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# Screened Coulomb interactions in metallic alloys: I. Universal screening in the atomic sphere approximation

## I Introduction

The coherent potential approximation (CPA)  as implemented on the basis of multiple scattering theory  and combined with density functional theory (DFT)  constitutes the basis for ab inito calculations of the electronic structure and physical properties of random metallic alloys. This combination of the CPA with DFT, or, in most cases, with the local density approximation (LDA), seems to be quite transparent  leading to expressions for the one-electron potential and total energy which are very similar to those for ordered systems. However, there is, by now, a well-recognized problem  with this description caused by the fact that the atomic or "muffin-tin" spheres, which artificially divide the crystal into regions associated with particular alloy components, may poses non-zero net charges.

The problem stems from the fact that the conventional single-site (SS) DFT-CPA method is based on the effective medium model of a random alloy which considers only conditionally averaged quantities and leads to the use of the single-site approximation not only in the electronic structure part of the problem during the solution of the CPA equations, but also in the DFT self-consistent loop in the calculations of the electrostatic contributions to the one-electron potential and energy. The single-site approximation provides no information as to the charge distribution beyond the atomic sphere of each alloy component and, since the surrounding effective medium is electroneutral, Poisson’s equation cannot be solved properly if the atomic spheres have non-zero net charges. Hence, to find the correct solution to Poisson’s equation one must somehow describe the effect of the missing charge. Since the electron density inside each atomic sphere is well-defined, any such description may be associated with a modification of the effective medium specifically for each alloy component. This may be regarded as an inconsistency since, in that case, the CPA and the electrostatic part of the DFT are based on different effective media.

One obvious solution to the problem is to use electroneutral spheres (see, for instance, Ref. ). However, in the methods based on the atomic sphere approximation (ASA) this frequently leads to large sphere overlaps and a quite poor description of the electronic structure, especially in the case of inhomogeneous system, such as partially ordered alloys or surfaces with an inhomogeneous concentration profile.

A more general solution can be found, however, in which the electrostatic potential is modified without making effective media for each alloy component in contradiction to the assumptions of the CPA. The way to do this is to introduce an additional shift of the one-electron potential due to the electrostatic interaction of the electrons inside each atomic sphere with the missing charge distributed outside of the sphere and postulate that the interaction comes from the boundary between the atomic sphere and the effective medium. Such a shift may be associated with an intrasite interaction, which has no connection, at all, to the effective medium.

This is exactly what is done in the locally self-consistent Green’s function method  where one goes beyond the single-site approximation for Poisson’s equation by means of a supercell which models the spatial distribution of the atoms in a random alloy while a CPA effective medium is used in the electronic structure calculations beyond a local interaction zone (LIZ). If the LIZ consists of only one atom, the LSGF method becomes equivalent to the CPA method with a properly defined electrostatic potential and energy . In this case, however, each atom in the supercell has its own electrostatic shift given by the Madelung potential from all the other atoms in the supercell while the effective medium is the same for all atoms. It is clear that such an additional shift for each alloy component does not interfere with the CPA because the CPA effective medium is determined on the basis of the one-electron potentials including these shifts and because the CPA itself does not impose any restriction on the one-electron potentials of the alloy components.

Following the above arguments two groups have proposed an ad hoc expression for the electrostatic shift of the one-electron potential due to non-zero net charges in the atomic spheres of the alloy . Although the basic models are seemingly different and based on different observations, either i), the net charge of an impurity in a metal is screened beyond the first coordination shell  or ii), the net charge of an alloy component is proportional to the number of the nearest neighbors of the opposite type , they lead to exactly the same expression for the one-electron potential, i.e.,

$$V_i=\frac{e^2q_i}{R_1},$$
(1)
where $`V_i`$ is the additional electrostatic shift of the one-electron potential of the $`i`$-th alloy component of net charge $`q_i`$ and $`R_1`$ the radius of the first coordination shell.

In fact, the models described above are practically identical to the model proposed more than three decades ago  to account for charge transfer effects in the self-consistent Hartree scheme based on the tight-binding CPA. In this scheme the variation of the $`i`$-th atom energy level, $`\delta ϵ_i`$, is proportional to the corresponding charge transfer $`q_i`$, i.e., $`\delta ϵ_i=Iq_i`$, where $`I`$ is some average intra-atomic Coulomb interaction. The non-self-consistent limit corresponds to $`I=0`$, while $`I=\mathrm{}`$ provides local neutrality . In the present context one may identify $`\delta ϵ_i`$ with $`V_i`$ and it therefore follows that $`e^2/R_1`$ may be considered an intrasite Coulomb interaction.

Although there is at least some consensus concerning the definition of the additional electrostatic shift (1), which gives charge transfers quite close to the values obtained in supercell calculations , different workers do not agree on the corresponding electrostatic contribution to the total energy of the random alloy. Some completely deny even the possibility of having such a term in a "consistent" SS-DFT-CPA theory  while others argue about the details of how this term should be defined . It would seem that the presently suggested models of charge transfer effects in the single-site approximation to the electrostatic problem, except the trivial elimination of the net charges by adjusting the radii of the atomic spheres of the alloy components, may be considered neither exact nor even "a consistent theory". It is the main purpose of the present paper to shown that a consistent SS-DFT-CPA theory including a correct description of the charge transfer effects does indeed exist.

Here, we define the electrostatic shift of the one-electron potential and the corresponding contribution to the total energy in a form which is very similar to that proposed by Korzhavyi et al.  as well as Johnson and Pinski , and which provides a practically exact solution to the electrostatic problem in the single-site approximation. The actual expression for the electrostatic shift in the single-site model for Poisson’s equation includes one adjustable parameter the value of which is to be obtained in supercell calculations by the locally self-consistent Green’s function method in which the Madelung problem is solved exactly. It turns out that the value of the adjustable parameter is practically independent of lattice structure, volume, and alloy composition due to the fact that the screening of the electrostatic part of the problem, in the ASA at least, is almost universal.

The paper is organized as follows. In Sec. II we outline the main concepts behind the LSGF used in this work and the details of the calculations. In Sec. III we present a pragmatic solution to the problem of finding the Madelung shift in SS-DFT calculations on the basis of the average values of the net charges and Coulomb shifts, $`<q_i>`$ and $`<V_i>`$, from supercell calculations. We also demonstrate that the linear relation between the net charges, $`q_i`$, and the corresponding Coulomb shifts, $`V_i`$, of the alloy components discovered for metallic alloys by Faulkner et al.  is practically universal in the effective medium approach for the Green’s function. This means that the response of the electron system to the Coulomb field is linear and universal in such systems, and that the screening must be universal too. That this is indeed the case is demonstrated in the next section where we calculate the distribution of the screening charge in several systems and show that it is almost independent of the crystal structure, the alloy constituents, and the composition.

In Sec. V we present a formalism for the screened Coulomb interactions in the single-site mean-field approach for the electrostatic potential and energy and demonstrate that the conventional assumption of a vanishing Madelung potential and energy is not valid in general. Instead, one must include an additional term due to intrasite interactions which are, in fact, exactly the screened Coulomb interactions. We also discuss the ordering contribution to the Madelung energy and show why the screening contribution may be obtained in supercell calculations for ordered structures. The contribution from the screened Coulomb interaction to the generalized perturbation method and the $`S^{(2)}`$ formalism is also determined. Finally, in Sec. VI, we demonstrate that the total energy of a random alloy may be reproduced exactly in single-site CPA-DFT calculations with corrections due to the screening intrasite interaction.

## II Methodology

### A Spatial ergodicity and cluster expansion

In this paper we will consider only such alloy systems that on an underlying crystal lattice with perfect translational symmetry satisfy two conditions: i) spatial homogeneity and ii) no correlations between the one-electron potentials at sufficiently large distances. For the Coulomb interactions in a random alloy both conditions may be formulated explicitly in terms of the average monopole electrostatic potential $`V_i`$ in the atomic sphere around site $`i`$ due to the charge distribution in the whole of the remaining system. In an ordered alloy this potential is the Madelung potential. Specifically, the first condition means that any average values of products of potentials must be translationally invariant, i.e.,

$$<V_iV_j\mathrm{}V_k>=<T_a(V_iV_j\mathrm{}V_k)>,$$
(2)
where $`T_a`$ is the translation operator $`T_af(r)=f(r+a)`$, and the second condition is

$$<V_iV_j\mathrm{}V_kT_a(V_lV_m\mathrm{}V_n)>=<V_iV_j\mathrm{}V_k><V_lV_m\mathrm{}V_n>,$$
(3)
for $`a\mathrm{}`$.

According to Lifshitz et al.  the space formed by the complete set of distinct realizations of the potential $`V_i`$ on the lattice, the operator $`T_a`$, and the property of spatial homogeneity plays the same role in the theory of disorder as the phase space, the operator of dynamical evolution, and Liouville’s theorem do in statistical mechanics. Moreover, according to Birkhoff’s ergodic theorem, for any functional $`f[V_i]`$, where $`V_i`$ is some random realization of the potential on the lattice we have

$$\underset{V\mathrm{}}{lim}\frac{1}{\mathrm{\Omega }}_\mathrm{\Omega }f[T_aV_i]=<f[V_i]>,$$
(4)
i.e., the spatial and the phase-space average are equivalent . This equation constitutes the principle of spatial ergodicity, according to which all possible finite atomic arrangements may be realized in a single infinite sample if the conditions (2) and (3) are satisfied.

What makes the above principle work in practice is the fact that for self-averaging or "measurable" quantities, which have a well-defined limit when the volume of the systems approaches infinity, all the correlations of the atomic distribution become unimportant at some distances and, hence, the sample may be chosen finite. This may be formulated explicitly by means of the cluster expansion theorem  which defines the corresponding measurable quantity in terms of the site occupation correlation functions

$$\mathrm{\Pi }=\pi _0+\underset{f}{}\pi _f\xi _f,$$
(5)
where $`\pi _q`$ are the coefficients or interaction parameters, $`\xi _f=<\delta c_i\delta _j\mathrm{}\delta c_k>`$ the correlation function of the figure or cluster $`f`$ which corresponds to a specific position of the sites $`i`$, $`j`$, and $`k`$ in the lattice, and $`\delta c_i`$ = $`c_i<c_i>`$ is the fluctuation of the site occupation numbers $`c_i`$ taking on values 0 and 1 depending on whether site $`i`$ is occupied by one or the other component.

According to (5) there are two practical ways of calculating the properties of a random system for which we have $`\xi _f=0`$ and, thus, $`\mathrm{\Pi }_{rand}=\pi _0`$: i) the cluster or supercell approach, where $`\xi _f=0`$ is satisfied on average only for those clusters $`f`$ for which $`\pi _f0`$, or ii) the effective medium approach, which directly gives $`\pi _0`$ from some knowledge of the alloy components. The first approach is realized, for instance, in the so-called special quasirandom structure (SQS) method  while the second approach is realized by the coherent potential approximation where the real atoms are substituted by a specifically chosen effective medium on the lattice.

### B The LSGF method: a combined supercell-effective medium approach

The supercell and the effective medium approaches are combined into a single computational scheme in the locally self-consistent Green’s function (LSGF) method . In the LSGF method the supercell approach is used to provide the correct solution to the Madelung problem for a given alloy modeled by an appropriate supercell. It is also used in part in the electronic structure calculations, which are performed separately for every atom in the supercell by means of the local interaction zone centered at each atom. Inside the LIZ the multipole scattering equations are solved exactly, while the region outside the LIZ is represented by the effective medium, which is usually taken to be the CPA effective medium built on all the one-electron potentials in the supercell. This means that every atom of the supercell "sees" only the CPA effective medium outside the LIZ, which according to the CPA definition represents a random alloy. In other words, the one-electron Green’s function of the supercell (sc) obtained in LSGF calculations may be presented as

$$G^{sc}=\underset{i}{}[G_i^0+\underset{f}{}\mathrm{\Delta }G_{if}\xi _{if}^{LIZ}],$$
(6)
where $`G_i^0`$ is the Green’ function of the $`i`$th atom in the supercell embedded in the CPA effective medium, $`\mathrm{\Delta }G_{if}`$ the contribution to $`G_i^0`$ due to the presence of the specific atomic arrangements on the figure $`f`$ in the LIZ as specified by the correlation function $`\xi _{if}^{LIZ}`$, which is equal to that of the supercell $`\xi _{if}^{sc}`$ if the figure $`f`$ is circumscribed by the LIZ, i.e., it can be put inside the LIZ in such a way that one of its vertices coincides with the central atom of the LIZ, otherwise $`\xi _{if}^{LIZ}`$=0.

Equation (6) clearly shows how the LSGF works, and in particular, how the effective medium approach, represented by $`G_i^0`$, is combined with the cluster or supercell approach, represented by by the second term. It follows from (6) that the LIZ allows one effectively to cut off the contributions from the clusters which are not circumscribed by the LIZ (an equivalent formulation in terms of effective interactions is given in Ref. ). If the LIZ is single-site, i.e., it consists of only one atom (LIZ=1), the contributions from the second term in (6) vanish and we are left with the usual CPA or pure effective medium approach to the electronic structure problem. It is this single-site approach, referred to as SS-LSGF, which will be used in most of the present work. It has the advantage over the usual SS-DFT-CPA method that Poisson’s equation is solved exactly within a given approximation for the form of the electron density.

Note, however, that the LSGF method by no means is restricted to the single-site approximation. In fact, it allows us to include local environment effects in the electronic structure calculations for the figures circumscribed by the LIZ if on average $`\xi _f^{<LIZ>}=\xi _f^{sc}=0`$ which is the case in a random alloy. In this respect the LSGF method may be considered a self-consistent embedded cluster method (ECM) of the kind proposed by Gonis et al.  more than two decades ago. With a proper choice of the supercell used to model a given random alloy  the LSGF solves two major problems of the ECM: i) it provides a set of clusters to represent an alloy with a given short range order and ii) it allows one to close the DFT loop with the correct treatment of the electrostatics.

There is one important point concerning the electronic structure obtained in the LSGF with the CPA effective medium which should be mentioned: Despite the fact that it can be quantitatively accurate, it is qualitatively different from the electronic structure which would result from direct supercell calculations with periodic boundary conditions. That is, the electronic spectrum in the LSGF-CPA method is always complex, unless all the atoms are equivalent in the supercell (pure metal) or the size of the LIZ is infinite. Thus, in the LSGF-CPA the electronic structure of an ordered alloy is never correct, although it may be calculated with arbitrarily high accuracy. On the other hand, since Blochs’ theorem is not applied to the supercell during the electronic structure calculations, the LSGF method is a perfect tool for calculating SQS as opposed to the ordinary band structure methods, which in this case lead to a real, i.e., qualitatively incorrect, electronic structure of the random alloys due to the fact they present purely a supercell approach.

### C The choice of the supercell in the LSGF and details of the calculations

It is possible to obtain the Madelung potential and energy by a combined supercell (cluster) and effective medium approach similar to that used in the Green’s function approach to the electronic structure problem within the LSGF method. However, this requires some knowledge of the charge-charge correlations or the screening in the alloy. Hence, the only way to solve the problem is to use a supercell model with the Madelung potential and energy determined exactly from the bare electrostatic interactions, as it is usually done. Here, another problem arises: The supercell should be constructed such as to provide zero correlation functions up to the distance where the net charges of the alloy components become uncorrelated or completely screened.

In the calculations presented below we assume at the outset the existence of a short-range screening which occurs over the distance of the first several coordination shells. This assumption is based on results obtained by the charge-correlated model , on single-impurity calculations  as well as on the most recent LSGF calculations by Ujfalussy et al. . The latter authors demonstrated that a 16-atom supercell for an fcc equiatomic random alloy, in which the SRO parameter at the 8’th coordination shell must be equal to 1 due to the translation symmetry, i.e., all the atoms in the 8’th coordination shell are the same as that at the central site, yields practically the same average charge transfer and total energy as a 250-atom supercell, in which the SRO parameter at the 8’th coordination shell corresponding to a random number generator distribution of the alloy components on the lattice should be $`<<`$ 1 (see also ).

Thus, in all the random alloys considered below the distribution of the atoms in the supercell was chosen such that the SRO parameters (or pair correlation functions, $`\xi _f^{(2)}`$) were exactly zero at least in the first 6 coordination shells and small (not greater 0.01 in absolute value) up to the 8th coordination shell. Although the multisite correlation functions have not been optimized, they should not play a significant role in the ASA where only monopole intersite Coulomb interactions are taken into account.

The electronic structure calculations were in all cases performed in the scalar relativistic approximation by the KKR-ASA technique  with an $`s`$-, $`p`$-, and $`d`$basis in the framework of either the usual SS-DFT-CPA or the LSGF methods with a CPA effective medium. The ASA (no multipole corrections to the Madelung potential and energy) has been used in the electrostatic part of the problem. The integration of the Green’s function over energy was performed in the complex plane over 16-20 energy points on a semicircular contour. The local density approximation was used in the DFT part with the Perdew and Zunger  parameterization of the results by Ceperly and Alder .

## III Net charge and Madelung potential in metallic alloys

Here we discuss a pragmatic solution to the following problem: Can one devise a Madelung potential for the alloy components to be used in SS-DFT-CPA calculations such that the charge transfer effects, i.e., the net charges of the alloy components, are consistent with those obtained in SS-LSGF calculations where charge transfer effects are treated properly? The fact, that such a potential can be found, may seem surprising in view of the principle difference between the LSGF and the SS-DFT-CPA methods. In the LSGF approach all the atoms in the supercell are different due to their different local environment while in the usual SS-DFT-CPA approach one deals only with average quantities, i.e., in terminology of the Ref. , the LSGF supercell approach is equivalent to the polymorphous model of the alloy while the effective-medium approach is equivalent to the isomorphous model. However, it is obvious, that this can be done on average.

It was discovered by Faulkner et al.  from supercell calculations that the net charges on different sites $`i`$, $`q_i`$, and the corresponding Madelung potentials, $`V_i`$, obey a linear relationship. In Fig. 1 we show such a $`qV`$ relation for a 512-atom supercell which models a random Al<sub>50</sub>Li<sub>50</sub> alloy on an underlying fcc lattice. For comparison we also show the charge and Madelung shift for AlLi in the ordered L1<sub>0</sub> structure. All results are obtained by LSGF calculations with the CPA effective medium in i) the single-site approximation for the electronic part of the problem, SS-LSGF, i.e., LIZ=1, (upper panel) and ii) with the perturbation in the electronic structure caused by the local environment up to the second coordination shell, i.e., embedded cluster(EC)-LSGF, LIZ=3,(lower panel), included in the Green’s function. For random alloys the inclusion of more distant coordination shells do not affect the results significantly and thus the LIZ=3 results may be considered to be converged in the LIZ size.

The most striking feature of the $`qV`$ relation obtained in the SS-LSGF calculations is the perfect alignment of the $`qV`$ points along two almost straight lines, one for each alloy component. This is, in fact, very similar to what has been observed by Pinski  in model calculations using the Thomas-Fermi approximation. Furthermore, a change of the ratio of the atomic sphere radii of the alloy components, $`r=S_{Al}/S_{Li}`$, leads to a rescaling of the $`qV`$ points. Hence, for a specific ratio, $`r=1.12`$ in the present case, the $`qV`$ relation collapses into the single point: $`(q,V)=(0,0)`$. The existence of this point in the SS-LSGF is a consequence of the fact that all Al atoms as well as all Li atoms become indistinguishable if the net charges of the alloy components are zero: The difference between the atoms caused by local environment effects is solely due to the Madelung shift, which is zero in this case. Thus, for this particular choice of $`r`$ the polymorphous model is identical to the usual isomorphous model, or the SS-LSGF method is identical to the SS-DFT-CPA method.

On the other hand, it is clear that the two models are not equivalent when local environment effects are included in the electronic structure part of the LSGF method, i.e, for LIZ$`>`$1. This is demonstrated in the lower panel of Fig. 1 where the local environment effects are clearly seen to destroy the strict alignment of the $`qV`$ points and, as consequence, the possibility of choosing electroneutral atomic spheres by a single $`r`$ value. However, even if this were possible, all the atoms, or the corresponding one-electron potentials, would still be different.

The discussion of local environment effects is beyond the scope of the present paper, and the results are included only to demonstrate the qualitative difference between the correct results and those obtained by the LSGF method in the single-site approximation: Inclusion of intersite correlations in the electronic structure calculations leads to a real polymorphous description of random alloys which cannot be mimicked by a single-site LIZ. As a consequence, as we will show later the SS-DFT-CPA method can reproduce the results of the SS-LSGF exactly, but will, in general, reproduce only approximately the correct solution to the supercell or polymorphous model of a random alloy.

The two $`qV`$ points for the ordered L1<sub>0</sub> structure are seen to fall on the $`qV`$ lines for the random alloy as already noted in Ref. ), and, in fact, all the points on the $`qV`$ relation obtained by the SS-LSGF method may be reproduced by a series of ordinary SS-DFT-CPA calculations, by using the shift of the one-electron potential defined in a way similar to (1), i.e.,

$$V_i=\alpha \frac{e^2q_i}{S},$$
(7)
where $`q_i`$ is the net charge of the alloy components, $`S`$ the Wigner-Seitz radius, and $`\alpha `$ a parameter which may be varied arbitrarily in the SS-DFT-CPA calculations without specifying its physical meaning. However, it is important to note, that $`\alpha =\mathrm{}`$ corresponds to the electroneutral case ($`q_i=0`$) and $`\alpha =0`$ to the limit where there is no response of the system to charge transfer effects. As we will see later, the values of the net charges $`q_{0i}`$ obtained in the SS-DFT-CPA calculations with $`\alpha =0`$ are important scaling parameters. It is also useful to note, that for the L1<sub>0</sub> structure $`\alpha _{L1_0}`$=0.8811575 , and in the screened impurity model (1) $`\alpha _{SIM}=`$ 0.552669 and 0.568542 for the fcc and bcc crystal structures, respectively.

Fig. 1 shows the $`qV`$ relation, indicated by the black line, obtained in the SS-DFT-CPA calculations including (7) with $`\alpha `$ varying from $``$1.5 to 5 together with the SS-LSGF results, gray circles. It is clearly seen that the "isomorphous" and polymorphous $`qV`$ relations coincide, and this allows one to make an isomorphous model consistent with the polymorphous results. The point is that all the net charges and corresponding Coulomb shifts in the polymorphous model have significance only in terms of the average values they produce. This is so, because every supercell has its own set of net charges and Madelung shifts and, in the case of an infinite system, there is an infinite number of different $`qV`$ points. Their average values, $`<q_i>`$ and $`<V_i>`$, however, have a well-defined physical meaning as conditional averages of self-averaging quantities, and thus it is the average $`<qV>`$ point which must be reproduced by the isomorphous model. Hence, for a random alloy $`\alpha `$ is given by

$$\alpha _{rand}=\frac{S}{e^2}\frac{<V_i>}{<q_i>}.$$
(8)
Note, that in a binary AB alloy, it clearly does not matter, for which alloy component, $`i=A,B`$, $`\alpha _{rand}`$ is determined, since $`<V_A>/<q_A>=<V_B>/<q_B>`$ . The same is true for multicomponent alloys, but in this case, rather than being a trivial consequence of the charge neutrality condition, it follows from the physical origin of $`\alpha _{rand}`$, which will be discussed in the next two sections. For an fcc Al<sub>50</sub>Li<sub>50</sub> alloy at $`S`$=2.954 a.u. we find from the LSGF calculations $`\alpha _{rand}=`$0.60716.

Of course, the coincidence of ($`<q_i>,<V_i>`$) is a necessary, but not sufficient condition for the equivalence of the isomorphous and polymorphous models. The two models may be called equivalent only if the electronic structure of the random alloy and its conditional averages agree. In Fig. 2 we show that this is indeed the case: The local densities of states (DOS) for the Al and Li atoms in Al<sub>50</sub>Li<sub>50</sub> calculated by the SS-DFT-CPA method coincide with the corresponding conditional average state densities obtained in the SS-LSGF calculations for the 512-atom supercell. For comparison we also show the DOS obtained with $`\alpha =`$0 corresponding to the "conventional" CPA. Although the latter differs from the correct state density, it is obvious, that the neglect of the electrostatic shift (7) has only a minor effect on the DOS.

The reason why the average state densities coincide is the following: In the SS-LSGF method the difference between the atoms of the same type comes only through the corresponding Madelung shift. A shift in potential leads to a change in the charge transfer through a skewing  of the local DOS as seen in fig. 3. Therefore, when the conditionally averaged DOS is obtained, the skewing contributions from the individual atomic sites caused by $`V_i`$ will cancel and leave only the DOS given by the average $`<V_i>`$. Of course, this is true only in the SS-LSGF method (LIZ=1). In fact, the local environment effects in concentrated random alloys may influence quite strongly the electronic structure of the central site of the LIZ.

To investigate how the $`qV`$ relation depends on the system we show in Fig. 4 $`qV`$ relations for five different systems including a Cu impurity in Pt ($`S=`$ 3 a.u.) and four random alloys: fcc Cu<sub>50</sub>Pt<sub>50</sub> ($`S=`$ 3 a.u.), fcc Al<sub>50</sub>Li<sub>50</sub> ($`S=`$ 2.954 a.u.), bcc Cu<sub>50</sub>Zn<sub>50</sub> ($`S=`$ 2.7 a.u.), and ternary fcc Cu<sub>50</sub>Ni<sub>25</sub>Zn<sub>50</sub> ($`S=`$ 2.65 a.u.). In the plot all charges have been normalized by $`q_{0i}`$ obtained in the no response limit, i.e., $`\alpha =0`$ or $`V_i=0`$, and all Madelung shifts have been normalized by $`q_{0i}/S`$. To partly simplify the plot we have used $`|q_{0i}|`$ in the normalizations, thereby separating the $`qV`$ relations into two lines rather than one.

The results presented in Fig. 4 show the existence of a universal $`qV`$ relation. Or in other words, the linear-response function $`\chi `$ which gives the change in the net charge relative to $`q_{0i}`$ caused by $`V_i`$, i.e., $`q_iq_{0i}=1/e^2\chi V_iS`$, is a universal constant in metallic alloys in the ASA. From the results presented in the figure we find that $`\chi `$0.63. This unavoidably leads to the existence of a single, unique $`\alpha _{rand}`$ as witnessed by the coincidence of all the $`<qV>`$ points in Fig. 4. Strictly speaking, the slopes of the $`qV`$ lines are not exactly identical and, in fact, $`\alpha _{rand}`$ varies from 0.6 in Cu<sub>50</sub>Zn<sub>50</sub> and Cu<sub>50</sub>Ni<sub>25</sub>Zn<sub>50</sub> to 0.615 in LiMg alloys, not included in the figure. However, for most practical purposes the choice $`\alpha _{rand}=0.607`$ provides a sufficiently accurate description of the electronic structure of random alloys in the SS-DFT-CPA method in the ASA for the electrostatic part.

## IV Screening charge in metallic alloys

In the previous section we have, in effect, defined a procedure whereby SS-DFT-CPA calculations may provide the exact solution to the electrostatic problem in random alloys. The only requirements are that the Madelung shift (7) is included and that the constant $`\alpha _{rand}`$ is obtained from (8) with the average Madelung potential and net charges of the alloy components determined in supercell calculations by the SS-LSGF method. In the derivation of the procedure we have used some general arguments which do not clarify the physical origin of the universal value of $`\alpha _{rand}`$. However, it is clear, that (7) accounts for the missing charge $`q_i`$ in the single-site Poisson equation for the $`i`$’th atomic sphere. Thus, $`\alpha _{rand}`$ must be connected to the screening.

The linear character of the $`qV`$ relation indicates that the screening in the impurity case as well as in the case of a random alloy may be very well described by linear response theory. Owing to enhanced electron scattering at opposite regions of the Fermi surface linear response predicts in the case of a free-electron gas the existence of long-range Friedel oscillations, which however decrease relatively fast ($`r^3`$) with the distance. In a random alloy, on the other hand, the screening is much more efficient due to the finite life time of the Bloch states for the underlying crystal lattice and the spatial distribution of the screening density decays exponentially. In this respect charge correlated model  adopted by Johnson and Pinski  in the cc- and scr-CPA method or the equivalent screened impurity model  may be viewed as the first approximations for the screening.

Based on the fact, that a single impurity in a metallic host is a particular case of a dilute random alloy, one would expect, and the results for a single Cu impurity in Pt presented in the previous section unambiguously indicate this, that the screening effects in the two cases are similar. It is therefore surprising that Faulkner et al.  and Ujfalussy et al.  claim that the screening in a random alloy is qualitatively different from that found in a single impurity system. In fact, these authors found extremely long-range correlations between the Madelung potential at some particular site and the net charges at the other sites. Since the Madelung shift on a site is proportional to the net charge on the site, this may happen only if there are extremely long-ranged correlations between net charges or, in other words, there is no screening. However, this result has been obtained on the basis of summations of the direct or bare Coulomb interactions which is, at best, an ill-defined procedure, even mathematically.

To clarify the issue of screening we will perform the following computer experiment which will allow us to establish the range of the net-charge correlations or the screening in random alloys for one particular site. We set up a 512-atom supercell which represents an fcc Cu<sub>50</sub>Pt<sub>50</sub> random alloy (all SRO parameters are equal to zero up to the sixth coordination shell and $``$ 0 for at least the next 10 coordination shells) and perform self-consistent SS-LSGF (LIZ=1) and EC-LSGF (LIZ=3) calculations. We then substitute one Pt atom with one Cu atom in some site which, in general, may be chosen arbitrarily. However, to keep the atomic distribution as close as possible to the random distribution we chose a site the local environment of which corresponds to the random alloy (having equal number of Cu and Pt atoms) for the first three coordination shells. We then repeat the self-consistent LSGF calculations for the supercell with the substituted atom and find new values for the net charges in the supercell. It is clear that, when LIZ=1, the difference between the net charges in the two calculations, $`\mathrm{\Delta }q_i`$, gives the charges induced by the change of the net charge at the substitution site (in the case of LIZ=3 the local environment effects also effect the charge transfer). This charge is simply the screening charge.

In the upper panel of Fig. 5 we have plotted the normalized, induced charges

$$Q_i=\frac{\mathrm{\Delta }q_i}{\mathrm{\Delta }q_0}$$
(9)
at the first eight coordination shells around the substitution site $`i=0`$ for Cu-Pt substitution in a Cu<sub>50</sub>Pt<sub>50</sub> random alloy and for Cu-Pt substitution in pure Pt ($`S=`$ 3 a.u.) obtained in the single-site approximation for the electronic structure (LIZ=1) as well as with local environment effects included (LIZ=3). One may see that, while the local environment in a pure metal hardly affects the distribution of the net charges, it does introduce a dispersion in the distribution of the net charges in the random alloy, which is quite substantial at the first coordination shell but which practically disappears beyond the 5’th coordination shell where, in fact, all the induced charges almost vanish.

To demonstrate that the net charge of the Cu "impurity" indeed becomes screened we show in the lower panel of Fig. 5 the total normalized induced charge in the $`i`$’th shell

$$Q_{tot}^i=\underset{j=0}{\overset{i}{}}z_jQ_j,$$
(10)
where $`z_j`$ is the coordination number of the $`j`$’th shell. I is seen that $`Q_i`$ vanishes beyond the 7’th coordination shell in all cases, and we conclude that the screening in a random alloy in the single-site approximation is practically the same as the screening in the case of a single impurity in a pure metal. There is neither qualitative nor quantitative differences between the impurity and the alloy cases.

In the upper panel of Fig. 6 we show the distribution of the screening charge (not to be confused with the screening density: the screening charge is, in fact, the screening density integrated in the corresponding atomic sphere) for a Cu impurity in fcc, bcc, and bct Pt plotted as a function of the distance from the impurity site in units of the Wigner-Seits radius, $`S`$. It is clear that the screening charge follows a single, common curve which does not depend on the structure. In fact, by changing the $`c/a`$ ratio in the bct structure one may completely fill the remaining gaps in the calculated curve. In the lower panel of the figure we have collected the results for the distribution of the screening charges in seven different systems including such hosts as Pt, Al, Cu, V, Na, and K. It appears that the screening in metallic alloys depends neither on the crystal structure nor on the nature of the alloy components, at least, when described within the ASA.

The universal picture of the screening in alloy systems found above is partly destroyed when the electrostatics is treated more correctly, for instance by including multipole moment contributions to the one electron Madelung potential and energy. However, the ASA still gives a qualitatively correct picture and catches the main physics behind the phenomenon. Hence, it is worth to discuss the origin of such a universality in both the screening and the response function.

First of all, it was understood long time ago that the net charges in the atomic spheres of the alloy components has very little in common with the "charger transfer" in terms of the redistribution of the electron charge between the alloy components (see, for instance Ref. ). Even in the case of the so-called ionic solids the self-consistent charge distribution is very close to that obtained from a linear superposition of the free-atom electron-densities  and this is the reason for the success of the charge-correlated model , in which the net charge is proportional to the number of nearest neighbors of the opposite type (see also Ref. ).

What we are seeing is basically a size effect: The net charges originate from the redistribution of the electron density in the interstitial region between the atomic spheres. The electron density in metals and their alloys in this region is very smooth and may be well described by a free-electron model, even for transition metal alloys. The interstitial density is much easier to perturb than the density closer to the atomic nuclei and it participates in the screening. On this basis one may, in fact, developed a model based on linear response theory which leads to a semi-analytical description of the universal screening. However, this is beyond the scope of the present paper.

The calculated distribution of the screening net charge may be used to obtain the screening contribution to the one-electron potential in the single-site model for the Poisson equation given by (7) with $`\alpha `$ equal to

$$\alpha _{scr}=\frac{S}{e^2}\underset{i}{}z_i\frac{Q_i}{R_i},$$
(11)
where $`R_i`$ is the radius of the $`i`$’th shell with coordination number $`z_i`$. Using the results for the screening charge, $`Q_i`$, in the case of Cu-Pt substitution for one particular site (not on average!) in the Cu<sub>50</sub>Pt<sub>50</sub> random alloy we find from (11) after summation up to the 8’th coordination shell that $`\alpha _{scr}`$ = 0.60572. At the same time, the average values of the net charges and the Madelung potentials, $`<q>`$ and $`<V>`$, in conjunction with (8) gives $`\alpha _{rand}`$ = 0.60530. That is, $`\alpha _{rand}=\alpha _{scr}`$. Since, there is only one effective medium in the supercell LSGF calculations, it is obvious that the screening is the same for all the sites and, thus, should not depend on the alloy component, that is, the ratio $`<V_i>/<q_i>`$ does not depend on the alloy components.

It is important to understand that $`\alpha _{rand}`$ appears in the formalism due to the intrasite interactions between the electron density inside an atomic sphere and its screening (or missing) charge. Therefore the inclusion of (7) in SS-DFT-CPA calculations does not in any way contradict the "conventional" mean-field picture according to which the contribution from intersite interactions to the Madelung potential is zero in the SS-DFT-CPA. In fact, neglecting the term will lead to incorrect results. On the other hand, the parameter $`\alpha _{L1_0}`$ which allows one to perform SS-DFT-CPA calculations identical to those of the SS-DFT-CPA for the L1<sub>0</sub> structure, has an origin different from that of $`\alpha _{scr}`$ determined by (11). The former is a constant, which apart from the $`L1_0`$ symmetry does not depend on anything, and in particular, not on the screening, while the latter is a system dependent parameter which is entirely determined by the type of intersite interactions or the screening in a given system.

This means that there is no connection between the Madelung constants for ordered structures and $`\alpha _{scr}`$. The reason why it is possible to obtain $`\alpha _{scr}`$ from the supercell calculations for the completely ordered structures, as we have just done, is the fact that at the large distances, where the atomic-distribution correlation-functions are not zero anymore, the "real" intersite interactions do not contribute to the electrostatics due to the short-ranged screening. We will return to this point in the discussion of the Coulomb energy of a random alloy, but here we would like to comment on the use of the single-site approximation in the Green’s function calculations.

Our LSGF calculations of impurities in different metals indicate that the problems observed in the single-site Green’s function impurity calculations by Stefanou  and Drittler et al.  do not originate from the single-site approximation for the Dyson equation, but from Poisson’s equation, which these authors also solve in the single-site approximation. The use of the screening electrostatic shift for the one-electron potential allows one to solve the impurity problem in the single-site Green’s function formalism in the ASA or in the MT approximation almost exactly. This is so because the impurity case corresponds to the dilute limit of a random alloy where the concentration of one of the alloy components approaches zero. In this case, the contribution to the electronic structure due to the local environment effects becomes negligible, and the electronic structure of the impurity obtained by the single-site or the cluster Dyson equations become almost identical. Such an effect may be seen, for instance, in Fig. 5: The dispersion of the screening net charge found in the concentrated alloy case, i.e., Cu<sub>50</sub>Pt<sub>50</sub> (LIZ=3), vanishes in the case of a Cu impurity in Pt. The effect is, in fact, the origin of the increasing accuracy of the CPA with decreasing concentration of one of the alloy components.

## V Screened Coulomb interactions

### A The Madelung energy of a random alloy in the single-site mean-field approximation

The formalism describing the electrostatics of random alloys in the single-site mean-field approximation, where all the A and all the B atoms are represented only by the appropriate conditional averages, is indeed a trivial one, although it has remained quite a confusing issue for more than 30 years, starting from the definition of the electrostatic energy of a random alloy given by Harrison in 1966 in connection with pseudopotential theory . According to Harrison the Madelung energy, which may be associated with the electrostatic interactions of the net charges of the ions of a random A<sub>c</sub>B<sub>1-c</sub> alloy, is given by

$$E_{Mad}^{randss}=\frac{e^2}{2}\frac{\alpha _0}{S}c(1c)(Z_AZ_B)^2+\frac{e^2}{2}\frac{\alpha _M}{S}\stackrel{~}{Z}^2,$$
(12)
where $`Z_i`$ are the ion charges of the alloy components, $`\alpha _M`$ is the Madelung constant of the underlying lattice, $`S`$ the radius of the Wigner-Seitz sphere, $`\stackrel{~}{Z}`$ the average charge equal to $`cZ_A+(1c)Z_B`$, and $`\alpha _0`$ some constant.

Equation (12) was, in fact, not derived specifically for Coulomb interactions. Rather, it was suggested on the basis of a more general consideration of the band-structure contribution to the total energy of a random alloy within second order perturbation theory. Later, it was shown by Krasko  that in a system with randomly distributed A and B ions, having charges $`Z_A`$ and $`Z_B`$, respectively, embedded in a medium of compensating charges, the electrostatic energy included only the second term in (12) while the first term vanished.

It is obvious that (12) is valid also in the CPA-DFT if one substitutes the ion charges $`Z_i`$ by the net charges $`q_i`$ of the atomic spheres. In the ASA the average charge $`cq_A+(1c)q_B`$ is zero, and in this particular approximation the contribution to the Madelung energy of a random alloy given by the second term in (12) will also vanish. Note, however, that the term vanishes neither in inhomogeneous systems  nor in the MT-approximation .

This result was criticized by Magri et al.  who a decade ago deduced from calculations for ordered compounds that the net charge of the atomic sphere of an alloy component is proportional to the number of nearest neighbors of the opposite type, and on this basis developed the charge correlated model in which the Madelung energy of a binary random alloy is given by

$$E_{Mad}^{randss}=\frac{e^2}{2}\frac{\alpha _{cc}}{S}c(1c)(q_Aq_B)^2,$$
(13)
where $`\alpha _{cc}`$ is a constant equal to 0.5947049 and 0.60817846 for the fcc and bcc structures, respectively. Exactly the same result has been obtained later by Korzhavyi et al.  and by Johnson and Pinski  in their "screened" models for the single-site CPA-DFT. The difference between these models lies only in the way the parameter $`\alpha _{cc}`$ is determined (from 0.4397212 for bcc in Ref.  to 0.54282038 for fcc in Ref. ). A discussion of the issues involved may be found in Refs. .

It is certainly surprising, that (13) is exactly the first term in (12) which was shown to vanish in the case of two charges, here $`q_A`$ and $`q_B`$, randomly distributed on an underlying lattice in a compensating homogeneous effective medium. This means that either the models are inconsistent with general theory or that there should be some reason, not accounted for in the derivation by Krasko, for the presence of the first term in (12).

Assuming the existence of only on-site and pair-wise interactions the Hamiltonian of a binary A<sub>c</sub>B<sub>1-c</sub> alloy may be written

$`H`$ $`=`$ $`{\displaystyle \underset{R}{}}[ϵ_0^Ac_R+ϵ_0^B(1c_R)]+{\displaystyle \frac{1}{2}}{\displaystyle \underset{RR^{}}{}}[v_{RR^{}}^{AA}c_Rc_R^{}+v_{RR^{}}^{AB}(1c_R)c_R^{}`$ (14)
$`+`$ $`v_{RR^{}}^{AB}c_R(1c_R^{})+v_{RR^{}}^{BB}(1c_R)(1c_R^{})],`$ (15)
where $`ϵ_0^X`$ are on-site or intrasite interactions, which we will assume depend only on the type of atom on site $`R`$, $`v_{RR^{}}^{XY}`$ are pair potentials acting between X and Y atoms at site $`R`$ and $`R^{}`$, respectively, and $`c_R`$ is the site-occupation operator taking on the value 1 if there is an A atom on site $`R`$ and 0 otherwise. Using $`\delta c_R`$, defined by $`c_R=c+\delta c_R`$, we may rewrite the Hamiltonian in the equivalent form

$$H=\frac{1}{2}\underset{R,R^{}}{}V_{RR^{}}\delta c_R\delta c_R^{}+\frac{1}{2}\underset{RR^{}}{}[c^2v_{RR^{}}^{AB}+2c(1c)v_{RR^{}}^{AB}+(1c)^2v_{RR^{}}^{BB}],$$
(16)
where the first term includes the intrasite interaction ($`R=R^{}`$)

$$V_{R=0}=2[\frac{1}{(1c)}ϵ_0^A+\frac{1}{c}ϵ_0^B]$$
(17)
as well as the intersite interactions ($`RR^{}`$)

$$V_{RR^{}}=v_{RR^{}}^{AA}+v_{RR^{}}^{BB}2v_{RR^{}}^{AB}.$$
(18)
Upon Fourier transformation of the first term we find

$`H`$ $`=`$ $`{\displaystyle \frac{N}{2\mathrm{\Omega }_{BZ}}}{\displaystyle _{BZ}}𝑑qV(q)c_qc_q^{}+{\displaystyle \frac{1}{2}}{\displaystyle \underset{RR^{}}{}}[c^2v_{RR^{}}^{AB}+2c(1c)v_{RR^{}}^{AB}+(1c)^2v_{RR^{}}^{BB}],`$ (19)
where the second term is the average contribution to the energy due to pair interactions which in the case of direct Coulomb ion-ion interactions is $`q_xq_y/|𝐑𝐑^{}|`$ combined with the corresponding contribution from the interaction between the ions and the homogeneous compensating charge. This is exactly the second term in (12).

The first term in (19) is usually associated with the configurational contribution to the energy of the system, but this is correct only if the contribution from intrasite interactions is zero. It is easily evaluated in a completely random alloy, where all the occupation numbers are uncorrelated and therefore $`c_qc_q^{}=c(1c)/N`$ (which provides the normalization of the ordering energy per atom). One finds

$$_{BZ}𝑑qV(q)c_qc_q^{}=c(1c)_{BZ}𝑑qV(q)=\mathrm{\Omega }_{BZ}c(1c)V_{R=0},$$
(20)
which according to (14) is equal to $`cϵ_0^A+(1c)ϵ_0^B`$.

It now remains to define the on-site interaction term $`ϵ_0^i`$, which results from the interaction of the net charge $`q_i`$ in the alloy with the corresponding screening charge, in such a way that $`ϵ_0^i`$ and the corresponding on-site Coulomb potential $`V_i`$ given by (7) are consistent within DFT, i.e., $`V_i=\delta ϵ_0^i/\delta q_i`$:

$$ϵ_0^i=\frac{e^2}{2}\frac{\alpha _{scr}}{S}q_i^2.$$
(21)
Using this definition the first term in the Hamiltonian (19) may be written

$`E_{Mad}^{randss}=E_{Mad}^{scrss}`$ $`=`$ $`{\displaystyle \frac{e^2}{2}}{\displaystyle \frac{\alpha _{scr}}{S}}[cq_A^2+(1c)q_B^2]={\displaystyle \frac{e^2}{2}}c(1c){\displaystyle \frac{\alpha _{scr}}{S}}(q_Aq_B)^2`$ (22)
$``$ $`c(1c)V_{scr}(R=0),`$ (23)
which is exactly the first term in (12) and which, according to the above derivation, arises from on-site or intrasite interactions such as the screening interactions in metallic alloys.

It is now clear why the first term in (12) is absent in the work by Krasko: His derivation is based on inter-site Coulomb interactions only. Thus, Krasko’s result is valid in the absence of the screening intrasite interactions, which is the case, for instance, in the pseudopotential formalism within second order perturbation theory . However, at the same time Harrison’s result is in fact correct under the more general assumptions needed in the SS-DFT-CPA calculations.

### B The configurational part of the Madelung energy and potential

The previous section may seem trivial: First we define our inter- and intrasite interactions in real space, then we Fourier transform, and from the Fourier transform we return to the initially defined intrasite term. However, in some formalisms, such as pseudopotential theory or the $`S^{(2)}`$ formalism , $`V(q)`$ is already defined and this may lead to problems with the correct definition of the configurational part of the total energy. The point is that the intrasite interactions do not contribute to the configurational part of the total energy which in real space may be written as (here, we do not consider the contribution from multi-site interactions)

$$H_{conf}=\frac{1}{2}\underset{RR^{}}{}V_{RR^{}}\delta c_R\delta c_R^{}.$$
(24)
Therefore, if the configurational Hamiltonian is written in terms of $`V(q)`$, e.g., in the concentration wave formalism, it must be corrected by the subtraction of the corresponding intrasite interaction, i.e.,

$`H_{conf}`$ $`=`$ $`{\displaystyle \frac{1}{2\mathrm{\Omega }_{BZ}}}{\displaystyle _{BZ}}𝑑qV(q)c_qc_q^{}{\displaystyle \frac{1}{2}}c(1c)V_{R=0}`$ (25)
$`=`$ $`{\displaystyle \frac{1}{2\mathrm{\Omega }_{BZ}}}{\displaystyle _{BZ}}𝑑q[V(q)V_{R=0}]c_qc_q^{},`$ (26)
where we have used the sum rule for the concentration wave density $`c_qc_q^{}`$: $`_{BZ}𝑑qV(q)c_qc_q^{}=\mathrm{\Omega }_{BZ}c(1c)`$.

The subtraction of the intrasite term in (25) is crucial for obtaining the correct ordering energy in pseudopotential theory and the $`S^{(2)}`$ formalism  as well as for making the whole theory consistent. Let us, for instance, consider the Madelung energy of a binary completely ordered alloy with two non-equivalent sublattices. It is easy to show that its Madelung energy can be presented exactly in the form (12). For instance, the Madelung energy of the L1<sub>0</sub> ordered phase is

$$E_{Mad}^{L1_0}=\frac{e^2}{2}\frac{\alpha _{L1_0}}{S}c(1c)(q_Aq_B)^2+\frac{e^2}{2}\frac{\alpha _{fcc}}{S}\stackrel{~}{q}^2,$$
(27)
where the last term is zero in the ASA since $`\stackrel{~}{q}`$=0 as in the random alloy case, but now $`\alpha _{L1_0}`$ is a constant which appears due to the intersite Coulomb interactions. In the Appendix of Ref.  it is shown that, in fact, $`\alpha _{L1_0}(q_Aq_B)^2/S`$ is the Fourier transform of the effective direct electrostatic interaction at the corresponding superstructure vector $`k_{L1_0}=2\pi /a(100)`$, i.e., $`V_{es}(k_{L1_0})=\alpha _{L1_0}(q_Aq_B)^2/S`$.

On the other hand, $`E_{Mad}^{L1_0}`$ may also be found as the sum of the electrostatic energy of the completely random alloy, $`E_{Mad}^{randss}`$, given by (22) and the ordering energy, $`\mathrm{\Delta }U`$: $`E_{Mad}^{L1_0}=E_{Mad}^{randss}+\mathrm{\Delta }U`$. Since the Madelung energy of the ordered L1<sub>0</sub> alloy, $`E_{Mad}^{L1_0}`$ is uniquely defined in terms of the corresponding Madelung constant, which has nothing to do with the screening in the alloy, it is obvious that such a screening term must be present in the ordering energy, $`\mathrm{\Delta }U`$, to compensate the screening contribution.

Indeed, as shown in the Appendix of Ref.  the ordering energy in the L1<sub>0</sub> structure can be written in the form as

$$\mathrm{\Delta }U_{Mad}=\frac{1}{8}\eta ^2[V_{es}(k_{L1_0})V_{scr}(R=0)],$$
(28)
from which it is easy to see that in the in the completely ordered state, where the long range order parameter $`\eta `$=1, the last term in (28) is exactly the Madelung energy of random alloy at the stoichiometric composition ($`c(1c)`$ = 1/4), and thus $`E_{Mad}^{randss}+\mathrm{\Delta }U=1/8\alpha _{L1_0}(q_Aq_B)^2/S`$.

This illustrates an important point: The ordering energy represented in reciprocal space in the concentration wave formalism must be corrected by the exclusion of the intrasite term, otherwise the theory will not be consistent. Equation (25) gives the correct definition of the ordering energy considered more thoroughly in the Appendix of Ref. . The intrasite interaction must also be subtracted when one considers the energy of SRO effects, and thus the correct Krivoglaz-Clapp-Moss expression must have $`V(q)V_{R=0}`$ instead of $`V(q)`$, which is exactly the case in Krivoglaz’s derivation . Note, however, that this problem does not exist if the Krivoglaz-Clapp-Moss expression is used together with the so-called Onsager correction  under the condition that it is properly defined.

The reason, why it was possible to calculate $`\alpha _{scr}`$ on the basis of the ordered structures, is the fact that, in an ordered binary alloy with only two non-equivalent sublattices, one has an exact cancellation of the screening contribution to the Madelung energy and potential. This does not happen, however, in the general case of a supercell with $`n>2`$ non-equivalent sublattices. Here, the Madelung energy may written as sum of the contribution from the intrasite screening interactions

$`E_{Mad}^{scrsc}`$ $`=`$ $`{\displaystyle \frac{e^2}{2N}}{\displaystyle \frac{\alpha _{scr}}{S}}{\displaystyle \underset{i}{}}q_i^2={\displaystyle \frac{e^2}{2}}{\displaystyle \frac{\alpha _{scr}}{S}}[c{\displaystyle \frac{1}{N_A}}{\displaystyle \underset{i=A}{}}q_{iA}^2+(1c){\displaystyle \frac{1}{N_B}}{\displaystyle \underset{i=B}{}}q_{iB}^2]`$ (29)
$`[`$ $``$ $`{\displaystyle \frac{e^2}{2}}{\displaystyle \frac{\alpha _{scr}}{S}}(c<q_A>^2+(1c)<q_B>^2)],`$ (30)
where $`N_A`$ and $`N_B`$ are the number of A and B atoms, respectively, and the ordering energy due to the intersite interactions

$$\mathrm{\Delta }U_{Mad}=\frac{e^2}{2S}\underset{i}{}\gamma _i(\alpha _{k_i}\alpha _{scr})\mathrm{\Delta }q_{k_i}^2.$$
(31)
Here, $`\gamma _i`$ is a normalizing coefficient, $`\alpha _{k_i}`$ a constant due to the bare electrostatic interactions between the net charges for the superstructure vector $`k_i`$ which may be calculated from the Madelung constants $`\alpha _M^{ij}`$ of the corresponding supercell similar to the $`\alpha _{L1_0}`$ considered above, and $`\mathrm{\Delta }q_{k_i}`$ the difference between the charges in the crests and in the troughs of the concentration wave in the supercell. In the case of a binary alloy with two non-equivalent sublattices, there is only one $`k_i`$ and $`\mathrm{\Delta }q_{k_i}=(q_Aq_B)`$.

If $`\alpha _{k_i}`$ depends only on the structure and describe the bare electrostatic interaction between net charges, then $`\mathrm{\Delta }q_{k_i}`$ "dresses" these interactions according to the real charge distribution in the alloy (an equivalent description in real space in the charge correlated model is given by Wolverton and Zunger , who also show that the Madelung energy of the random alloy has intrasite character). If the net charges in the supercell are screened (or uncorrelated) at distances less than half the period of the concentration wave with wave-vector $`k_i`$ then $`\mathrm{\Delta }q_{k_i}`$=0 and the corresponding contribution to the ordering energy vanishes. If the supercell includes only long-range concentration waves, the corresponding ordering contribution to the Madelung potential and energy becomes zero.

Let us finally mention the fact that the Madelung energy of a random alloy obtained in supercell calculations (29) is not equal to the Madelung energy in the single-site calculations, and thus it cannot be used to obtain $`\alpha _{scr}`$. The reason is simply that the Madelung energy is not a self-averaging quantity. However, the Madelung potential is, and it is clear that

$$<V_X>^{sc}=\frac{e^2}{N_X}\frac{\alpha _{scr}}{S}\underset{i=x}{}q_{iX}=e^2\frac{\alpha _{scr}}{S}<q_X>=V_X^{ss},$$
(32)
which allows one to use (8) to obtained $`\alpha _{scr}`$ in the supercell calculations and shows why $`\alpha _{rand}`$ is exactly equal to $`\alpha _{scr}`$.

### C Intersite screened Coulomb interactions

Although the screened Coulomb interactions have an intrasite character, they may contribute to the effective pair intersite interactions of the kind obtained in the generalized perturbation method (GPM)  because the screening charge is located on several of the coordination shells around each atom. This was, in fact, already recognized by Ducastelle  who derived the contribution to the GPM potentials from the screened Coulomb interactions in the framework of the Hartree-Fock tight-binding CPA theory.

The existence of an additional electrostatic term due to the screening is also consistent with Andersen’s the force theorem , which states that the change in the total energy of a system due to some perturbation to first order is given by the change in the sum of the one-electron energies obtained from frozen one-electron potentials plus the change of the electrostatic energy due to the perturbation. In fact, this latter contribution from the screened Coulomb interaction has been completely neglected in a number of first-principles calculations of GPM interactions . Here, we will therefore show how the screening contribution to the GPM potentials may be defined and obtained on the basis of the calculated spatial distribution of the screening charge.

GPM-like pair interactions, usually defined by (18) for a specific lattice vector $`𝐑`$, may be determined as the site-projected part of the change in the total energy when two atoms of different types in a completely random alloy are exchanged between sites infinitely far apart in such a way that their neighbors at the relative position $`𝐑`$ are of the opposite type after the exchange. This is schematically illustrated in Fig. 7. That part of the total energy which should be accounted for is half the site-decomposed total energy written in terms of the intersite interactions or interatomic potentials, i.e.,

$$V^{(2)}(R)=\frac{1}{2}[E_1^{(2)}(R)E_2^{(2)}(R)].$$
(33)
Here, $`E_1^{(1)}`$ is the total energy due to pairwise interactions of the unperturbed system projected onto site $`0`$ and $`E_2^{(2)}`$ is the same quantity after the exchange. A similar expression is also valid in the case of multisite interactions, but this will involve a more complex exchange of atoms and will not be considered here because the screened Coulomb interactions do not contribute to the effective multisite interactions in the ASA.

Within multiple scattering theory as well as in the tight-binding approximation a Green’s function formulation allows both site- and "path"-decomposition of the electron density and thereby makes it possible to write down an analytical expression for the one-electron contribution to the $`n`$-site interactions, $`V^{(n)}(R)`$, in the CPA . Concerning the screened Coulomb interactions one must, however, proceed differently. There are several ways to do so, but here we will present a straightforward approach.

In the sense of the CPA and single-site mean-field theory we will use an effective medium approach, assuming that at all sites, i.e., within the atomic spheres assigned to each site, there is an electroneutral effective medium except at the two sites $`\mathrm{𝟎}`$ and $`𝐑`$ under consideration. In those two sites we must use the actual values of the net charges of the alloy components, which in the effective medium approach, are the average net charges, $`q_A`$ and $`q_B`$, of the alloy components.

In the first-principles methods, however, these net charges depend on the specific choice of the size of the atomic spheres and thus they must, in principle, go together with the corresponding screening cloud. Since we calculate the change in the electrostatic energy of the two systems shown in Fig. 7 projected onto site $`\mathrm{𝟎}`$ due to the exchange of A and B atoms in positions $`𝐑`$, we must include only the interaction of the net charge at site $`\mathrm{𝟎}`$ with the net charge at site $`𝐑`$ and its screening charge. That is, the interaction of the net charge with its own screening charge must be excluded as it is included in the definition of the screened on-site interactions, see (11). Thus, the first term in (33) for the system before the exchange of atoms has been made, $`E_1^{scr}(R)`$, is

$$E_1^{scr}(R)=e^2q_A\underset{𝐑^{}0}{}\frac{q_{A𝐑^{}}}{R^{}}+e^2q_B\underset{𝐑^{}0}{}\frac{q_{B𝐑^{}}}{R^{}}.$$
(34)
Here, $`q_{i𝐑^{}}`$ is either the net charge of the $`i`$th component, $`q_i`$, if $`𝐑^{}=𝐑`$ or the corresponding screening charge if $`𝐑^{}𝐑`$. A similar expression may be written for $`E_2^{scr}(R)`$, after the exchange of the A and B atoms in the $`𝐑`$-sites, i.e.,

$$E_2^{scr}(R)=e^2q_A\underset{𝐑^{}0}{}\frac{q_{B𝐑^{}}}{R^{}}+e^2q_B\underset{𝐑^{}0}{}\frac{q_{A𝐑^{}}}{R^{}}.$$
(35)
The resulting expression for the screened Coulomb interactions which should be added to the usual one-electron term is therefore

$`V_{scr}(R)`$ $`=`$ $`{\displaystyle \frac{e^2}{2}}[q_A{\displaystyle \underset{𝐑^{}0}{}}{\displaystyle \frac{q_{A𝐑^{}}q_{B𝐑^{}}}{R^{}}}q_B{\displaystyle \underset{𝐑^{}0}{}}{\displaystyle \frac{q_{B𝐑^{}}q_{A𝐑^{}}}{R^{}}}]`$ (36)
$`=`$ $`{\displaystyle \frac{e^2}{2}}(q_Aq_B)^2{\displaystyle \underset{𝐑^{}0}{}}{\displaystyle \frac{Q(|𝐑^{}𝐑|)}{R^{}}},`$ (37)
where $`Q(R)`$ is the normalized screening charge defined in (9), and where we have used the condition that the screening does not depend on the type of the atom. Finally, performing the summation in (36) one may define the screened Coulomb interactions as

$$V_{scr}(R)=\frac{e^2}{2}(q_Aq_B)^2\frac{\alpha _{scr}(R)}{S}.$$
(39)
It is easy to see from (36) and (11) that $`\alpha _{scr}(R=0)=\alpha _{scr}=\alpha _{rand}`$ and therefore, $`V_{scr}(R=0)`$ is exactly the on-site screened interactions that defines the Madelung energy of the binary alloy which has exactly the same form (22). This on-site interaction must be included in the definition of the $`S^{(2)}`$ interactions , as has been demonstrated in the previous section (see also Ref. ). When $`R0`$, $`V_{scr}(R)`$ defines the intersite screened Coulomb interaction contribution to the GPM-like effective interactions. Since the screening in the ASA, is practically universal these interactions have the universal form presented in Fig. 8.

## VI The total energy in the single-site CPA and the supercell LSGF methods

The fact that the Madelung energy of a random alloy described either by the effective medium model defined by the SS-DFT-CPA method or by the supercell model in conjunction with the SS-LSGF method differ from each other, has neither consequences for the final result for the total energy of the random alloy nor even for the partial and local contributions to the total energy. This follows simply from the fact that the density of states and its average local contributions are the same in the two methods, as shown above.

In Table I we compare the total energy and its components in a Cu<sub>50</sub>Pt<sub>50</sub> random alloy calculated by the SS-DFT-CPA method with $`\alpha _{scr}=`$0.60572 and by the SS-LSGF method on the basis of a 512-atom supercell, in which the atomic positions of Cu and Pt have been chosen such that the SRO parameters are equal zero at the first 7 coordinations shells (LSGF-1). The agreement between the two calculations is seen to be excellent if one combines the electron-nucleus, the electron-electron, and the Madelung contributions to form a total Coulomb energy, $`E_{coul}=E_{elnuc}+E_{elel}+E_{Mad}`$.

The accuracy of the SS-DFT-CPA method with the appropriate screening contribution to the Madelung potential and energy may be appreciated if one compares the results of a 512-atom supercell calculation performed by the SS-LSGF method (LSGF-2) where the distribution of the Cu and Pt atoms have not been optimized after the application of the random number generator leading to quite small, but not zero, SRO parameters. The values of the SRO parameters for the first 7 coordination shells are $``$0.005208 (1), 0.026041 (2), 0.007161(3), -0.014323(4), -0.021484(5), 0.0390625(6), $``$0.0136718 (7), respectively, which are approximately the same, as in the LSMS calculations in Ref. . The agreement between SS-DFT-CPA results and SS-LSGF calculations with a properly chosen supercell (LSGF-1) is obviously better than between two SS-LSGF calculations.

## VII Conclusion

The screened Coulomb interactions which are due to the interaction between the net charge of an alloy component and its screening charge must be included in a consistent single-site mean-field theory of the electrostatics in random alloys. In this paper we have shown how this may be done and we have calculated the spatial distribution of the screening charge which in the ASA is found to be practically universal for homogeneous systems. A formalism that describes the contribution from for the screened Coulomb interaction to Madelung potential and energy as well as to the effective interactions of the GPM-type is presented.

## VIII Acknowledgements

Valuable discussions with Dr. P. A. Korzhavyi, I. A. Abrikosov, A. Yu. Lozovoi, Prof. A. Gonis and Prof. S. Faulkner are greatly acknowledged. Center for Atomic-scale Materials Physics is sponsored by the Danish National Research Foundation.


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# Adaptive Spatial Binning of 2D Spectra and Images Using Voronoi Tessellations

## 1. Introduction

Spatially resolved astronomical observations commonly span orders of magnitude variations in the signal-to-noise (S/N) across the detector elements. For this reason data are often grouped together in the spatial direction (binned) and averaged before analyzing them. More spatial resolution is retained in the high-S/N regions compared to the low-S/N ones. A well known example is galaxy photometry, where logarithmically spaced radial bins are often adopted. Many more pixels are used to compute the value of a galaxy profile at large radii than in the center.

Binning is essential in the case of spectroscopic observations of the stellar kinematics. In fact a minimum S/N is *required* for a reliable and unbiased extraction of kinematical information from the spectra (e.g., Rix & White 1992; van der Marel & Franx 1993; Kuijken & Merrifield 1993). For this reason binning is invariably used to analyze one-dimensional (1D, e.g., long slit) spectroscopic observations. New developments with Integral Field Spectroscopy (IFS; e.g., OASIS on CFHT, SAURON on WHT, VIMOS on VLT, GMOS on Gemini) require methods to perform spatial binning of spectra in two dimensions (2D) too.

The related process of adaptively smoothing is not acceptable for our purposes since it correlates the information of different bins which complicates the quantitative interpretation of spectroscopic measurements. For the same reason smoothing is never used for the quantitative analysis of 1D spectra.

Little work has been done on the subject of adaptive 2D-binning. Sanders & Fabian (2001) developed an algorithm to be used with X-ray imaging data. The bins that their method produces however can contain other bins and are not compact. In the case of spectroscopic data it makes little sense to bin together spectra coming from pixels that are not close to each other and whose properties may differ considerably. Other schemes have to be developed.

## 2. Formulation of the Problem

We tackle here the problem of binning in the spatial direction(s). In what follows the term ‘pixel’ refers to a given spatial element of the dataset: it can be an actual pixel of a CCD image, or a spectrum position along the slit of a long-slit spectrograph or in the field of view of an IFS.

Each pixel $`i`$ has an associated signal $`𝒮_i`$ and its corresponding noise $`𝒩_i`$. The pixel signal-to-noise ratio is therefore $`(\text{S/N})_i=𝒮_i/𝒩_i`$. Our considerations do not depend on the details used to estimate these quantities, which we assume to be known beforehand for every pixel $`i`$. In the case of spectrography for instance, the quantity $`𝒮_i`$ associated to a given spectrum $`S_i(\lambda )`$ can be the average signal over a given spectral range $`\mathrm{\Delta }\lambda `$: $`𝒮_i=\frac{1}{\mathrm{\Delta }\lambda }_{\mathrm{\Delta }\lambda }S_i(\lambda )d\lambda `$; while the corresponding average noise can be defined as $`𝒩_i^2=\frac{1}{\mathrm{\Delta }\lambda }_{\mathrm{\Delta }\lambda }N_i^2(\lambda )d\lambda `$. It is important to note that, in our case, the term ‘binning’ will only refer here to the averaging of observations taken at different positions on the sky (i.e., different pixels), and *not* along the spectral direction.

To bin in 1D one only has to make sure that the spatially binned data satisfy a minimum S/N requirement (or better a minimum scatter around the target S/N). In 2D (and higher dimensions) the situation is more complex and a good binning scheme has to satisfy the following requirements:

the bins should at least properly tessellate the region $`\mathrm{\Omega }`$ of the plane under consideration, i.e., create a partition of $`\mathrm{\Omega }`$, without overlapping or holes. While this requirement is trivial to enforce in 1D, it is tricky to implement in higher dimensions, as the bin shapes must then be taken into consideration;

the bin shape has to be as ‘compact’ (or ‘round’) as possible, so that they are associated with a well-defined position, and correspond to the overall best spatial resolution;

the bin S/N should be as uniform as possible around a target value. While a minimum S/N is generally required, one does not want to sacrifice spatial resolution to increase the S/N even further.

In what follows we consider different methods and we apply each one to observations of the barred Sa galaxy NGC 2273 (Fig. 1) taken with the panoramic IFS SAURON (Bacon et al. 2001). These observations, based on 8 single 1800 s exposures, have been selected for having high S/N contrast between the inner and the outer parts, and a complex S/N-distribution, caused by the presence of spiral arms, S/N-jumps and irregular outer boundaries due to the merging of multiple exposures.

## 3. Quadtree Method

It is useful to first consider the Quadtree algorithm (Samet 1984), which we believe is close to the best ‘regular’ image processing method available for the present application. We show that the Quadtree method cannot produce an *optimal* binning and more complex schemes are required. These we discuss in Section 4.

The Quadtree method consists of a recursive partition of a region of the plane into axis-aligned squares. One square, the *root*, covers the entire region. A square is divided into four *child* squares, by splitting with horizontal and vertical segments through its center. The collection of squares then form a tree, with smaller squares at lower levels of the tree. The splitting of squares terminates when all squares meet some convergence criterion.

In Fig. 2 the Quadtree method was used to rebin the S/N map of Fig. 1 into squares satisfying a minimum S/N requirement. The nice feature of this binning method is that the resulting bins are squares of various sizes (except at the border). In this way bins are easy to handle, and require little information to be described completely.

There are however two major problems with this method:

* a S/N spread of a factor $`2`$ is unavoidable due to the fact that bin area varies by construction in steps of a factor of 4;
* unless the original image has a size which is a power of two, some bins at the border will not be square and generally will not meet the minimum S/N criterion, becoming unusable for later analysis.

## 4. Voronoi Tessellation

Given the inability of methods employing ‘regular’ bins to produce optimal 2D tessellations, we now consider schemes which do not have square or rectangular bins. Accordingly we consider the *Voronoi Tessellation* (VT), that can be used to generate binnings satisfying all the three requirements of Section 2.

Given a region $`\mathrm{\Omega }`$ and a set of points $`\{z_i\}_{i=1}^N`$, called *generators*, in $`\mathrm{\Omega }`$, a VT is a partition of $`\mathrm{\Omega }`$ into regions $`\{V_i\}_{i=1}^N`$ enclosing the points closer to $`z_i`$ than to any other generator. Each $`V_i`$ is referred to as the *Voronoi region* or *bin* associated to $`z_i`$ (see Okabe, Boots, & Sugihara 1992, for a comprehensive treatment).

The VT presents many interesting features for the binning problem:

* it naturally enforces the Topological requirement;
* it is efficiently described by the coordinates of its generators;
* it is very easy to implement in the discrete case: given the generator positions, it is sufficient to locate the closest generator to any given pixel to determine the bin to which it belongs.

On the other hand, the fact that a VT is adopted for binning does not enforce by itself the Morphological requirement: the bins are convex by construction, but can have very sharp angles. Furthermore, the Uniformity requirement is not addressed in any way by the use of a VT. These two requirements have to be tackled through a properly tailored distribution of the Voronoi generators. We present now a way to produce such a distribution.

### 4.1. Centroidal Voronoi Tessellation

The *Centroidal Voronoi Tessellation* (CVT) is a technique which can be used to generate an optimally uniform *and* regular VT in the continuous case, or in the limit of a large number of pixels. We initially assume that the observed signal $`S_i`$ can be described by a continuous function $`\rho (𝐫)`$ in the sky-plane. Moreover we assume the noise $`N_i`$ to be a monotonic function of $`S_i`$ (e.g., Poissonian noise $`N_i=\sqrt{S_i}`$). With these assumptions the problem of generating equal-S/N bins reduces to that of producing a tessellation enclosing equal-mass, according to the density distribution $`\rho (𝐫)`$.

Given a density function $`\rho (𝐫)`$ defined in a region $`\mathrm{\Omega }`$, a CVT of $`\mathrm{\Omega }`$ is a special class of VT where the generators $`z_i`$ happen to coincide with the mass centroids $`z_i^{}=_{V_i}𝐫\rho (𝐫)d𝐫/_{V_i}\rho (𝐫)d𝐫`$ of the corresponding Voronoi regions $`V_i`$. As illustrated in the review by Du, Faber, & Gunzburger (1999), the CVTs are useful to solve a variety of mathematical problems, but can also be observed in many real-life natural examples (living cells, territories of animals, etc.).

One of the most striking characteristics of CVT in the 2D case is its ability to partition a region into bins whose size varies as a function of the underlying density distribution, but whose shape tends asymptotically to a hexagonal-like lattice for a large number of bins. Another nice feature of CVT is that a simple algorithm exists for its practical computation: the Lloyd (1982) method, for which the CVT is a fixed point.

Although CVT bins are naturally smaller where the density is higher, the area-$`\rho `$ relation of the bins is not such that the mass enclosed in every bin is the same: the CVT cannot be used directly to produce equal mass bins (equal S/N in the case of photon noise). However, it can be shown that if a CVT is constructed for the density $`\rho ^2`$, the tessellation obtained will enclose equal mass according to the original density $`\rho `$ (see Cappellari & Copin in prep. for details).

Fig. 3 presents a CVT produced by applying the Lloyd’s algorithm to the density $`\rho ^2`$, where $`\rho `$ was obtained by linearly interpolating the surface brightness of Fig. 1 onto a grid with pixel size $`8\times `$ smaller than the original size. This interpolation is used here to ‘simulate’ an observation with a much higher spatial resolution, but is not an accurate way of dealing with lower resolution data. In this case of a large number of pixels the cells of the VT tend to the theoretical hexagonal shape and adapt nicely to density variations and to the irregular boundary of the region. The scatter of the S/N is also close to optimal with RMS scatter of $`4\%`$.

This CVT method illustrates the goals towards which an optimal 2D-binning algorithm should tend, but it has still some practical limitations:

* it generates equal-mass bins and *not* necessary equal-S/N bins, unless the noise is a monotonic function of the signal. It is e.g., useful to produce equal S/N bins when all the noise in the pixel can be attributed to photon noise. This is often the case, but not always;
* more importantly the method does not work well when the bins are constituted of just a few pixels. In Fig. 4 the same generators as in Fig. 3 where used to construct a VT for the coarser SAURON pixel grid of Fig. 1. The obtained VT is similar to that of Fig. 3, but the S/N scatter increases considerably, due to discretization effects.

In practice an optimal 2D-binning method has to preserve the good characteristics of the CVT, in the limit of many pixels, but has to be able to take the discrete nature of pixels into account, when dealing with bins constituted by just a few pixels. This algorithm is the subject of the next section.

### 4.2. Bin-Accretion Algorithm

We describe a method we developed to find the generators for the optimal VT of an image or IFS observation taking the discrete nature of pixels into account from the beginning. The algorithm described here constructs an initial binning trying to generalize to 2D the standard pixel-by-pixel binning algorithm used in 1D. The centroids of the bins found in this way are then used as starting generators for a CVT. The method reduces to the previous CVT in the limit of many pixels, but works on a pixel basis with bins made by just a few pixels.

A natural 1D-binning algorithm starts a bin from the highest S/N unbinned pixel and accretes pixels until a given target S/N is reached. To extend this idea to 2D, we need to make a choice for the direction toward which new pixels are accreted to a 2D-bin. The adopted method always tries to add to the current bin the pixel that is closest to the bin centroid. Furthermore, when a new bin is started, the first pixel is also selected as the one closest to the centroid of all the previously binned pixels. This simple scheme automatically *tends to* generate bins that are compact, and the bin S/N can be carefully monitored on a pixel-by-pixel basis during the accretion phase. Some small imperfections remain at the end of the accretion phase: these are corrected by performing a CVT, using as starting generators the centroids of the previous bins.

An example of the application of the bin-accretion algorithm to the binning of the actual SAURON data of NGC 2273 is shown in the left panel of Fig. 5, while the resulting S/N scatter is shown in the right panel: the RMS value is $`6\%`$. The S/N values, symmetrically clustered around the target $`\text{S/N}=50`$, essentially represent the lowest S/N scatter obtainable from a binning of these data: all the scatter is due to discretization noise, which increases towards to the galaxy center, where the bin are made of a smaller number of pixels. The velocity field extracted from the binned data is shown in Fig. 6.

The binning resulting from this algorithm is qualitatively similar to the one obtained using the CVT (see Fig. 3). But, by contrast to the CVT alone, this method is able to produce bins that are essentially optimal also in the ‘small-bins’ regime, with bins of only 2–4 pixels.

## 5. Conclusions

We presented a method to adaptively perform spatial binning of 2D data (e.g., IFS or imaging data). As an example of its application we have extracted the stellar mean velocity field from the 2D-binned SAURON data of the barred spiral galaxy NGC 2273. Adaptive 2D-binning should become common practice for the analysis of 2D data (in particular spectral data), as it is for 1D observations.

#### Acknowledgments.

We thank Tim de Zeeuw for useful comments on the draft and Gijs Verdoes Kleijn for lively discussions on this subject.

## References

Bacon, R., et al. 2001, MNRAS, 326, 23

Du, Q., Faber, V., & Gunzburger, M. 1999, SIAM Review, 41, 637

Kuijken, K., & Merrifield, M. R. 1993, MNRAS, 264, 712

Lloyd, S. P. 1982, IEEE Transactions on Information Theory, 28, 129

Okabe, A., Boots, B., & Sugihara, K. 1992, Spatial tessellations concepts and applications of Voronoi diagrams (Chichester, UK: Wiley)

Rix, H.-W., & White, S. D. M. 1992, MNRAS, 254, 389

Samet, H. 1984, The Quadtree and Related Hierarchical Data Structures. ACM Computing Surveys, 16, 187

Sanders, J. S., & Fabian, A. C. 2001, MNRAS, 325, 178

van der Marel, R. P., & Franx, M. 1993, ApJ, 407, 525