Therefore, $`G`$ has a cut whose weight is at least $`w`$ if and only if $`H`$ has an eigenvalue that is smaller or equal to $`|E|w`$. Since all eigenvalues of $`H`$ are natural numbers, we may formulate this question as the $`2`$-local Hamiltonian by choosing $`a:=|E|w+0.5`$ and $`b:=a+0.25`$. This choice ensures that either the first or the second situation occurs in Definition 2. Furthermore, we have $`ba>1/n^2`$ for all $`n3`$. Hence, we have shown that the SIMPLE MAX CUT problem can be reduced to the $`2`$-local Hamiltonian problem defined by Kitaev.

## 4 Independent set

We show that the INDEPENDENT SET problem may be formulated as the $`2`$-local Hamiltonian problem defined by Kitaev.

The INDEPENDENT SET problem is defined as follows \[GJ79\]:

* INSTANCE: Graph $`G=(V,E)`$, positive integer $`v|V|`$.
* QUESTION: Does $`G`$ contain an independent set whose cardinality is at least $`v`$, i.e., a subset $`V^{}V`$ such that $`|V^{}|v`$ and such that no two vertices in $`V^{}`$ are joined by an edge in $`E`$?

The INDEPENDENT SET problem remains NP-complete for cubic planar graphs \[GJS76\]. A graph is called cubic if all vertices have degree $`3`$, i.e., all vertices are connected to exactly three vertices.

Following the idea of \[Bar82\] we associate a variable $`X_k\{0,1\}`$ to each vertex $`kV`$. There is an independent set whose cardinality is at least $`v`$ if and only if there is an assignment to the variables $`\{X_kkV\}`$ such that

$$\underset{kV}{}X_k\underset{(k,l)E}{}X_kX_lv.$$
(6)
This is seen as follows. If $`V^{}`$ is an independent set whose cardinality is at least $`v`$, then the assignment $`X_k=1`$ for $`kV^{}`$ and $`X_k=0`$ for $`kVV^{}`$ fulfills inequality (6).

Now let $`X_1,\mathrm{},X_n`$ be an assignment that fulfills inequality (6). If $`V^{}=\{kX_k=1\}`$ is not an independent set, then we must have $`|V^{}|v+p`$, where $`p:=_{(k,l)E}X_kX_l>0`$ is the “penalty” for $`V^{}`$ not being an independent set. Let $`(\stackrel{~}{k},\stackrel{~}{l})E`$ with $`X_{\stackrel{~}{k}}=X_{\stackrel{~}{l}}=1`$. By removing $`\stackrel{~}{k}`$ from $`V^{}`$ (i.e. setting $`X_{\stackrel{~}{k}}:=0`$) the cardinality of $`V^{}`$ drops by $`1`$, while $`p`$ drops by at least $`1`$. After repeating this several times, we end up with an independent set whose cardinality is at least $`v`$.

To construct our $`2`$-local Hamiltonian encoding the INDEPENDENT SET problem we start from the inequality

$$\underset{kV}{}(1X_k)+\underset{(k,l)E}{}X_kX_l|V|v.$$
(7)
that is equivalent to inequality (6). We use the $`1`$-local projection

$$P_0=\left(\begin{array}{cc}1& 0\\ 0& 0\end{array}\right)=|00|$$

and the $`2`$-local projection

$$P_{11}=\left(\begin{array}{cccc}0& 0& 0& 0\\ 0& 0& 0& 0\\ 0& 0& 0& 0\\ 0& 0& 0& 1\end{array}\right)=|1111|$$

to define our $`2`$-local Hamiltonian such that its eigenvalues are given by the left hand side of (7). The Hamiltonian is defined as

$$H=\underset{kV}{}P_0[k]+\underset{(k,l)E}{}P_{11}[k,l].$$
(8)
Clearly, the eigenstates of $`H`$ are given by the computational basis states. We denote them by $`|X_1\mathrm{}|X_n`$. The energy of the state $`|X_1\mathrm{}|X_n`$ is the left hand side of (7). Therefore, $`G`$ has an independent set whose cardinality is at least $`v`$ if and only if $`H`$ has an eigenvalue that is smaller or equal to $`|V|v`$. Since all eigenvalues of $`H`$ are natural numbers, we may formulate this question as the $`2`$-local Hamiltonian by choosing $`a:=|V|v+0.5`$ and $`b:=a+0.25`$. This choice ensures that either the first or the second situation occurs in Definition 2. Furthermore, we have $`ba>1/n^2`$ for all $`n3`$. Hence, we have shown that the INDEPENDENT SET problem can be reduced to the $`2`$-local Hamiltonian problem defined by Kitaev.

## Acknowledgments

This work was supported by grants of the BMBF project MARQUIS 01/BB01B. We would like to thank H. Rosé, T. Asselmeyer, and A. Schramm for interesting discussions.


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# Relaxation and reconstruction on (111) surfaces of Au, Pt, and Cu

## I Introduction

The properties of close-packed noble and transition metal surfaces have been extensively studied in recent years. The research has made great advances since the introduction of new experimental techniques, in particular scanning tunneling microscopy (STM), and the improvement of first-principle computational methods based on the density functional approach. These surfaces show a wide variety of behavior with respect to reconstruction, preferred site and strength of chemisorption of reactive species, adsorbate diffusion, etc.

Owing to the abrupt change of the electronic structure on metal surfaces the first layer of atoms may have rather different properties from the bulk. Often, a large intrinsic tensile surface stress appears, which is the driving force leading to compressive reconstruction on many close-packed metal surfaces. The stability of a particular surface is the result of the interplay of several physical quantities characteristic of surface, such as surface energy, surface stress, interatomic force constants, etc. The reconstruction is more likely to occur the larger the intrinsic stress and the smaller the energy for sliding the atoms of the first layers into positions out of registry with the substrate.

In this paper we consider (111) surfaces of copper, platinum, and gold. The Au(111) surface reconstructs forming a uniaxially compressed layer, which can be seen in STM experiments.Woll89 ; Harten85 ; Repain00  The Pt(111) reconstructs only at high temperatures,Sandy92 ; Grubel93  or in the presence of saturated Pt vapour,Bott93 ; Hohage95  and Cu(111) does not reconstruct. We report on first-principle numerical calculations of the properties of these surfaces using the density functional theory (DFT). In Sec. II we first describe the generalities of the computation procedure. We then calculate the important physical quantities, such as the effective force constants in the first layer, the surface energies, and the intrinsic surface stress. In Sec. III we use these quantities in order to estimate the stability of the first layer of atoms with respect to a quasi-one-dimensional reconstruction, which can be treated theoretically by the Frenkel-Kontorova model. In the Sec. IV we discuss the results.

## II Calculations of surface properties

The reconstructed phase of some close-packed metal surfaces may have a periodicity which involves many surface atoms. For example, the reconstruction of Au(111), one of the surfaces considered in this paper, involves a uniaxially compressed first atomic layer with a period of around 70 Å. Full first-principle calculations with such large supercells are not feasible. One instead evaluates the stability by calculating the relevant quantities of the unreconstructed surface, and uses them in phenomenological models of reconstruction.

There have been a number of papers in which the stability of (111) surfaces of noble metals was evaluated using the Frenkel-Kontorova (FK) modelFrenkel38 ; Frank49 ; Zangwill96  of uniaxially compressive reconstruction. Ravelo and El-Batanouny (Ref. Ravelo89, , see also references therein) have constructed effective potentials between surface atoms and performed molecular-dynamics simulations of the reconstructed phase. Mansfiled and NeedsMansfield90  have derived conditions of stability of (100) and (111) surfaces towards a compressive reconstruction in the FK model, and evaluated it for several metals. Apparently, their values of the parameters are not good enough, as they have found no reconstruction of Pt(111) and Au(111). In particular, the strength of the interatomic potentials seems to be overestimated. Takeuchi et al.Takeuchi91  have constructed a two-dimensional potential between first- and second-layer atoms of a Au(111) surface using the results of first-principle calculations. They have calculated the reconstruction pattern using simulation techniques in a two-dimensional FK model. Using the two-dimensional potential in a molecular-dynamics simulation, Narasimhan and VanderbiltNarasimhan92  have concluded that the herringbone pattern of the reconstruction stripes observed on Au(111) is favored by the long-range elastic interactions mediated by the substrate. Recently, Narasimhan and PushpaNarasimhan02  have studied a two-dimensional FK model of the Pt(111) surface for which the parameters have been obtained from ab initio calculations. They have obtained simulated STM images of the reconstruction stripes recombining and intersecting in various ways, similarly to the structures observed in STM experiments.

The aim of this paper is to re-evaluate with highest accuracy the properties of the surfaces which determine the stability towards reconstruction. In this section we report on such calculations for the (111) surfaces of Au, Pt, and Cu in the density functional theory (DFT) approach. In the following subsections we describe, in order, the generalities of the numerical calculations, the calculation of surface energies, surface stress, surface spring constants, and the calculation of energy required to slide the complete first layer to various positions away from the most stable one. In the next section we use these results as input parameters in the (effectively one-dimensional) Frenkel-Kontorova model of uniaxially compressive reconstruction.

### II.1 DFT calculations

We have performed first-principle calculations of the electronic structure of (111) surfaces within the density functional theory approach, using the dacapo program.Hammer99  We have used the provided ultrasoft pseudopotentials for the Perdew-Wang exchange-correlation functional PW91 and the generalized gradient approximation (GGA).

We have first made calculations for bulk metal, in order to determine the lattice constant at which the energy per atom is minimum, using the primitive fcc unit cell. The lattice constant found often differs slightly from the experimental value: for example, our value is 4.00 Å compared with the experimental value 3.92 Å for Pt, 4.18 Å compared with the experimental value 4.08 Å for Au, and 3.66 Å compared with 3.61 Å for Cu. We have followed the common practice using the computed value of the lattice constant in susequent calculations, which ensures that no spurious bulk stresses appear.

The surfaces were described by a slab of five or more hexagonal layers of atoms. Since the calculation assumes periodicity in all three dimensions, the metallic slabs were separated by typically five layers of vacuum. In addition to ideal surfaces, we calculated surfaces perturbed in various ways in order to deduce quantities like surface stress and surface energy, which can be used to estimate the stability of the surface. More details are given in the respective subsections.

In the case of a clean surface, the unit cell in the directions along the surface plane $`(xy)`$ consisted of one atom, and 56 $`k`$-points in the two-dimensional first Brillouin zone were used. In some calculations described in the following subsections, e.g., when alternate rows of first-layer atoms were displaced in opposite directions, in order to probe the restoring forces within the first layer, unit cells with four atoms in each plane were used, and the number of $`k`$-points was reduced to 18. In the $`z`$-direction, perpendicular to the layers, only $`k=0`$ was considered, consistent with the assumption that the slabs, which repeat periodically because of the computational method, did not couple to each other. In most calculations, the two bottom layers were kept fixed at the bulk separation. We used an energy cutoff for the plane-wave basis set of 340 eV, and the electronic occupation was smeared by a pseudothermal distribution of $`T=0.2`$ eV. We performed some checks with a lower value, $`T=0.1`$ eV, and found that the changes of the calculated quantities were irrelevant.

Next, we calculated the structure of clean (111) surfaces. The relaxation of the surface layers from truncated bulk positions was found to be rather small for the three metals considered. For gold, the first and second layers relax less than 0.3% of the interlayer distance in the $`111`$ direction, with an energy gain of 1 meV, which is irrelevant considering the accuracy of the calculation. The first platinum layer relaxes outwards by about 1%, with an energy gain of 2.5 meV. This unusual expansion of the interlayer distance has been observed experimentally.Materer95  On copper, the first three layers move inwards by less than 1%, and the energy gain is 4 meV.

### II.2 Surface energy

We obtained the surface energy per atom as the difference of the energy of the bulk and of a slab. In order to minimize the influence of the computational details, we calculated the energy of the bulk using a six layer slab (i.e., twice the $`abc`$ stacking of the $`111`$ fcc direction) with no vacuum layers. After that, we changed the configuration by introducing four layers of vacuum which created two (111) surfaces, and calculated the energy, allowing both surfaces to relax. The surface energies $`\gamma `$, one half of the difference of the energies obtained in the two calculations, are given in the GGA column in Table 1. These values are consistently smaller by about one third than those calculated recently by Vitos et al.Vitos98  and Galanakis et al.Galanakis02a ; Galanakis02b  and various experimental values reported therein. One possible source of the discrepancy are the different pseudopotentials and exchange-correlation functionals used. We therefore also report the surface energies calculated using the LDA functional for the electronic densities obtained in the GGA calculations, in the column labeled as LDA in Table 1. These electronic densities are, of course, non-self-consistent with respect to the LDA functional. They are always larger than the GGA results, in better agreement with Refs. Vitos98, ; Galanakis02a, ; Galanakis02b, . Another possible source of discrepancy is the small thickness of the slab in our calculation. In the bulk calculation (i.e., 6 layers without vacuum) we used only one $`k`$-point in the $`z`$-direction, in order to keep the similarity with the surface calculations, and consequently the long-distance contributions in the $`z`$-direction might not be correctly taken into account. This can be investigated by using elementary cells with more layers, i.e., repeating the $`abc`$ structure three or more times, but we have not done such checks. Also, we used the equilibrium lattice constants obtained self-consistently in our GGA calculations which were larger than the experimental values and those obtained by other authors from LDA calculations.

In the following section, when discussing the stability of the surfaces, we shall use the LDA results, which seem to agree well with the best values reported in the literature.

### II.3 Surface stress

The surface stress can be found by considering the change of energy when the lattice constant in the $`x`$ and $`y`$ direction (i.e., in the surface plane) is varied. In the bulk calculations the leading correction to the energy when the lattice constant is varied around the equillibrium value is quadratic by construction, since we used the lattice constant corresponding to the energy minimum. Owing to the reduced coordination, the optimum interatomic distance in the surface layer is smaller than the bulk lattice constant, as already mentioned, causing an intrinsic tensile surface stress.Ibach97 ; Haiss01  Therefore, the surface contibution to the energy has a leading linear term if the lattice constant in the $`x`$ and $`y`$ direction is varied.

In order to find the intrinsic surface stress, we calculated the energy of slabs consisting of six layers, as in the preceding subsection, both unperturbed and with the unit cell compressed or expanded along the coordinates $`x`$ and $`y`$ (i.e., in the directions in the surface plane) for around 0.1%, not allowing any additional relaxation in the $`z`$ direction. We also calculated similar configurations without vacuum layers, in order to subtract the quadratic bulk term, as discussed earlier. The diagonal element of the surface stress tensor $`\tau `$, which is the relevant quantity for the surface reconstruction, is

$$\tau =\frac{\mathrm{\Delta }E}{2\mathrm{\Delta }A},$$
(1)
where $`\mathrm{\Delta }E`$ is the change of energy when the lattice constant is varied (after subtracting the quadratic bulk term) and $`\mathrm{\Delta }A`$ is the associated change of the surface area. The numerical values are given in Table 2. We have found that in this case there is almost no change if the non-self-consistent LDA values of the energy are used instead of the GGA values.

### II.4 Surface spring constants

The simplest atomic-scale model of the lattice dynamics of fcc metals is to assume central harmonic forces between nearest neighbor atoms. In this model there is a universal scaling of phonon spectra and different elements of the elasticity tensor, which is obviously an oversimplification. Nevertheless, this model is sufficient for the purpose of this work. The force constant $`k_{0B}`$ of the nearest neighbor bond in the bulk can be found from the bulk modulusKittel71  $`B=1/3(C_{11}+2C_{12})`$:

$$k_{0B}=\frac{1}{2aB},$$
(2)
where $`a`$ is the lattice constant of the conventional fcc unit cell.

However, the effective force constant between the atoms in the first surface layer can differ from the value in the bulk, since the lower coordination can substantially alter electronic properties, and an ab-initio DFT calculation is necessary. (Note that this force constant also contributes to the quadratic energy term in the preceding subsection, where we did not consider the possibility that it was modified within the first layer. However, the possible error which this introduces in the calculation of the surface stress is negligible.)

We made slab calculations (with relaxation turned off) in which rows of atoms in the first layer were displaced by about 0.05 Å either in the direction of the rows or perpendicularly to it, as shown in Fig. 1. Unlike other calculations in this paper, here we were not interested in the total energy, but rather in the restoring forces appearing owing to the nonequlibrium configurations. We analyzed the results assuming central harmonic interactions (“springs”) between nearest neighbors, neglecting the coupling to the second layer. Taking into account the number of nearest neighbor bonds and the angles, we calculated the force constants $`k_{0S}`$. The results for both the bulk values obtained from Eq. (2) and the surface DFT calculations are shown in Table 1. We note once again that this approach does not attempt to give a complete description of the lattice dynamical properties of the first surface layer. In general, even if the interactions with subsurface atoms are not taken into account, a set of force constants between second and further neighbours and/or angular force constants would be necessary in order to reproduce accurately the lattice dynamics, i.e., the phonon spectra. The present approach is a simplification to be used only in an estimation of the stability of the surface layer. One may further object that the reconstruction has a large wavelength, while the displacements shown in Fig. 1 correspond mainly to short-wavelength modes around the edge of the Brillouin zone, and the estimated $`k_S`$ need not be the same. In our opinion, the differences are small.

### II.5 Potential between the top layer and the bulk

When reconstruction occurs, some first-layer atoms are displaced to energetically less favorable positions with respect to the second layer. The last quantity which we need for an estimate of the stability is the amount of energy lost by the atoms when displaced to various nonoptimal positions. Since the periodicity of the reconstruction pattern is large compared with the substrate periodicity (e.g., by a factor of around 22 on Au(111)), the position of each subsequent atom along the reconstruction direction with respect to the second layer changes only slightly. A good estimate of the energy involved can be obtained by considering structures in which all atoms in the first layer are simultaneously displaced by the same vector. We performed DFT calculations of such configurations, keeping the displacement in the $`xy`$ plane fixed and allowing the atoms to relax in the $`z`$ direction.

We first calculated the energy of the regular fcc configuration, denoted by $`f`$ in figures and tables, which is energetically the most favorable. Next, we considered the configuration with the first layer atoms in the hcp hollows of the second layer ($`h`$), which is also a local energy minimum. We furthermore calculated the energy of some other configurations which are not local energy minima, keeping the $`x`$ and $`y`$ coordinates fixed, so that the algorithm for the atomic relaxation ignored the lateral forces acting on the first-layer atoms. These are (see Fig. 2) the “bridge” position ($`b`$) in which the first-layer atoms are halfway between fcc and hcp hollows, the on-top configuration ($`t`$), the configurations ($`ft`$) and ($`ht`$) halfway between ($`f`$) and ($`t`$), and ($`h`$) and ($`t`$), respectively, etc. (Not all calculations were performed for all three metals.) For the quasi-one-dimensional compressive reconstruction, the relevant configurations are along the path $`ffbbbhh`$ and back to $`b`$ and $`f`$. (The on-top configuration, which is not occupied in the reconstruction, was calculated with the aim to obtain a better insight into the difference between various metals.) In practice, the calculations were performed so that initially, all layers except the top one were kept fixed at the bulk configuration, the top layer had fixed $`x`$ and $`y`$ coordinates, and the $`z`$ coordinate was allowed to relax. In a second step, the bottom two layers were kept fixed, the intermediate layers were allowed to relax in all directions, and the top layer was allowed to relax in the $`z`$ direction only. The second step produced only minor changes for the symmetrical configurations ($`f`$), ($`h`$), ($`t`$), and ($`b`$), but the nonsymmetric configurations changed significantly, as the atoms in the second layer (and to a lesser degree in deeper layers) relaxed laterally under the force exerted by the first-layer atoms.

In Fig. 3 we show the calculated energies, measured with respect to the energy of the fcc configuration, which was the lowest for all three metals. The “bridge” position, midway between fcc and hcp hollows, is approximately a saddle point. All points were calculated for five layers (first one fixed in $`x`$ and $`y`$, two free, two fixed), and some points were also calculated for six and seven layers. It was found that the energies changed by several meV, but the qualitative behavior remained similar, and the estimates of stability towards reconstruction in the following section are not affected. Generally, the energies of symmetric configurations ($`h,b,t`$) increase with increasing number of layers, while those of nonsymmetric configurations, like ($`fb`$) or ($`ht`$), decrease. This can be attributed to the fact that in the latter case there are more atomic layers which are free to relax laterally, leading to a more complete relaxation.

The first-layer atoms in positions other than the regular fcc one ($`f`$) are also protruding further out. For all three metals, the values are similar, namely, around 0.1 Å for the bridge ($`b`$), 0.02 Å for the hcp ($`h`$), and $`0.30.4`$ Å for the on-top position ($`t`$).

The relevant quantity for the stability estimate is the average energy $`W`$ along the path $`fbhbf`$, in the approximation of making a Fourier expansion and keeping only the two lowest terms:

$$W=\mathrm{\Delta }E(b)+\mathrm{\Delta }E(h)/2.$$
(3)
## III Stability and reconstruction

In this section we use the calculated quantities to discuss the stability of the surfaces of platinum, gold and copper. We first introduce the one-dimensional Frenkel-Kontorova model, and then discuss, in order, each of the considered surfaces, calculating the stability criteria, and comparing the results with the known experimental findings.

### III.1 Reconstruction of (111) surfaces

As already said, the electronic structure of closed-packed metal surfaces is very different from that in the bulk, with an abrupt decrease in density of conduction electrons. The consequences may be a change of the length of the bonds between surface atoms, occasionally accompanied by a reconstruction which involves a change of the number of atoms in the first surface layer.

The reconstruction of the fcc (111) surface involves a large number of atoms in inequivalent positions with respect to the underlying layer of atoms. In scanning tunneling microscopy experiments, the reconstruction of the Au(111) surface can be clearly seen as bright stripes,Woll89 ; Repain00 ; Bach97  owing to the increased height of atoms which are out of registry with the second layer. On a larger scale, the stripes form a herringbone pattern, as the quasi-one-dimensional reconstruction proceeds along three equivalent directions on the surface. A typical size of the reconstructed Au(111) supercell is $`70\text{Å}\times 280\text{Å}`$. The reconstruction of the Pt(111) surface is similar, but occurs only at high temperaturesSandy92 ; Grubel93  or in the presence of saturated Pt vapour.Bott93 ; Hohage95  STM micrographs show that the stripes do not form continuous patterns, but are instead well separated, with various types of intersections.Hohage95  The stripes in both systems consist of quasi-one-dimensional compressive reconstructionWoll89 ; Harten85  and can be treated as solitonic solutions of the Frenkel-Kontorova model.Takeuchi91 ; Narasimhan92  The large-scale two-dimensional structure of the reconstructed phase depends upon details of the interactions, and will not be discussed here.

### III.2 The Frenkel-Kontorova model

The one-dimensional Frenkel-Kontorova modelFrenkel38 ; Frank49 ; Zangwill96  consists of a linear chain of atoms, subject to two competing interactions with different intrinsic periodicities. The atoms interact via a nearest-neighbor harmonic coupling with a preferred lattice constant $`b`$. In addition, there is an external periodic potential (i.e., the potential of the second atomic layer) of a periodicity $`a`$. Depending on the strength of the external potential and the magnitude of the spring constant $`\mu `$, various stable solutions are possible. At small “pressures” (i.e., small difference of $`a`$ and $`b`$, small $`\mu `$) the external periodic potential dominates and all atoms are in potential minima, forming a commensurate phase. As the “pressure” increases, the natural periodicity of the atomic chain becomes more important. If, say, $`b<a`$, solitons appear in which the atoms are closer to each other, thus gaining energy from the harmonic interaction but paying the cost of increased potential energy in the external potential. Finally, when the external potential is weak compared with the elastic energy needed to stretch the atomic chain, the atoms follow the periodicity $`b`$, forming an incommensurate phase.

Mansfield and NeedsMansfield90  have applied the Frenkel-Kontorova model to the reconstruction of (111) surfaces of the fcc metals. They have found that the relevant quantity is

$$P=\frac{A(\gamma 4\tau /3)}{\frac{2}{\pi }\sqrt{2\mu Wa^2}}=\frac{W\beta }{W\alpha },$$
(4)
where the parameters of the Frenkel-Kontorova model have already been expressed in terms of the physical properties of real (111) surfaces. Thus, $`\gamma `$ is the surface energy, $`\tau `$ is the surface stress, $`\mu `$ is 3/2 of the surface force constant, and $`W`$ is the average potential energy. (The factors 4/3 in the stress term and 3/2 in the definition of $`\mu `$ appear because the path $`fhf`$ is not straight.) $`a`$ is the distance from the fcc hollow site to the nearest hcp hollow site on the (111) surface, and $`A`$ is the surface area per atom. These quantities are the same (or closely related to) those calculated in the preceding section for real metal surfaces. There is no reconstruction for $`|P|<1`$, the reconstruction is compressive for $`P<1`$ and expansive for $`P>1`$. The quasicontinuum approach is valid if the magnitudes of the dimensionless quantities $`\alpha `$ and $`\beta `$ defined in Eq. (4) are large, say larger than 5.

In the following subsections we apply this analysis to the (111) surfaces of gold, platinum, and copper. The relevant quantities derived in Section II are summarized in Table 2, and the resulting $`\alpha `$ and $`\beta `$ are given.

### III.3 Au(111)

In our calculations the first layer of an ideal Au(111) surface relaxes outwards by about 0.005 Å, less than 0.3%, which is at the limit of accuracy of the calculations. The energy per surface atom of the hcp configuration is higher than that of the ideal (fcc) structure by around 10 meV per atom, and that of the bridge by 33 meV (Fig. 3). This is in excellent agreement with the calculations of Takeuchi et al.Takeuchi91  and Galanakis et al.,Galanakis02a ; Galanakis02b  who used a density functional approach with a mixed basis set. These energies are the smallest of all metals considered here. The surface energy is also small, and owing to a moderately large tensile surface stress we obtain that $`\beta `$ is slightly larger than $`\alpha `$, indicating that the surface reconstructs. Experimentally, the surface appears particularly prone to reconstruction, and a dense pattern of stripes of $`23\times \sqrt{3}`$ reconstruction is observed at room temperatures with STM.Woll89 ; Bach97 ; Repain00

### III.4 Pt(111)

Our calculations show that the first atomic layer on Pt(111) relaxes outwards by 0.023 Å or 1%. This somewhat exceptional behavior has also been found in other calculations and confirmed experimentally.Materer95  It has been attributed to an outward pointing electrostatic force on the positively charged atoms of the first layer owing to the kind of spill-out of electrons away from the surface.Needs87  The energy of the bridge configuration is around 46 meV larger than that of the regular fcc surface. The energy of the hcp configuration is only slightly smaller than the bridge (even less so in calculations with 6 and 7 layers), which is different from the other surfaces considered. The force constant $`k_{0C}`$ calculated assuming a “longitudinal” displacement of rows of first-layer atoms is reduced by about 30% compared with that derived from the bulk compressibility. The intrinsic tensile surface stress is large, more than twice larger than in the other two metals considered. Although the surface energy is also quite large, the quantity $`\beta `$ is much larger than $`\alpha `$, predicting a strong tendency to reconstruct.

Experimentally, the reconstruction of Pt(111) is observed only at high temperatures or in the presence of saturated platinum vapor.Sandy92 ; Grubel93 ; Bott93 ; Hohage95  The nature of the reconstruction is similar to that of Au(111), but the stripes of compressive “solitons” do not form a dense pattern. Instead, they are sparse, and occasionally intersect in several distinct ways.Hohage95 ; Narasimhan02

### III.5 Cu(111)

Unlike the other two metals considered, we find that the first layer on an ideal (fcc) Cu(111) surface relaxes inwards by 0.014 Å. The contraction of the interlayer distance is usual for close packed surfaces of many transition metals. The hcp configuration is a clear local energy minimum, and the energy of the on-top configuration is found to be exceptionally large at about 250 meV. The intrinsic surface stress is again tensile, but rather small. The calculated $`\beta `$ is clearly smaller than $`\alpha `$, indicating that the surface does not reconstruct. Indeed, no reconstructruction has been observed experimentally.

### III.6 Discussion

The use of the stability condition of (111) surfaces derived in the one-dimensional Frenkel-Kontorova model, Eq. (4), gives correct qualitative answers, namely, that the surfaces of gold and platinum reconstruct compressively and the surface of copper does not. From a quantitative point of view, the agreement between theory and experiment is less satisfactory. We find that the condition for reconstruction, $`|\beta |>\alpha `$, is barely satisfied for the Au(111) surfaces, while in experiments a dense pattern of reconstruction stripes is always found on this surface. On the other hand, we obtain that the condition of Eq. (4) is amply fulfilled for the Pt(111) surface, while experimentally, reconstruction is observed only under favorable thermodynamic conditions, at high temperatures, or in the presence of Pt vapor. It has already been noticed that calculations predict only a marginal tendency for reconstruction on Au(111), at variance with experiment. It has been suggested that the ordering of the reconstruction stripes into a herringbone pattern is indeed an essential contributing factor to the stability of the reconstructed phase.Bach97 ; Narasimhan92  The theoretical overestimate of the tendency to reconstruct in the case of Pt(111) may be due to the large value of the surface energy, which makes it unfavorable to bring additional atoms to the surface once the surface stress has been reduced by the formation of a few sparse reconstruction stripes. For a more complete treatment, a two-dimensional Frenkel-Kontorova model with a more realistic potential, calculated in a region around the minima, should be used.

The approach used in this paper can also give relevant parameters for other physical properties. We have calculated relaxations around adatoms of the same species on the surfaces considered in this paper, and found that the force–relaxation ratio is consistent with the model of elastic constants calculated in Section II. Surprisingly, in our calculations (one adatom per four surface atoms) the adsorption into a hcp hollow site was slightly more favorable than into a fcc hollow site for all three metals considered. We have not found any conclusive experimental data about this property.

The approach can also be applied to relaxation around defects and chemisorbates of different species, energetics of self- and heterodiffusion, and other properties of (111) surfaces.

## IV Conclusions

Using the density functional theory approach we have calculated key properties of (111) surfaces of several metals, and evaluated the stability towards reconstruction into a uniaxially compressed reconstructed layer, using a one-dimensional quasicontinuum Frenkel-Kontorova model. The intrinsic surface stress is tensile for all surfaces, i.e., the atoms in the first layer prefer a denser packing than dictated by the potential of the second layer, which reflects the bulk periodicity. On the opposite side of the energy balance is the energy required to bring an extra atom into the surface layer, and the energy lost owing to the fact that surface atoms in a reconstructed phase are no longer in the minima of the potential of the second layer. We have found that Pt(111) reconstructs owing to a large intrinsic tensile surface stress. The stress on Au(111) is considerably smaller, but the surface energy is also smaller and the reconstruction criterion is satisfied. The intrinsic surface stress in Cu(111) is somewhat smaller than that in Au(111), but other quantities are unfavorable, and the surface does not reconstruct, in agreement with experimental observations. Experiments show that Au(111) has the largest tendency to reconstruct, and dense reconstruction patterns are observed using STM, while Pt(111) reconstructs only under favorable conditions, and only a small fraction of the surface is reconstructed. This is the opposite from what our reconstruction criteria suggest, where Pt(111) is much deeper in the reconstruction regime. The reason may be further stabilization of the reconstruction of the gold surface by the formation of a two-dimensional herringbone structure,Bach97 ; Narasimhan92 ; Bulou02  which is not included in the one-dimensional model used in the derivation.

###### Acknowledgements.

This work was supported by the Ministry of Science and Technology of the Republic of Croatia under contract No. 0098001. One of us (R. B.) acknowledges helpful discussion with Dr. S. Narasimhan.


text:
# Mott transition from a diluted exciton gas to a dense electron-hole plasma in a single V-shaped quantum wire

## I Introduction

Non-linear effects in one-dimensional (1D) systems have been recently the subject of many theoretical as well as experimental investigations, due to the potential applications for optoelectronic devices and especially for incorporating low dimensional heterostructures, like quantum wires, in lasers.

It has been predicted that due to the suppression of the 1D singularity in the density of states because of the important Coulomb correlations in one dimension, the exciton transition has an enhanced oscillator strength and stability compared to quantum wells Ogawa-PRB91 ; Rossi-PRB96 . Many questions arise then: up to what carrier densities is the exciton stable ? When does the Mott transition occur in a quantum wire (QWR) and what is the origin of the emission line in 1D systems when the carrier density is increased ? There is a controversy in theory on this point, especially for the critical carrier density at the Mott transition DasSarma-PRL00 ; Piermarocchi-PRB01 ; Stopa-PRB01 . A typical predicted feature of a Mott transition in optical experiments is the existence of gain in the absorption spectrum at some energy range. But in some studies excitonic lasing is told to be possible in one-dimensional structures. Rossi et al Rossi-PRB96  found optical gain at a carrier density of $`\mathrm{4\; 10}^6cm^1`$ while the calculated Mott transition occurs at $`\mathrm{8\; 10}^5cm^1`$. So, the authors predict that lasing due to electron-hole pairs may occur in a QWR. Piermarrochi et al Piermarocchi-PRB01  predict that optical gain occurs at $`10^5cm^1`$, below the Mott transition, while Das Sarma et al DasSarma-PRL00  found no gain at any carrier density. However in photoluminescence experiments where the emission is observed, there is no signature of the presence of gain in the structure, and it is more difficult to evidence a Mott transition. The existence of the Mott transition is still under debate, depending also on the definition itself. In many-body theories treating the Coulomb correlations between free carriers, the transition occurs when an electron and a hole cannot form a bound pair and the obtained critical density is $`na_X0.11`$ Rossi-PRB96 ; DasSarma-PRL00 ; Piermarocchi-PRB01 ; Stopa-PRB01  where $`n`$ is the carrier density and $`a_X`$ is the exciton Bohr radius in the system. However in many-body theories treating Coulomb interactions between excitons, the transition occurs as soon as carriers (electron or hole) can be exchanged between two excitons. Then the Mott criterion is very much weakened, by a factor 100 in two-dimensionnal systems Combescot-EPL01 .

Experimentally, optical non-linearities under high pump excitation have been studied previously by other groups in less confining QWRs Greus-EPL96 ; Cingolani-PRB93 . Band filling has been evidenced and according to a theoretical modelisation of the results, band gap renormalization has been observed. Ambigapathy et al Ambigapathy-PRL97  have studied dynamics of excitons under high density regime. The authors conclude that the band gap renormalization is exactly compensating the exciton binding energy and the exciton remains the stable excitation under very high pump power ($`n=\mathrm{3\; 10}^6cm^1`$, $`na_X=3`$). The high density dynamics is also of crucial importance in the understanding of the lasing mechanism in QWR structures Kim-PhysE00 . Recently excitonic lasing in QWRs has been reported Wegsheider-PRL93 ; Sirigu-PRB00 ; Rubio-SSCom01 , based on the observation that the emission energy remains nearly constant within the inhomogeneously broadened photoluminescence line. We believe that this experimental evidence is not a sufficient criterion since at the high carrier density for which lasing is obtained, an electron-hole plasma (EHP) is formed in the wire and emits at the same energy. Therefore excitonic lasing in 1D structures is still an open question to our point of view.

We have performed systematic studies of continuous and time resolved photoluminescence of a single quantum wire, as a function of carrier density, by means of optical imaging spectroscopy. We show that the different non-linearities observed, depend strongly on the kind of local disorder in the wire especially in the low density limit. As pump power is increased the exciton emission line gets broader but remains at a constant energy position within a few $`meV`$. No distinct features appear in the spectra, for instance a line that could be attributed to the EHP emission. However we show that a gradual transition in the nature of excitations has occured in the system. Indeed, the time-resolved photoluminescence experiments in the high density regime reveal that the emission is due to the formation of an EHP and not to excitons.

$`\mathrm{1.2\; 10}^6cm^1`$, which is to our knowledge the first experimental estimation of the Mott density in this system.

## II Disorder effects in V-shaped QWRs

The studied samples are $`5nm`$ thick V-shaped GaAs/Ga0.57Al0.43As QWRs grown by flow rate modulation epitaxy on a $`4\mu m`$ pitched V-grooved GaAs substrate Wang-APL95 . These samples are very high quality structures with strong confinement (the energy spacing between the first and second subbands e1h1 and e2h2 is $`60meV`$) and showing specific 1D properties, like large optical anisotropy due to 1D valence band mixing. The localization of excitons in these QWRs has been studied by microphotoluminescence ($`\mu `$-PL). The low temperature $`\mu `$-PL confocal setup is composed of a microscope objective with a large numerical aperture ($`0.6`$) which is fixed on a three axis piezoelectric stage. This allows to scan images along a single QWR. The spatial resolution is $`0.8\mu m`$, which is the limit of diffraction of the microscope objective at 750 nm. The spectral resolution is $`40\mu eV`$ and the temporal resolution is $`20ps`$. Excitation wavelength was always adjusted with a Ti-Sa or a dye laser in order to create carriers only in the wire. This is important for the correct calibration of the carrier density in the wire. Details of the set-up can be found elsewhere Bellessa-PRB98 ; Guillet-Loc .

Our former studies have shown that at low temperatures, the optical properties of excitons in the previous generation of QWRs are governed by localization effects leading to a discrete spectrum of states Bellessa-PRB98 . Monolayer thickness fluctuations along the growth axis occur, leading to the formation of local potential minima with a mean size of $`50nm`$ along the wire axis. Optical imaging spectroscopy has allowed to characterize the local confining potential along the wire axis and to relate the local disorder to the optical properties Guillet-Loc . Excitons are localized in such quantum boxes and at very low pump power, the emission is composed of very sharp lines corresponding to the emission of the lowest lying exciton states in each box. The energy spectrum is discrete and the exciton dynamical properties are those of a zero-dimensional (0D) system Bellessa-PRB98 . We say then that the QWRs are in a 0D regime. When the density of excitons created in average is increased, different effects appear depending on the size of the box along the wire axis. The density threshold for non-linear effects being one exciton per box, the interaction between excitons will be weak if they are trapped in different boxes and more effective when trapped in the same box. Two different behaviours have been reported Wu-PRB00 ; Bellessa-EPJB01 : biexciton formation or Auger scattering depending on the size of the box. As the density is further increased, state filling effects occur with an important broadening of the emission band due to exciton-exciton or exciton-free carriers interactions.

Recent progresses in the growth techniques allowed to further reduce the heterointerfaces roughness of the QWR Wang-JCrystG00B . In this new generation of QWRs, the optical imaging spectroscopy shows that the thickness fluctuations on the (001) facet occur every $`5\mu m`$ while the other heterointerfaces (311) and (111) present monolayer fluctuations from $`0.5`$ to $`2\mu m`$ Guillet-Loc . A typical scanning image of a single QWR is shown in figure 1. Each bright spot corresponds to the emission from the lowest lying level in local potential minima along the wire axis. The linear density of the emitting sites is about 1 per $`\mu m`$ and the mean potential minimum length is $`400nm`$ as it is obtained after statistical analysis Guillet-Loc . Sometimes the emitting region can reach $`3\mu m`$ on one wire, for example at the position indicated by a white arrow on the image. In such a very long island, the localization length is much larger than the thermal de Broglie wavelength of the excitons, and the excitonic states form a quasi-continuum of states leading to 1D behaviour of the system. These samples are told to be in a 1D regime. The emission spectrum is then composed of a single homogeneously broadened line as it shown on figure 1. Another evidence for the 1D character of the system is that the radiative lifetime as a function of temperature shows the characteristic $`\sqrt{T}`$ dependence Guillet-Loc . This behaviour reflects the $`1/\sqrt{E}`$ 1D local density of states.

## III Many-body effects in 1D regime QWRs

We have studied continuous and time-resolved PL in different carrier density regimes in the 1D regime QWRs described above. Three density limits can be distinguished if we compare the average distance between excitons $`1/n`$, to the exciton Bohr radius $`a_X`$ which is equal to $`70\text{Å}`$ in our structure for a binding energy of $`20meV`$ Guillet-X1D . When the density of excitons $`n`$ is very low then $`na_X<<1`$ and the excitons form a weakly interacting gas, we say in that case to be in a “dilute” regime. On the opposite, the “dense” regime corresponds to very high carrier density where $`na_X>>1`$ and in this case we expect a dense EHP to be formed. Inbetween, there is also an “intermediate” regime for which a Mott transition should occur in the system.

Figure 2 represents typical $`\mu `$-PL spectra under continuous excitation of a very long island (about $`3\mu m`$) as a function of carrier density in the low density regime. Excitation energy is at $`1.75eV`$ in the e3h3 transition of the QWR. At very low pump power ($`P=0.1W.cm^2`$) one main $`\mu `$-PL peak appears, labelled A on the figure, corresponding to the emission of the lowest lying exciton level in this island. As a matter of fact, two other peaks labelled B, and C appear in the spectrum due to the presence of neighbouring islands that are excited by the laser spot, as it has been shown by the scanning images of the QWR (figure 1). However, their intensity is less than peak A intensity by a factor 10 and 30 respectively. As the pump power is increased up to $`\mathrm{5.4\; 10}^3W.cm^2`$, there is a slight blue shift of line A by $`0.2meV`$ and a new line appears in the spectrum corresponding to the formation of a biexciton (labelled A2). The biexciton binding energy can be deduced from the spectrum and is equal to $`1.5meV`$ which is in very good agreement with theoretical calculations Banyai-PRB87  and similar to other experimental observations Crottini-PSSB00 . The intensity of peak A has a linear behaviour with pump power and saturates above $`10^4W.cm^2`$ while peak A2 has a super-linear behaviour as expected for biexciton. The total integrated intensity of the luminescence line is linear with pump power. At the maximum pump power the lines get broader and a broad background grows up. This background can be attributed to the radiative recombination processes which are assisted by Coulomb collisions between excitons or excitons and free carriers. Similar observations have been reported by Vouilloz et al Vouilloz-SSCom98 .

The calibration of the carrier density created in the QWR is made from the data of saturation of exciton and biexciton emission intensities in the 0D regime QWRs These . We estimate that for a CW pump excitation at $`1.75eV`$, $`400W.cm^2`$ correspond to 1 exciton per $`\mu m`$, i.e. a carrier density of $`10^4cm^1`$ and to a number $`na_X`$ equal to $`\mathrm{7\; 10}^3`$. This calibration has been used for the estimation of the carrier density presented in all the following experiments.

As the upper limit of the dilute regime is reached ($`n=10^5cm^1`$, i.e. $`na_X0.1`$) the lines associated to exciton and biexciton transitions are still clearly marked showing that these are the stable elementary excitations in the system.

The intermediate ($`0.1<na_X<1`$) and dense regime ($`na_X>1`$) are represented in figure 3. In order to study the dense regime ($`na_X>1`$) pulsed laser excitation has been used to provide very high carrier concentration in the wire up to $`n10^7cm^1`$, i.e. $`na_X=20`$. For ($`0.1<na_X<1`$) the spectra obtained under continuous and pulsed excitation are similar. The peak labelled A corresponds to the main exciton line of a $`2\mu m`$ long island. The other peaks labelled B, C, and D correspond as usual to neighbouring islands excited by the tails of the laser spot. A2 is the biexciton emission line.

Let us first focus on the intermediate regime. A qualitative change of the spectra is observed above $`na_X=0.1`$. The exciton and biexciton lines are broadened, they shift towards higher energies by $`2meV`$ and finally disappear. The shift of the lines is a signature of the many-body interactions : it corresponds to a competition between the band gap renormalization (BGR) occuring as we fill the carriers subbands and the screening of the exciton binding energy. The sum of both effects give rise to small energy shifts in 1D structures, only a few $`meV`$, moreover an almost exact cancellation of these effects is predicted Rossi-PRB96 ; DasSarma-PRL00 . The fast growing up of the broad background is attributed to the presence of free electron-holes pairs. It progressively overcomes the excitonic transition as the excitation power is increased.

Another experimental evidence of the presence of free carriers in the intermediate regime is that there is a spatial diffusion of the carriers. Indeed we have measured the spatial distribution of the emission as a function of the carrier density by the optical imaging setup. In the case of 1D regime QWRs the emission spatial distribution is about $`1.2\mu m`$ thus larger than the limit of resolution ($`0.8\mu m`$) because of the larger spatial extension of the islands ($`400nm`$)Guillet-Loc . The recorded $`\mu `$-PL spatial profile can be very easily fitted by a Gaussian curve whose width is reported in figure 4 as a function of carrier density. For $`na_X<0.1`$, the spatial distribution width is limited by our experimental resolution. Above this density, the emitting region gets larger, showing that diffusion of carriers takes place along the wire axis before radiative recombination. We have checked that in the low density regime, excitons do not diffuse even up to $`70K`$ These , because the exciton-exciton scattering mechanism is less efficient than interaction with free carriers Honold-PRB89 . Here, the observed diffusion for a carrier density above $`10^5cm^1`$ is due to the presence of free carriers that are responsible for the scattering with excitons. The temperature of the carriers deduced from the high energy tail of the PL spectrum is $`40K`$ at the highest density, so that the diffusion isn’t thermally activated and is due to collisions between carriers. The density where this process occurs is $`n10^5cm^1`$, i.e. $`na_X0.1`$ and corresponds to the qualitative change observed in the luminescence spectrum (figure 3) Carrier-Density . Both the diffusion of the carriers and the spectral broadening of the exciton and biexciton transitions show that free electrons and holes coexist with excitons and progressively overcome them above $`na_X=0.1`$.

The $`\mu `$-PL spectra reported on Figure 3 also present the dense regime. Above $`na_X=1`$, higher order subbands (e2, h2, h3, …) are also filled : the optically allowed transitions e1h5 and e2h2 appear in the PL spectra at the same position as in the PLE spectra. It is worth noticing that the PL line centered at the exciton energy position does not shift significantly up to the highest excitation power. This is consistent with previous experimental findings Cingolani-PRB93 ; Ambigapathy-PRL97  and reflects the almost cancellation of BGR and screening of the exciton binding energy in 1D systems.

The temporal evolution of the $`\mu `$-PL provides a more detailed understanding of the system and is shown on figure 5 at the highest carrier density, corresponding to the top curve of Fig. 3 ($`n=\mathrm{2.5\; 10}^7cm^1`$, i.e. $`na_X=20`$, at $`t=0`$). The detection energy is set at different positions labelled $`E_0`$, $`E_1`$, $`E_2`$ on the figure 3. For the three curves, we first observe a very fast rising time ($`0<t<50ps`$), then a slowing down during $`200ps`$ which corresponds probably to the setting up of the quasi-equilibrium in the system. Then a characteristic saturation plateau is observed which persists longer as the detection energy is lower in the band. The PL intensity at the plateau is the same within 20% at the three detection energies, and a slight increase at $`E_1`$ and $`E_2`$ is observed, which is not explained at the moment. The temporal decay is different for the three curves. It is non-exponential for the case of higher detection energies ($`E_1`$ and $`E_2`$) and reflects the complicated carrier dynamics at high energy. When detecting on the band edge energy $`E_0`$ after $`1ns`$, the carrier density has decreased and we end up with an exciton population that recombines. Thus the decay is nearly mono-exponential with a characteristic time corresponding to the exciton radiative lifetime (about $`300ps`$) Bellessa-PRB98  as also confirmed by the low density temporal decay also shown on figure 5.

The dependence of the saturation plateaux with detection energy is characteristic of an EHP emission and not of exciton luminescence. Indeed if this were the case, due to the conservation of the k-selection rule, only $`k=0`$ excitons could recombine and then the saturation should be independent on the energy position in the line. On the contrary, we may qualitatively interprete the PL temporal evolutions as follows : at $`t=0`$, as the laser pulse excites the system, the carrier density is about $`\mathrm{2.5\; 10}^7cm^1`$ ($`na_X20`$). An EHP out of equilibrium is likely formed at this high density regime. Electron and hole subbands are filled over hundreds of $`meV`$ up to the chemical potentials $`\mu _{e,h}`$, and luminescence comes from the vertical transitions between electrons and holes of the different subbands. In a simplified single electron-hole band scheme described by only one potential $`\mu `$, the carrier density is progressively reduced as recombination takes place, then $`\mu `$ decreases in energy and the subband empties. When $`\mu `$ is larger than the detection energy $`E`$ by an amount larger than $`kT`$, the occupancy factor at energy $`E`$ is unity and the luminescence intensity saturates. When $`\mu =E`$, the occupancy factor decreases and the luminescence decreases rapidly as well. When $`E\mu >>kT`$, the occupation factor at energy $`E`$ is a Maxwell-Boltzmann distribution and the carriers at energy $`E`$ are at thermal equilibrium with the band-edge. The carrier density corresponding to $`\mu =E_0`$ is actually the density above which electron and hole subbands are filled and the electron-hole plasma ends to be degenerate. The whole process is schematically drawn on top of figure 5. The time-resolved PL reflects in fact the chemical potential temporal evolution and can be related to the carrier density. In a first order approximation we may assume that the entire population decays with the same lifetime (the exciton radiative lifetime). The carrier density we found in this way, corresponding to $`\mu =E_0`$ is about $`n\mathrm{1.2\; 10}^6cm^1`$, i.e. $`na_X0.8`$. This threshold density corresponds to the transition to a degenerate EHP, i.e. to the filling of the first electron and hole subbands.

However in order to have a full description of the chemical potential evolution as a function of $`n`$ in the degenerate EHP, one would have to study the temporal decay of the whole PL line and know more precisely the population decay. This would also allow to measure the precise shape of the plateaux, which depends on the selection rules governing the recombination process (conservation of energy, momentum, or both of them) and the renormalization of electron and hole energy dispersion as a function of the density.

In ref. Ambigapathy-PRL97  where similar results have been obtained, the authors present the time decay of the integrated PL in order to analyse the radiative decay of the carriers. Their main conclusion is that the recombination is dominated by “excitonic correlations” even at high density ($`\mathrm{3\; 10}^6cm^1`$) since the decay is mono-exponential with the characteristic exciton lifetime. We show here the energy- ad time-resolved PL provides a more complete understanding of the dynamics and proves that a fully degenerate EHP is formed at high density, excluding the presence of excitons.

## IV Conclusion

We have monitored the apparition of free carriers as well as the degeneracy of the EHP in a QWR by an extended study of their spectroscopy and dynamics, coupled to a local study relieving the inhomogeneous broadening of the transitions. Our results clearly show that the energy position of the emission line is not a sufficient criterion in order to determine the nature of the excitations in the system, as it was previously argued concerning the lasing mechanism in QWR lasers Wegsheider-PRL93 ; Sirigu-PRB00 ; Rubio-SSCom01 . In the low density regime the situation depends on the localization regime. In 0D regime QWRs with a localization length of the order of $`50nm`$, a competition between Auger effects and biexciton formation has been observed. But in 1D regime QWRs, in which each island is extended over $`0.5`$ to $`3\mu m`$ and can be considered as a small portion of really 1D QWR, excitons are stable until $`na_X1`$, and they coexist with free charges above $`na_X0.1`$. For $`na_X>0.01`$, biexcitons are formed and the slight shifts of the exciton line are a signature of Coulomb interactions between excitons. Above $`na_X=0.1`$ ($`10^5cm^1`$) free electrons and holes coexist with excitons, leading to a broad spectral background and the diffusion of carriers along the wire axis. In the dense regime ($`na_X>1`$, $`n>10^6cm^1`$) the saturation observed is the signature of a degenerate EHP luminescence excluding the possibility of exciton formation and reflects the temporal evolution of the chemical potential. Our results are in quite good agreement with recent theoretical calculations which predict that no new emission line attributed to the EHP should appear in the emission spectrum. This is due to the fact that the energy shifts associated to the screening of the exciton binding and to BGR occuring at high density are small (few $`meV`$) in QWRs because of the compensation of these two effects.


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# Specific Heat of the 𝑆=1/2 Two-Dimensional Shastry-Sutherland Antiferromagnet SrCu2(BO3)2 in High Magnetic Fields

## Abstract

We characterize the field-induced magnetic phases of SrCu2(BO3)2, a frustrated spin-1/2 Heisenberg antiferromagnet in the two-dimensional Shastry-Sutherland lattice, using specific heat in magnetic fields up to 33 T. We find that the spin gap persists above the expected critical field $`H_c=\mathrm{\Delta }/\mathrm{g}\mu _\mathrm{B}`$ of 21 T despite the appearance of magnetic moment in the ground state. At the magnetization plateau at 1/8 of the saturation, the $`S_z=+1`$ triplets that carry the magnetization of the ground state are observed to form a two-dimensional spin gas of massive bosons. A spin gas consisting of the same number of massive particles continues to completely dominate the specific heat in the field region above the plateau, although the magnetization increases with increasing field. Ordering is observed at a temperature immediately below the spin-gas regime.

Geometrical frustration is one of the important subjects in strongly correlated systems Ram . In particular, the fascinating interplay of geometrical frustration and quantum fluctuation in two dimensions provides a fertile ground for new physics, as has been theoretically demonstrated for Heisenberg antiferromagnets in the triangular lattice and the kagomé lattice. For the $`S=1/2`$ triangular antiferromagnet, there now appears to be a consensus that Néel order must exist despite the strong frustration Trig . The $`S=1/2`$ kagomé antiferromagnet has been predicted to possess a gap separating the ground state from upper triplet levels and a band of low-lying singlet excitations within the triplet gap, although the exact nature of the ground state is still under debate Kag . These predictions are yet to be borne out by experiment, because no isotropic $`S=1/2`$ model system has been identified in the laboratory for these lattices.

In the last few years, there has been a rapid progress in the understanding of the $`S=1/2`$ Heisenberg antiferromagnet in the Shastry-Sutherland lattice SS , another two-dimensional frustrated geometry, for which the exact ground state is known at zero and low magnetic fields despite geometrical frustration. The progress owes largely to the discovery of the spin gap and other novel magnetic properties in SrCu2(BO3)2 1 , the only known laboratory model for the geometrically frustrated $`S=1/2`$ two-dimensional Heisenberg antiferromagnet.

The low-field ground state of the Shastry-Sutherland antiferromagnet is simply a product of spin-dimer singlet wave functions, and the dimerization by the diagonal bond $`J`$ causes a gap to form SS . The gapped triplet excitations, which are also spin dimers at least to a good approximation, have a large mass as a result of the unique lattice topology involving orthogonal arrangement of dimers Miya ; Zheng2 ; MH ; Miya2 . In SrCu2(BO3)2, the coupling strengths extracted from experiments are $`J=85\mathrm{K}`$ for the intra-dimer exchange and $`J^{}=54\mathrm{K}`$ for the inter-dimer exchange Miya3  or $`J=70\mathrm{K}`$ and $`J^{}=42\mathrm{K}`$ Knet . The large $`J^{}`$ makes the energy gap $`\mathrm{\Delta }`$ substantially smaller than $`J`$ 1 ; C . In fact, the ratio $`J^{}/J`$ is very close to the critical value 0.70 Miya ; MH ; Zheng  for the quantum phase transition to a square-lattice Néel state. In other words, $`J`$ and $`J^{}`$ are extremely frustrated.

The striking feature of SrCu2(BO3)2 is the existence of magnetization plateaus at 1/8, 1/4, and 1/3 of the saturation magnetization 1 ; 2 . Although there is a substantial spin-phonon coupling in this compound Phon , the plateaus are an intrinsic property of Heisenberg spins in the Shastry-Sutherland lattice and due to geometrical frustration Miya ; Mis . The spin state at any magnetization plateau is obviously gapped Oshi , and a possible connection between magnetization plateaus and quantized Hall-conductance plateaus has been pointed out Mis . In contrast, the states between $`H_c`$ and the first plateau, between two adjacent plateaus, and between the highest plateau and the saturation field have been believed to be all gapless by a prevalent view on magnetization plateaus.

In this paper, we examine three field-induced magnetic phases of SrCu2(BO3)2: the one between $`H_c`$ and the first plateau with 1/8 of the saturation magnetization, the plateau phase, and much of the phase between the 1/8 and 1/4 plateaus. The results refute the conventional view on the nature of the first phase and uncover the presence of a two-dimensional spin gas in the other phases, as well as ordering in the third phase.

Prior to our work, two-dimensional Bose gas has been realized in spin-polarized atomic hydrogen adsorbed on the surface of superfluid 4He Mosk . However, the spin gas in SrCu2(BO3)2 is the first example that is amenable to thermodynamic studies.

The calorimeter for this investigation employed the relaxation method Rel . In order to optimize the relaxation time at different temperature and magnetic-field regions, three samples of different sizes were used, all taken from a high-purity single crystal whose growth procedure has been described in Ref. X . The sample sizes were roughly 3 $`\times `$ 3 $`\times `$ 0.07 mm3, 4 $`\times `$ 3 $`\times `$ 0.3 mm3, and 3 $`\times `$ 3 $`\times `$ 1.3 mm3, and the magnetic field was applied parallel to the crystalline c axis, perpendicular to the two-dimensional layers of the $`S=1/2`$ Cu2+ spins. In this field orientation, the spin gap for the $`S_z=+1`$ triplets is split into two branches that are 4.1 K apart ESR ; ESR2  by the Dzyaloshinskii-Moriya interaction DM ; Neutr . According to the g factor measured by ESR ESR , the lower gap is expected to close at $`H_c=\mathrm{\Delta }/\mathrm{g}\mu _\mathrm{B}`$ of 21 T.

The measurements were done primarily in magnetic fields between 22 T and 33 T at temperatures between 0.53 K and 15 K. Additional data were taken at zero field and 14 T for comparison with earlier specific-heat results at magnetic fields up to 12 T C . At zero field, there was excellent agreement between the present data and the earlier result, indicating a high sample quality and reproducibility. The 14 T data precisely follow the field dependence observed in the earlier experiment, with the spin gap decreasing linearly with magnetic field and the position of the broad maximum remaining at 8 K.

Figure 1 shows the specific heat at 22 T and 24 T, where the spin gap is expected to be absent and the ground state is magnetic 1 ; 2 , together with the 14 T result for comparison. The $`T^3`$ phonon contribution to the specific heat has been subtracted from all the data presented in this paper, as determined by Kageyama et al. C  Instead of a broad maximum at 8 K, a new hump appears at 22 T and 24 T at temperatures below 1.4 K. The position of this low-temperature maximum decreases with increasing magnetic field. At 22 T, the low-temperature tail of the hump clearly shows a gapped behavior, whereas the 24 T data do not extend to a sufficiently low temperature.

The overall behavior of the specific heat can be explained in terms of the dimer-quadrumer model of Hofmann et al. Hof , who incorporated the repulsion between triplet spin dimers and bound pairs of triplet dimers as a mean field. The line for 14 T in the figure is a calculation using exactly the same parameters chosen by these authors to fit the specific-heat data at fields up to 12 T. Similar to their fits, the 14 T calculation reproduces the experimental data very well at temperatures below the broad peak.

In order to fit the data at 22 T and 24 T, we have found that it is necessary to allow the gap energy $`\mathrm{\Delta }_+`$ of the $`S_z=+1`$ triplets and the mean-field strength $`v_0`$ of the repulsion term to be fitting parameters V . The best fits shown in the figure are obtained by choosing $`\mathrm{\Delta }_+=4.6\mathrm{K}`$ and 3.2 K for 22 T and 24 T, respectively, and $`v_0=10\mathrm{K}`$ for both fields. The fit at 22 T is good primarily at temperatures below the broad low-temperature peak, whereas the fit at 24 T agrees well with the data up to 4 K. The good overall agreement leads us to conclude that the ground state is gapped at both fields.

The remarkable persistence of the gap in the field-induced magnetic phase contradicts the widely held view that the ground state above $`H_c`$ evolves with increasing magnetic field by simply increasing the number of $`S_z=+1`$ triplets within itself. We propose in contrast that mixing of at least one of the $`S_z=+1`$ triplet levels with the singlet ground state is responsible for the evolution of the magnetization below the 1/8 plateau and for the anticrossing that keeps the gap open even above $`H_c`$. The mixing is probably caused by the Dzyaloshinskii-Moriya interaction. The gap keeps the ground state in a spin-liquid phase with a non-zero magnetization. This explains why the translational symmetry is maintained in this field region even at a temperature as low as 35 mK, as has been found by NMR N . We conclude that the region from zero field up to the lower edge of the 1/8 magnetization plateau is a contiguous phase, with no ordering even at fields above $`H_c`$.

The situation resembles the behavior of the Haldane-gap antiferromagnet NENP, where the staggered g tensor of two non-equivalent Ni sites causes the triplet excitation to anticross the ground state at $`H_c`$ Palme ; End  and magnetization develops with no long-range order due to the inter-chain coupling Katsu . It is interesting to note that isolated triplet spin dimers in the Shastry-Sutherland lattice have been predicted to be unstable below the 1/8 plateau and they cannot be constituents of the ground state in this field region F .

The present result is consistent with the ESR experiments ESR ; ESR2 , which have found no excitation level that reaches the ground state at $`H_c=21`$ T. In fact no such level has yet been discovered up to 40 T. Instead, the behavior of the lower $`S_z=+1`$ branch, and possibly also the upper branch, suggests anticrossing around $`H_c`$ ESR2 .

The fitting parameters are also in good agreement with the ESR data ESR2 , which give $`\mathrm{\Delta }_+=4.8`$ K and 6.6 K for the two branches of excitations at 22 T. The ESR values at 24 T are 5.2 K and 5.5 K. Our value for the repulsion parameter $`v_0=10`$ K at 22 T and 24 T is considerably smaller than 17 K for fields up to 12 T Hof  and at 14 T. This is expected, since the mixing of an $`S_z=+1`$ excited state with the ground state at fields above $`H_c`$ turns it into a more singlet-like object, which experiences less repulsion due to the inter-dimer exchange $`J^{}`$.

Figure 2 shows the specific heat for fields of 27.5 T and higher. 27.5 T corresponds to the midpoint of the 1/8 magnetization plateau, where Cu NMR has found evidence for a rhomboid ordered structure involving $`S_z=+1`$ triplets N . Within our experimental accuracy, the specific heat at this field is 1/8 of the gas constant $`R`$ over a wide temperature range except for a gradual rise at temperatures above 5 K and a small decrease at temperatures below 1 K. This is conclusive evidence that a two-dimensional spin gas is formed by the $`S_z=+1`$ triplets whose number equals 1/8 of the total spin dimers. This conclusion is consistent with the 11B NMR spectra N , according to which the spin superstructure disappears somewhere between 35 mK and 1.5 K. Evidently, the transition from a rhomboid spin solid to the spin gas occurs at a temperature below 0.63 K, our lowest temperature for the plateau region.

The solid line drawn in Fig. 2 through the 27.5 T data points below 5 K is the heat capacity of 1/8 mole of ideal two-dimensional Bose gas BE , with the particle mass being the only fitting parameter. The fit yields a bosonic mass of $`(8.7\pm 1.0)\times 10^{28}`$ kg, which is 960 times the electronic mass. It is 62% of the mass of the lowest triplet excitation, $`(1.4\pm 0.1)\times 10^{27}`$ kg, obtained from a sinusoidal fit of the dispersion measured by inelastic neutron scattering at zero field NeutrK . The similarity of the two masses suggests that the triplet excitations at lower fields are somewhat extended objects N  similar to the ground-state triplets at the magnetization plateau. It is important to note that the thermal de Broglie wavelength of the spin gas at 0.63 K is as large as 1.7 times the average interparticle distance. Hence, the freezing of the spin gas into a rhomboid structure takes place in a highly degenerate regime.

Surprisingly, the specific heat between 29.6 T and 33 T, in the field region above the magnetization plateau, is completely different from that in the region below the plateau and is identical with the 27.5 T data except for the low-temperature anomaly that signals phase transition. In particular, it remains at $`R/8`$ in the mid-temperature range within our experimental accuracy, demonstrating that the same number of particles form a two-dimensional spin gas at these fields as at the plateau. It is natural to conclude that these particles at the two field regions are identical.

On the other hand, the magnetization above the plateau increases continuously with increasing field and reaches a 52% higher value at 33 T 1 ; 2 . It is very unlikely that the extra magnetization is carried by the particles of the spin gas, since $`S_z`$ will then have to be larger than unity and this would require mixing of an $`S_z=+2`$ excited state. A presence of such a state should result in a low-temperature specific-heat hump whose position changes with magnetic field, very much like the behavior shown in Fig. 1 for the field region below the magnetization plateau. We propose that the extra magnetization is carried by additional $`S_z=+1`$ particles that are thermodynamically inert at least up to the highest temperature of this experiment.

Phenomenologically, the particle-number conservation that underlies the two-dimensional gas behavior can be explained by large energy required for excitations that do not conserve the particle number. We believe, however, that this remarkable phenomenon deserves a fundamental explanation, which is presently lacking.

Momoi and Totsuka MT  have predicted that two species of $`S_z=+1`$ bosons compose the state above the 1/3 magnetization plateau, beyond the field region explored by experiments to date. They are those same particles that form the plateau phase and additional particles that condense into a magnetic superfluid, whose density increases with increasing magnetic field. A similar two-species state in the field region above the 1/8 magnetization plateau can explain why the number of particles that make up the spin gas remains the same as in the plateau phase. However, the robustness of the particle number against thermal excitations still remains a mystery.

The sharp transition marked by the low-temperature peak in the specific heat is probably due to freezing of the spin gas Nuc . The strong field dependence of the transition temperature indicates that either the particle mass or the strength of the repulsive interaction increases with the density of the thermodynamically invisible particles. Since freezing in two dimensions is generally a Kosterlitz-Thouless transition KT , which has no signature in specific heat, the sharp peak suggests an importance of spin-phonon coupling or inter-layer spin coupling.

In summary, we have uncovered a distinct spin behavior in each of three high magnetic-field regions of SrCu2(BO3)2. In the region below that of the 1/8 magnetization plateau, where translational symmetry exists, the spin gap remains open, indicating hybridization of at least one of the two $`S_z=+1`$ triplet states with the singlet ground state, which now acquires a magnetic moment. We conclude that there is no phase transition between this region and the low-field, non-magnetic region. The regions at and above the magnetization plateau constitute a second contiguous phase, where those triplets whose number equals 1/8 of the spin dimers form a two-dimensional gas of massive bosons above the field-dependent freezing temperature. In addition, the region above the plateau contains thermodynamically inert particles that carry the magnetization in excess of 1/8 of the saturation value. Further studies are called for to identify these carriers and to elucidate their role in the ordering.

We thank N. Aso, T. C. Kobayashi, G. Misguich, S. Miyahara, Y. Narumi, M. Nohara, H. Nojiri, M. Takigawa, N. Tateiwa, and G. S. Uhrig for useful communications and/or for providing data, some prior to publication. We have benefited from stimulating discussions with E. Dagotto, S. Haas, J. S. Kim, P. Kumar, D. L. Maslov, S. P. Obukhov, and M. Takigawa. The experiment above 22 T was performed at the National High Magnetic Field Laboratory, which is supported by NSF Cooperative Agreement No. DMR-0084173 and by the State of Florida. We thank B. L. Brandt, S. T. Hannahs, T. P. Murphy, and E. C. Palm for their help and hospitality. This work was funded by the NSF through DMR-9802050 and DMR-0104240 and by the MECSST (Japan) through Grant-in-Aid for Scientific Research No. 40302640.