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# Charge Distributions in Metallic Alloys: a Charge Excess Functional theory approach

## Abstract

The distribution of local charge excesses (DLC) in metallic alloys, previously obtained as a result of the analysis of order N electronic structure calculations, is derived from a variational principle. A phenomenological Charge Excess Functional (CEF) theory is obtained which is determined by three concentration dependent, material specific, parameters that can be obtained from ab initio calculations. The theory requires modest computational efforts and reproduces with an excellent accuracy the DLC and the electrostatic energies of ordered, substitutionally disordered or segregating metallic alloys and, hence, can be considered an efficient approach alternative to conventional electronic structure calculations. The substantial reduction of computing time opens new perspectives for the understanding of metallic systems and their mechanical properties.

The application of metallic alloys in a huge variety of high-tech areas, ranging from medical prosthesis Kohn (1996) to jet engines Naka (1996), requires a careful assessment of the mechanical properties of these materials. The determination of their phase diagrams is crucial to this end since the performances of alloys are heavily influenced by the various crystalline phases of which they are made Cahn (2001); Lee (1996); Pettifor (1995); T. Kraft (1997). Recently, Zhao Zhao (2001) introduced an innovative experimental method that allows for the rapid yet accurate assessment of alloy phase diagrams. However, theoretical methods with similar high-throughput performances seem much beyond the status of art.

Current theoretical approaches can be divided in two different classes. Theories in the first group are based on Landau’s idea that ordering occurs in alloys due to some instability of the high-T solid solution phase (HTSSP) with respect to certain concentration fluctuations Khachaturyan (1983); s2 . Such schemes often use the Coherent Potential Approximation (CPA) solution for the HTSSP as the reference state for a perturbation theory. They can be put in a very elegant form using a reciprocal space formalism, making contact with the concept of long-range order (LRO) and with the Fermi surfaces properties Bruno et al. (1994); Wilkinson et al. (2001). In spite of many successes, these approaches suffered from the criticisms moved to the CPA which, in its standard implementation within the density functional theory (DFT), fails to account for the electrostatic energies in the HTSSP. Theories in the second class are based on Ising hamiltonians. The corresponding parameters can be extracted from the experiment, from a perturbative expansion of the CPA HTSSP solution GPM  or, as it is nowadays more common, from the total energies of various alloy configurations as obtained by DFT calculations Colinet . In this case, accuracy is controlled by the cut-off length $`l`$ assumed for Ising interactions. In metallic alloys LRO and short-range order (SRO) are entangled in such a way that the convergence with $`l`$ is slow, while DFT calculations would be required for about $`N!`$ alloy configurations Franceschetti ; Sanati , with $`Nl^3`$. In turn, DFT calculations for a single configuration constitute a bottleneck: using the fastest available algorithms Wang et al. (1995); Abrikosov et al. (1996) the number of floating-point operations required is proportional to $`N`$, with huge prefactors note1 . Remarkable results have been obtained by a mixed approach Zunger  that includes the summation of series both in the direct and the reciprocal spaces. However, in this approach no estimate of the size of the truncation errors is available.

In the present Letter we shall show that the computational labour necessary to obtain total energies for any alloy configuration can be greatly reduced. At variance of existing simplified approaches Lee (1996); Franceschetti , we shall maintain accuracies comparable to those of DFT calculations.

The analysis Faulkner et al. (1995); Abrikosov and Johansson (1998); Ruban and Skriver (2002) of DFT calculations data in extended metallic systems indicates that the net charges at the crystal sites, $`q_i`$, and the site Madelung potentials, $`V_i`$, are strongly correlated. More precisely Faulkner et al. (1995), within numerical errors, i) the DLC is continuous over a certain interval and ii) the pairs $`(q_i,V_i)`$, lie on straight lines, one for each alloying species. For future reference, the statement (ii) is conveniently rewritten as

$$a_iq_i+V_i=k_i$$
(1)
For a specified configuration of the binary alloy A$`_{c_A}`$B$`_{c_B}`$, the coefficients in Eq. (1) take the values $`a_A`$ and $`k_A`$ if the i-th site is occupied by an A atom or $`a_B`$ and $`k_B`$ otherwise. The results (i) and (ii), in the following referred to as the $`qV`$ laws, have been numerically obtained within the Local Density Approximation (LDA) and the muffin-tin or the atomic sphere approximations for the crystal potential Ruban and Skriver (2002); Bruno et al. (2002) but not yet formally derived. Here their validity shall be assumed as an ”empirical” evidence.

Accurate calculations of the alloy total energies must necessarily keep into account the above results. It has been shown recently that an isomorphous CPA model including local fields (CPA+LF) Bruno et al. (2002) and a modified screened CPA approach Ruban and Skriver (2002) are able to catch the linear nature of the $`qV`$ laws and compatible with (i). However, the same models are not able to self-consistently determine the DLC. Here we shall obtain the DLC from a variational principle in terms of one electronic degree of freedom for each atom, the local charge excess $`q_i`$. In the resulting phenomenological Ginzburg-Landau theory, hereafter referred to as CEF, the site chemical occupations determine the $`q_i`$ at each site and the electrostatic energy. For all the (ordered or disordered) alloy configurations corresponding to the same mean concentration the theory is completely determined by three material specific parameters that can be obtained ab initio by supercell DFT calculations or by the CPA+LF theory. In the following the CEF theory shall be presented and tested vs. order N Locally Self-consistent Multiple Scattering (LSMS) DFT calculations Faulkner et al. (2001) for bcc CuZn alloys.

As in the case of LSMS calculations Wang et al. (1995), we study the binary alloy A$`_{c_A}`$B$`_{c_B}`$, $`c_A+c_B=1`$, by the means of supercells of volume $`V`$ containing N atoms with periodic boundary conditions. Each site can be occupied by an A or a B atom. The nuclear charge $`Z_i`$ and the volume 111 There is some arbitrariety in the way in which the $`\omega _i`$ can be chosen: they could be built using the Wigner-Seitz construction (and possibly approximated by spheres), or they could be non-overlapping muffin-tin spheres to which an appropriate fraction of the interstitial volume is added. $`\omega _i`$, $`_i\omega _i=V`$, are associated with each crystal site. Each alloy configuration is specified by a set of occupation numbers 222 In our notation Latin indices identify the sites in the supercell and Greek indices the chemical species. In the sums, Latin indices run from $`1`$ to N and Greek indices take the values A and B. , $`X_i^\alpha `$, where $`X_i^\alpha =1`$ if the $`i`$-th site is occupied by a $`\alpha `$ atom or $`0`$ otherwise and $`_iX_i^\alpha =Nc_\alpha `$. The site charge excesses, $`q_i=_{\omega _i}𝑑\stackrel{}{r}\rho (\stackrel{}{r})Z_i`$, defined in terms of the electronic density $`\rho (\stackrel{}{r})`$, satisfy the global electroneutrality constraint

$$\underset{i}{}q_i=0$$
(2)
As it is verified within spherical approximations for the crystal potential and the LDA, we assume that the system total electronic energy consists of the sum of site-diagonal terms plus a Madelung term Janak (1974); Faulkner et al. (1995), $`E_M=_{ij}M_{ij}q_iq_j=\frac{1}{2}_iq_iV_i`$. The Madelung matrix elements $`M_{ij}`$ are defined as usual Ziman (1969); Bruno et al. (2002), and the Madelung potentials are given by,

$$V_i=2\underset{j}{}M_{ij}q_j$$
(3)
Unless otherwise stated we use atomic units in which $`e^2=2`$.

We wish to develop a theory that determines the $`q_i`$ and incorporates the $`qV`$ laws. For a particular alloy configuration, Eq. (2) and the substitution of Eqs. (3) in Eqs. (1) give $`N+1`$ linear equations in the $`q_i`$. This implies that not all the coefficients $`a_\alpha `$ and $`k_\alpha `$ can be independent. The CPA+LF model gives a hint for the missing relationship. In this theory Bruno et al. (2002) the quantities $`1/a_\alpha `$ depend only on the mean alloy concentration and are viewed as the responses of impurity sites, embedded in the CPA ’mean’ alloy, to a local field designed to simulate the Madelung potential. Furthermore, the CPA ’electroneutrality’ condition for the zero-field charges, $`b_\alpha =k_\alpha /a_\alpha `$ gives $`c_Ab_A+c_Bb_B=0`$. These circumstances suggest that the theory we are elaborating should allow for a possible renormalization of the constants $`k_\alpha `$ in different configurations corresponding to the same mean alloy concentration.

To make further progresses, we consider the Ginzburg-Landau functional of the site charge excesses,

$$\mathrm{\Omega }([q],\mu )=\underset{i}{}\frac{a_i}{2}(q_ib_i)^2+\underset{ij}{}M_{ij}q_iq_j\mu \underset{i}{}q_i$$
(4)
where the Lagrange multiplier $`\mu `$ has been introduced to impose global electroneutrality. The minimization of Eq. (4) with respect to the order parameter field $`\{q_i\}`$ and to $`\mu `$ gives the set of Euler-Lagrange equations constituted by Eq. (2) and by

$$a_i(q_ib_i)+2\underset{j}{}M_{ij}q_j=\mu $$
(5)
Eqs. (5) are equivalent to Eqs. (1) only when $`\mu =0`$. When $`\mu 0`$, the renormalization $`k_\alpha k_\alpha +\mu `$ occurs to ensure global electroneutrality. Once the four constants $`a_\alpha `$, $`b_\alpha `$ have been obtained for a given alloy configuration, they also can be used for other configurations. As we shall see, the transferability of the parameters within fixed concentration ensembles is a peculiar strength of the present approach.

Now, since $`\mathrm{\Omega }`$ has the dimension of an energy and contains the electrostatic contribution $`E_M`$, we assume that, except but for an additive constant, its minimum value corresponds to the total electronic energy of the alloy configuration at hand. The quadratic terms in Eq. (4) can be interpreted as energetic contributions due to local charge rearrangements and $`\mu `$ as the chemical potential ruling charge transfers.

The explicit solution of the problem can be written in terms of $`𝚲`$, the inverse of the matrix of elements $`2M_{ij}+_\alpha a_\alpha X_i^\alpha \delta _{ij}`$. Straightforward calculations show that

$$q_i=(k_Ak_B)[(1y)\underset{j}{}\mathrm{\Lambda }_{ij}X_{j}^{}{}_{}{}^{A}y\underset{j}{}\mathrm{\Lambda }_{ij}X_{j}^{}{}_{}{}^{B}]$$
(6)
where $`\mathrm{\Lambda }_{\alpha \beta }=_{ij}X_{i}^{}{}_{}{}^{\alpha }\mathrm{\Lambda }_{ij}X_{j}^{}{}_{}{}^{\beta }`$, and $`y=_\alpha \mathrm{\Lambda }_{A\alpha }/_{\alpha \beta }\mathrm{\Lambda }_{\alpha \beta }`$. The set of four constants found by LSMS or similar calculations for a specific configuration is then equivalent to the three constants in the CEF theory, $`a_A`$, $`a_B`$ and $`k_Ak_B`$, and to the chemical potential $`\mu `$. The CEF formulation and solution are well defined for both ordered and disordered alloys.

In the following we shall apply the CEF theory to bcc Cu0.50Zn0.50 alloys and compare the results vs. LSMS calculations. We have selected several sample supercells described in Table I and designed to simulate random, partially ordered or segregated configurations. For each sample a set of the CEF parameters has been extracted by linear fits of the corresponding LSMS $`qV`$ data: CEF calculations made using parameters from the $`n`$-th sample are indicated below as CEF-$`n`$.

A detailed comparison between LSMS and CEF-1 calculations for sample 1 is reported in Table II. The two sets of calculations present very small differences: 5 parts over $`10^5`$ for the mean values of the charges and of the Madelung potentials, 2 parts over $`10^4`$ for the Madelung energies, less than 1 per cent for the widths of the DLC. The absolute values of the differences $`\mathrm{\Delta }q_i=q_i^{CEF1}q_i^{LSMS}`$ are smaller than 0.005 electrons at any lattice site and not correlated with the chemical occupations. The mean square deviation between the two set of charges, $`(\mathrm{\Delta }q)^2`$, is of the order of $`10^6`$, i.e. it is comparable with the numerical errors in LSMS calculations. The resulting DLC’s, plotted in Fig. (1), appear very similar.

The main source of the tiny differences is that all the CEF charges by construction satisfy the $`qV`$ laws, while the same laws hold only approximately for LSMS calculations.

Specific tests have been designed to check the transferability of the CEF parameters extracted from one sample to the others. The mean square deviations of the charges obtained from CEF-$`n`$ and LSMS $`(\mathrm{\Delta }q)^2`$ (Table III) clearly show that there is no appreciable loss of accuracy when the CEF parameters extracted from random samples are used in ordered, partially ordered or segregated samples and vice versa. Calculations BZWunpub  for CuPd alloys support the same conclusion. The transferability of the CEF parameters is a very remarkable result and implies that the theory is generally applicable to metallic alloys, no matters whether they are ordered, disordered or segregated. Furthermore, the very high accuracy obtained for the Madelung energies (Table IV) indicates that the theory can describe very carefully the electrostatic contributions to the energetics of ordering phenomena.

We conclude this Letter with remarks about interesting aspects of the CEF model in view of possible future applications.

The CEF operates a coarse graining over the electronic degrees of freedom that are reduced to one for each atom, the local excess of charge. This notwithstanding, the theory carefully reproduces the DLC and the energetics of metallic alloys in any ordering status. This has been possible because the Madelung potentials, through Eq. (3), weight as appropriate the long ranged effects of the occupations of all the crystal sites. Such a renormalization of the interactions holds exactly within CPA-based theories like the CPA+LF Bruno et al. (2002) or the PCPA Ujfalussy et al. (2000), where any site diagonal property is a unique function of the Madelung potential $`V_i`$ and the nuclear charge $`Z_i`$ at the same site. This uniqueness does not hold Bruno et al. (2002) for more exact approaches, where some residual dependence on the site nearest neighbours environment is expected for. Nevertheless, the fact that CPA-based theories accurately accounts for the spectral properties of metallic alloys Abrikosov and Johansson (1998) and the quantitative agreement with LSMS calculations, in the present work as well as in Refs. Bruno et al., 2002 and Ujfalussy et al., 2000, suggest that the errors introduced by neglecting the nearest neighbours effects not already conveyed by the $`V_i`$ are comparable with numerical errors in DFT calculations. We mention that, in a very different context, precedents of this idea of a coarse graining over quantum degrees of freedom can be found in the concepts of chemical valence and of electronegativity.

The calculations presented in this Letter require $`N^3`$ floating-point operations in order to obtain $`𝚲`$ by conventional linear algebra algorithms. Thus, for $`N=1000`$, the CEF is about $`10^4`$ times faster than LSMS note1 . We are convinced that, in the next future, such a large computational speed up and the mentioned transferability of the CEF parameters will make possible the development of accurate ab initio techniques for the investigation of ordering phenomena and the calculation of phase diagrams in metallic alloys.

We thank J.S. Faulkner who made the data of Ref. Faulkner et al., 2001 available in digital form and acknowledge discussions with E.S. Giuliano.


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# Geometric interpretation of the 3-dimensional coherence matrix for nonparaxial polarization

## 1 Introduction

In the standard theory of partial polarization in paraxial light , the $`2\times 2`$ hermitian coherence matrix (with unit trace) is decomposed into components with respect to the Pauli matrices. These components, the Stokes parameters, summarise the second order statistical information about the ensemble; in particular, the sum of their squares is 1 for a pure polarization state, and 0 for a completely unpolarized ensemble.

There has recently been a revival of interest in the corresponding coherence matrix in nonparaxial light, where in general there is no well-defined propagation direction, and the hermitian coherence matrix is $`3\times 3`$ . In these treatments, by analogy with the 2-dimensional case, generalised Stokes parameters are defined by decomposing the coherence matrix with respect to the Gell-Mann matrices; a generalized degree of polarization  may be defined using the sum of squares of these components.

Here, I propose a complementary interpretation of the $`3\times 3`$ coherence matrix, motivated by geometric reasoning. Rotational, rather than unitary, invariants of the coherence are emphasised, and the matrix is found to decompose into its real part, which is symmetric and interpreted geometrically as an ellipsoid, and its imaginary part, which is antisymmetric and equivalent to an axial vector. The ellipsoid and vector have natural interpretation in terms of the ensemble of polarization states, and are related by certain inequalities to be described.

Pure states are represented by a complex vector $`\mathrm{E}\mathbf{,}`$ representing the electric field, in either two or three dimensions. This is represented geometrically by an ellipse by taking $`\mathrm{Re}\{\mathrm{E}\mathrm{𝐞𝐱𝐩}\mathbf{(}\mathbf{}\mathbf{}𝝌\mathbf{)}\mathbf{\}}`$ and varying $`\chi `$ (this may represent time evolution) ; the ellipse therefore has a sense of rotation. In two dimensions, this is taken in the natural sense with respect to the plane, and polarization is either right- or left-handed. In three dimensions, the plane of the ellipse may vary, and the sense of rotation is a direction normal to the ellipse, defined in a right-handed sense with respect to the ellipse rotation . The eccentricity of the ellipse can be 1 (corresponding to linear polarization), 0 (corresponding to circular polarization), or any value in between. The ellipses are normalised in units of intensity $`|\mathrm{E}\mathbf{|}^2\mathbf{.}`$ Polarization ensembles may be visualised geometrically as the set of polarization ellipses in the ensemble, adding incoherently.

The paper proceeds as follows: the following section is a review of conventional 2-dimensional coherence matrix theory; in section 3, the geometric decomposition of the $`3\times 3`$ coherence matrix is described; section 4 is devoted to the properties of the coherence matrix, and section 5 to examples for certain ensembles. The paper concludes with a discussion in section 6.

Polarization coherence matrices are special (classical) occurrences of density matrices, perhaps more familiar in quantum mechanics  (pure polarization states corresponding to pure states, etc). Standard properties of density matrices (i.e. positive definite matrices with unit trace) will be employed without proof.

## 2 The two-dimensional coherence matrix

This section is included as a comparison for the $`3\times 3`$ case, and reviews standard material discussed, for example, in .

The 2-dimensional coherence matrix $`\rho _2,`$ assumed normalised (i.e. $`\mathrm{tr}\rho _2=1`$), is defined

$$\rho _2=\left(\begin{array}{cc}E_xE_x^{}& E_xE_y^{}\\ E_yE_x^{}& E_yE_y^{}\end{array}\right),$$
(2.1)
where $``$ denotes ensemble averaging over the ensemble of 2-dimensional complex vectors $`\mathrm{E}\mathbf{=}\mathbf{(}\mathrm{E}_\mathrm{x}\mathbf{,}\mathrm{E}_\mathrm{y}\mathbf{)}\mathbf{.}`$ $`\rho _2`$ is normally expressed in terms of the *Stokes parameters* $`S_1,S_2,S_3,`$ which are the components of $`\rho _2`$ with respect to the Pauli matrices:

$$\rho _2=\frac{1}{2}\left(\begin{array}{cc}1+S_1& S_2\mathrm{}S_3\\ S_2+\mathrm{}S_3& 1S_1\end{array}\right).$$
(2.2)
The three Stokes parameters may be written as a 3-vector, the *Stokes vector*

$$\mathrm{P}\mathbf{=}\mathbf{(}\mathrm{S}_1\mathbf{,}\mathrm{S}_2\mathbf{,}\mathrm{S}_3\mathbf{)}$$
(2.3)
whose length $`|\mathrm{P}\mathbf{|}`$ is written $`P.`$

Being a density matrix, $`\rho _2`$ is positive definite (its eigenvalues are nonnegative), so

$$det\rho _2=(1S_1^2S_2^2S_3^2)/40,$$
(2.4)
that is,

$$P1,$$
(2.5)
which geometrically restricts $`\mathrm{P}`$ to lie within a sphere of radius 1, the *Poincaré sphere.* This fundamental inequality is more commonly derived using the equivalent fact $`\mathrm{tr}\rho _2^2(\mathrm{tr}\rho _2)^2.`$

If the ensemble represents a single state of polarization (i.e. a ‘pure state’), the coherence matrix is idempotent,

$$\rho _{2,\mathrm{pure}}^2=\rho _{2,\mathrm{pure}}.$$
(2.6)
Taking the trace implies that $`P_{\mathrm{pure}}=1.`$ On the other hand, if the ensemble is completely unpolarized, so $`\rho _{2,\mathrm{un}}`$ is $`1/2`$ times the identity matrix, then $`P_{\mathrm{un}}=0.`$ This leads to the important decomposition of $`\rho _2`$ into pure and unpolarized parts,

$$\rho _2=(1P)\rho _{2,\mathrm{un}}+P\rho _{2,\mathrm{pure}}.$$
(2.7)
The state of polarization corresponding to $`\rho _{2,\mathrm{pure}}`$ here is the eigenvector corresponding to the larger eigenvalue of $`\rho _2,`$ and $`1P`$ is twice the smaller eigenvalue.

The previous statements justify $`P`$ as the *degree of polarization*. It is invariant with respect to any unitary transformation $`𝐮\rho _2𝐮^{},`$ by (2.4) (here, $`𝐮`$ represents an arbitrary $`2\times 2`$ unitary matrix). By the well-known relation between $`2\times 2`$ unitary and $`3\times 3`$ orthogonal matrices, such unitary transformations correspond to rotations of the Stokes vector $`\mathrm{P}\mathbf{.}`$ The operation of a unitary transformation on polarization states (or their ensemble average) is physically interpreted as the operation of a phase retarder , and the degree of polarization is unchanged when the ensemble is passed through a retarder, or series of them.

The Stokes vector (2.3) resides in an abstract, 3-dimensional (Stokes) space, and the representation of phase retarders by 3-dimensional rotations is correspondingly abstract. If $`\rho _2`$ is transformed by 2-dimensional rotations, corresponding to a real rotation of the transverse plane (i.e. $`𝐨\rho _2𝐨^\mathrm{T},`$ with $`𝐨`$ $`2\times 2`$ orthogonal), $`S_1`$ and $`S_2`$ may change keeping $`S_1^2+S_2^2`$ constant; $`S_3`$ remains unchanged. An example case is the rotation in which $`\mathrm{Re}\rho _2`$ is diagonalised:

$$\rho _{2,\mathrm{rot}}=\frac{1}{2}\left(\begin{array}{cc}1+\sqrt{S_1^2+S_2^2}& \mathrm{}S_3\\ \mathrm{}S_3& 1\sqrt{S_1^2+S_2^2}\end{array}\right).$$
(2.8)
For pure states, for which the Poincaré sphere representation is useful, the Stokes parameters provide geometric information about the polarization ellipse . $`S_1`$ and $`S_2`$ inform about the alignment of the ellipse axes, the major axis making an angle $`\mathrm{arg}(S_1+\mathrm{}S_2)/2`$ with the $`x`$-axis. $`S_3`$ gives the ellipse area $`\pi S_3,`$ signed according to polarization handedness, so $`S_3`$ is zero for linear, and $`\pm 1`$ for circular polarization. Obviously, 2-dimensional rotations only affect $`S_1`$ and $`S_2;`$ the rotation giving (2.8) represents aligning the major ellipse axis along $`x,`$ the minor along $`y.`$

## 3 Geometry of the 3-dimensional coherence matrix

The 3-dimensional coherence matrix $`\rho =\rho _3`$ is analogous to (2.1), but with $`\mathrm{E}\mathbf{=}\mathbf{(}\mathrm{E}_\mathrm{x}\mathbf{,}\mathrm{E}_\mathrm{y}\mathbf{,}\mathrm{E}_\mathrm{z}\mathbf{)}\mathbf{:}`$

$$\rho =\left(\begin{array}{ccc}E_xE_x^{}& E_xE_y^{}& E_xE_z^{}\\ E_yE_x^{}& E_yE_y^{}& E_yE_z^{}\\ E_zE_x^{}& E_zE_y^{}& E_zE_z^{}\end{array}\right).$$
(3.1)
As before, it is assumed that $`\mathrm{tr}\rho =1.`$

The Gell-Mann matrices  are the generators of 3-dimensional unitary matrices, just as the Pauli matrices generate 2-dimensional unitary matrices. Therefore, the *generalised Stokes parameters* $`\mathrm{\Lambda }_i,`$ $`i=1,\mathrm{},8`$ , may be defined

$$\rho =\frac{1}{3}\left(\begin{array}{ccc}1+\mathrm{\Lambda }_3+\mathrm{\Lambda }_8/\sqrt{3}& \mathrm{\Lambda }_1\mathrm{}\mathrm{\Lambda }_2& \mathrm{\Lambda }_4\mathrm{}\mathrm{\Lambda }_5\\ \mathrm{\Lambda }_1+\mathrm{}\mathrm{\Lambda }_2& 1\mathrm{\Lambda }_3+\mathrm{\Lambda }_8/\sqrt{3}& \mathrm{\Lambda }_6\mathrm{}\mathrm{\Lambda }_7\\ \mathrm{\Lambda }_4+\mathrm{}\mathrm{\Lambda }_5& \mathrm{\Lambda }_6+\mathrm{}\mathrm{\Lambda }_7& 12\mathrm{\Lambda }_8/\sqrt{3}\end{array}\right).$$
(3.2)
(Other accounts, such as , use a different set of generators.) The analogies between (2.2) and (3.2) are obvious: $`\mathrm{\Lambda }_3`$ and $`\mathrm{\Lambda }_8,`$ only appearing on the diagonal, generalise $`S_1;`$ the terms in the symmetric, off-diagonal part, $`\mathrm{\Lambda }_1,\mathrm{\Lambda }_4,\mathrm{\Lambda }_7,`$ generalise $`S_2;`$ and $`\mathrm{\Lambda }_2,\mathrm{\Lambda }_5,\mathrm{\Lambda }_7,`$ appearing in the antisymmetric, imaginary part, $`S_3.`$ In particular, if $`\mathrm{\Lambda }_4,\mathrm{},\mathrm{\Lambda }_7=0`$ and $`\mathrm{\Lambda }_8=\sqrt{3}/2,`$ then the remaining parameters are proportional to the usual Stokes parameters. This motivates the definition of the *generalised degree of polarization* $`P_3`$  as

$$P_3=\sqrt{\underset{i=1}{\overset{8}{}}\mathrm{\Lambda }_i^2/3}.$$
(3.3)
(A slightly different form was defined by .) This is the length of the 8-dimensional generalised Stokes vector, and, just as in the 2-dimensional case, it is invariant with respect to $`3\times 3`$ unitary transformations. Since $`(\mathrm{tr}\rho )^2\mathrm{tr}\rho ^20,`$ it is readily shown that $`0P_31.`$

Although this approach is mathematically correct, it is not clear physically what $`P_3`$ represents. Unlike the $`2\times 2`$ case, in which the Stokes vector represents the complete state of polarization using three dimensions (which is easily visualised), the generalised Stokes vector requires eight dimensions, which is not so intuitive.

There is a more serious problem with treating the $`3\times 3`$ coherence matrix completely in analogy with the $`2\times 2`$ case - there is no obvious physical interpretation via optical elements of $`3\times 3`$ unitary transformations (nor any corresponding nonparaxial Jones or Mueller calculus). In two dimensions, as an ensemble of plane waves with the same direction but different polarizations propagates through an optical element, the corresponding coherence matrix is transformed by the appropriate Jones matrix, which is unitary for a retarder. In three dimensions, the ensemble of plane waves averaging to the $`3\times 3`$ coherence matrix do not share a common propagation direction in general; any physical device, represented by a $`3\times 3`$ unitary transformation, should be insensitive to the propagation directions of the separate members of the ensemble. Mathematically, it is possible to find a unitary transformation which takes any 3-dimensional state of polarization $`\mathrm{E}\mathbf{=}\mathbf{(}\mathrm{E}_\mathrm{x}\mathbf{,}\mathrm{E}_\mathrm{y}\mathbf{,}\mathrm{E}_\mathrm{z}\mathbf{)}`$ to any other (leaving $`|\mathrm{E}\mathbf{|}^2`$ constant); there is no obvious physical situation in which different states of polarization in three dimensions undergo the same unitary transformation.

It is physically and geometrically natural, however, to consider $`\rho _3`$ under orthogonal transformations rather than unitary ones; if viewed as passive rotations, this is simply equivalent to redefining cartesian axes in 3-dimensional space, and no physical operation at all. Clearly, under rotation, where $`\rho `$ becomes $`𝐨\rho 𝐨^\mathrm{T}`$ ($`𝐨`$ $`3\times 3`$ orthogonal), the real and imaginary parts of $`\rho `$ transform independently of each other. The real part is a positive definite symmetric matrix with five parameters $`\mathrm{\Lambda }_1,\mathrm{\Lambda }_3,\mathrm{\Lambda }_4,\mathrm{\Lambda }_6,\mathrm{\Lambda }_8.`$ Since the (unit) trace is also unaffected by rotation, it may be considered as distinct from the rest of the real part. The imaginary part is a real antisymmetric matrix with three parameters $`\mathrm{\Lambda }_2,\mathrm{\Lambda }_5,\mathrm{\Lambda }_7,`$ and in fact the triple $`(\mathrm{\Lambda }_7,\mathrm{\Lambda }_5,\mathrm{\Lambda }_2)`$ transforms under rotation like an axial vector (noted in ). $`\rho `$ therefore decomposes into three parts: a real scalar (the trace), a real axial vector, and a real traceless symmetric matrix. These different parts (scalar, vector, tensor) are called *irreducible tensor operators* in group theory; the same decomposition occurs for density matrices of atoms with quantum spin 1, for which the vector part is called the *orientation*, the tensor part the *alignment* .

From an analytical viewpoint, it is convenient to represent $`\rho `$ using cartesian axes $`x_1,x_2,x_3`$ with respect to which the tensor part is diagonal, giving

$$\rho =\left(\begin{array}{ccc}M_1& \mathrm{}N_3& \mathrm{}N_2\\ \mathrm{}N_3& M_2& \mathrm{}N_1\\ \mathrm{}N_2& \mathrm{}N_1& M_3\end{array}\right).$$
(3.4)
The diagonal elements of (3.4) are restricted:

$$M_1+M_2+M_3=1,1M_1M_2M_30,$$
(3.5)
which follows from the fact that the tensor $`𝐌\mathrm{Re}\rho `$ is positive definite. It is geometrically convenient not to separate the scalar and (traceless) tensor parts of $`\rho ,`$ and this is not done in (3.4). (3.4) is analogous to (2.8); the real part $`𝐌`$ has been (passively) diagonalised, leaving an off-diagonal imaginary part, which transforms as an axial vector

$$\mathrm{N}\mathbf{=}\mathbf{(}\mathrm{N}_1\mathbf{,}\mathrm{N}_2\mathbf{,}\mathrm{N}_3\mathbf{)}$$
(3.6)
($`|\mathrm{N}\mathbf{|}`$ is invariant under rotations). $`𝐌`$ and $`\mathrm{N}`$ have a simple geometrical interpretation, as follows.

The real symmetric matrix $`𝐌`$ may be interpreted as the moment of inertia tensor of the ensemble. Geometrically, it is the moment of inertia of the set of polarization ellipses in the ensemble (taking each as an elliptical ring with uniform mass per unit length, insensitive to the ellipse handedness). As with moment of inertia tensors in mechanics, it may be represented in terms of its *inertia ellipsoid*, whose points $`(x_1,x_2,x_3)`$ satisfy

$$\frac{x_1^2}{M_1}+\frac{x_2^2}{M_2}+\frac{x_3^2}{M_3}=1.$$
(3.7)
The ellipsoid axes are aligned in the 1,2,3 directions, with lengths $`\sqrt{M_1},\sqrt{M_2},\sqrt{M_3}.`$ If $`M_3=0,`$ the ellipsoid is flat ($`x_3=0`$). In general, the inertia ellipsoid is specified by 6 parameters (the trace and $`\mathrm{\Lambda }_1,\mathrm{\Lambda }_3,\mathrm{\Lambda }_4,\mathrm{\Lambda }_6,\mathrm{\Lambda }_8`$); the diagonal form in (3.4), with three parameters, reflects that three Euler angles have been used implicitly in the choice of axes 1,2,3. The traceless part, dependent on the $`\mathrm{\Lambda }`$ parameters only, gives a measure of departure of this inertia tensor from isotropy.

The vector $`\mathrm{N}`$ also has a simple interpretation as half the expectation value for (spin) angular momentum in the ensemble,

$$\overline{\mathrm{S}}=\mathrm{tr}(𝐒\rho )=2\mathrm{N}\mathbf{,}$$
(3.8)
where the spin matrices $`𝐒_i`$ for spin 1 in a cartesian basis are given componentwise by $`S_{i,jk}=\mathrm{}\epsilon _{ijk}`$ , with $`\epsilon _{ijk}`$ the antisymmetric symbol. The axial vector $`\mathrm{N}`$ is therefore an average of the angular momentum, that is, the average sense of rotation of the ellipses, in the ensemble. Its direction, in general, has no relation to the principal axes of $`𝐌`$ (although its maximum length is limited by them, as described in the next section).

The inertia tensor $`𝐌`$ and orientation vector $`\mathrm{N}`$ therefore provide information about the real, 3-dimensional geometry of the polarization ensemble, and they rotate rigidly. Under more general unitary transformations (which have no physical interpretation), the eigenvalues of $`𝐌`$ and components of $`\mathrm{N}`$ may change arbitrarily (although keeping the unitary invariants $`\mathrm{tr}\rho ,\mathrm{tr}\rho ^2`$ and $`det\rho `$ fixed).

As an example of the geometric interpretation, figure 1 is a representation of the inertia ellipsoid, orientation vector and dual ellipsoid (defined in the next section) for the matrix

$$\rho _{\mathrm{ex}}=\frac{1}{20}\left(\begin{array}{ccc}14& 2\mathrm{}& 2\mathrm{}\\ 2\mathrm{}& 5& \mathrm{}\\ 2\mathrm{}& \mathrm{}& 1\end{array}\right).$$
(3.9)
$`\rho `$ may also be represented by its eigenvectors; if $`\rho _a,\rho _b,\rho _c`$ represent the pure, idempotent coherence matrices corresponding to the eigenvectors of $`\rho `$ with eigenvalues $`\lambda _a,\lambda _b,\lambda _c`$ (i.e. the principal idempotents ), then

$$\rho =\lambda _a\rho _a+\lambda _b\rho _b+\lambda _c\rho _c.$$
(3.10)
The 2-dimensional analogue to (3.10) immediately gives rise to the decomposition (2.7). Since the decomposition in (3.10) is in terms of three density matrices, a decomposition in terms of a single purely polarized part and unpolarized part is, in general, impossible (as previously noted in ). The eigenvalues of $`\rho ,`$ being unitary invariants, do not have a simple geometric interpretation in terms of the inertia ellipsoid or orientation vector; however, the set of three eigenvectors rotates rigidly. This eigenvector representation of $`\rho `$ provides a different geometric representation to that given by the inertia ellipsoid and orientation vector. However, it not not geometrically obvious when a given triple of polarization ellipses in three dimensions represent orthogonal polarization states, and solution of cubic equations is required to find the eigenvectors; moreover, the eigenvectors are not uniquely defined at a degeneracy. By comparison, the inertia tensor and orientation vector may be extracted directly from $`\rho `$ and are always unambiguously defined.

## 4 Inequalities satisfied by $`\rho `$

In this section, various inequalities for $`𝐌`$ and $`\mathrm{N}`$ shall be found, using the fact that $`\rho `$ is a statistical density matrix.

Firstly, the Cauchy-Schwartz inequality may be applied to the off-diagonal elements of $`\rho `$ in (3.1), giving expressions of the form

$$|E_xE_y^{}|^2|E_x|^2|E_y|^2.$$
(4.1)
Using the representation (3.4), these imply

$$N_1^2M_2M_3,N_2^2M_1M_3,N_3^2M_1M_2.$$
(4.2)
Geometrically, this implies that the orientation vector $`\mathrm{N}`$ is confined to a cuboid with vertices $`(\pm \sqrt{M_2M_3},\pm \sqrt{M_1M_3},\pm \sqrt{M_1M_2}).`$ Since $`\rho `$ is a density matrix, $`(\mathrm{tr}\rho )^2\mathrm{tr}\rho ^20,`$ that is

$$N_1^2+N_2^2+N_3^2M_2M_3+M_1M_3+M_1M_2,$$
(4.3)
which is the sum of the inequalities (4.2), and therefore is less strong, geometrically restricting $`\mathrm{N}`$ to lie within the sphere circumscribing the cuboid defined above. $`(\mathrm{tr}\rho )^2\mathrm{tr}\rho ^20,`$ which is the distance by which $`\mathrm{N}`$ fails to touch the surface of this sphere, is a unitary invariant. The traces of higher powers of $`\rho `$ satisfy other inequalities, such as $`\mathrm{tr}\rho ^3\mathrm{tr}\rho ^2\mathrm{tr}\rho ,`$ but such inequalities can be shown to be consequences of (4.2).

Nonnegativity of $`det\rho `$ implies that

$$M_1N_1^2+M_2N_2^2+M_3N_3^2M_1M_2M_3.$$
(4.4)
If $`M_30,`$ then

$$\frac{N_1^2}{M_2M_3}+\frac{N_2^2}{M_1M_3}+\frac{N_3^2}{M_1M_2}1,$$
(4.5)
which geometrically means that $`\mathrm{N}`$ lies within the ellipsoid with axes in the 1,2,3 directions, and lengths $`\sqrt{M_2M_3},\sqrt{M_1M_3},\sqrt{M_1M_2}.`$ This ellipsoid is therefore circumscribed by the cuboid (4.2), and (4.5) is a stronger inequality than (4.2). The relationship between this ellipsoid and the inertia ellipsoid (3.7) justifies calling this ellipsoid the *dual ellipsoid*. If $`M_3=0,`$ (4.4) implies that $`N_1=N_2=0,`$ and (4.2) gives $`|N_3|\sqrt{M_1M_2};`$ if the inertia ellipsoid is flat, the dual ellipsoid is a line normal to it. If $`M_1=1,M_2=M_3=0,`$ then the inertia ellipsoid is a line and $`\mathrm{N}\mathbf{=}0\mathbf{.}`$

As with (2.4), the fundamental inequality for the $`3\times 3`$ coherence matrix is nonnegativity of the determinant, which is stronger than inequalities constructed using the trace. The geometric interpretation of the unitary invariant $`det\rho `$ is the product of the distance by which $`\mathrm{N}`$ fails to touch the dual ellipsoid with the dual ellipsoid volume. This quantity, the trace, and the invariant discussed above are the only unitary invariants of $`\rho .`$ Unlike the 2-dimensional case, the properties of $`\rho `$ are complicated by the fact that polarization information is contained within both the inertia ellipsoid $`𝐌`$ and the orientation vector $`\mathrm{N}\mathbf{.}`$

## 5 Examples of $`3\times 3`$ polarization ensembles

Completely unpolarized waves in three dimensions are a common occurrence, for example black body radiation. In this situation, the $`3\times 3`$ coherence matrix is the completely unpolarized matrix $`\rho _{\mathrm{un}},`$ equal to one third times the $`3\times 3`$ identity matrix (and $`P_3=0`$).

Coherence matrices for pure states of polarization satisfy $`\rho _{\mathrm{pure}}^2=\rho _{\mathrm{pure}}.`$ Using (3.4) and (3.5), this implies that

$$\rho _{\mathrm{pure}}=\left(\begin{array}{ccc}M_1& \mathrm{}N_3& 0\\ \mathrm{}N_3& M_2& 0\\ 0& 0& 0\end{array}\right)$$
(5.1)
with $`|N_3|=\sqrt{M_1M_2},M_1+M_2=1.`$ This is equivalent to a pure state in two dimensions, and represents a polarization ellipse $`\mathrm{E}\mathbf{=}\mathbf{(}\sqrt{\mathrm{M}_1}\mathbf{,}\mathbf{\pm }\mathbf{}\sqrt{\mathrm{M}_2}\mathbf{,}0\mathbf{)}`$ in 1,2,3 coordinates. The ellipse major axis is in the 1-direction, the minor in the 2-direction, and $`\mathrm{N}`$ is normal to the plane of the ellipse (oriented in a right-handed sense of rotation around the ellipse). If $`M_1=M_2=1/2`$ in (5.1), the state is circularly polarized, and $`N_3=\pm 1/2.`$ If $`M_1=1,M_2=0`$ (implying $`N_3=0`$), it is linearly polarized. $`det\rho _{\mathrm{pure}}`$ is zero, but unlike the $`2\times 2`$ case this is not a sufficient condition for a pure state in general: $`\mathrm{tr}\rho ^2`$ must also be 1. The inertia ellipsoid of (5.1) is flat, and $`\mathrm{N}`$ lies on the ‘surface’ of the (linear) dual ellipsoid, with equality in (4.2).

If the state is not pure but $`M_3=0,`$ then $`\rho `$ satisfies (5.1) with $`M_1+M_2=1,`$ but $`|N_3|<\sqrt{M_1M_2}.`$ An example is the density matrix

$$\rho _{\mathrm{ex1}}=\frac{1}{3}\left(\begin{array}{ccc}2& 0& 0\\ 0& 1& 0\\ 0& 0& 0\end{array}\right).$$
(5.2)
The inertia ellipsoid here is flat, and $`\mathrm{N}\mathbf{=}0\mathbf{.}`$ It cannot be a pure state since $`\rho _{\mathrm{ex1}}^2\rho _{\mathrm{ex1}}.`$ This matrix provides an example of a $`3\times 3`$ coherence matrix which cannot be decomposed into the sum of a pure polarization matrix and the completely unpolarized matrix, since there is a zero on the diagonal - $`\rho _{\mathrm{ex1}}\alpha \rho _{\mathrm{un}},`$ for any positive $`\alpha ,`$ leaves a matrix which is not positive definite.

It is easy to visualise ensembles which have $`\mathrm{N}\mathbf{=}0`$: their average angular momentum is zero. This may be achieved, for instance, by requiring for every $`\mathrm{E}`$ in the ensemble, $`\mathrm{E}^{\mathbf{}}`$ has the same statistical weight as $`\mathrm{E}\mathbf{.}`$ $`\rho _{\mathrm{ex1}}`$ is therefore the coherence matrix for the ensemble consisting of the pair of states (with equal weight)

$$_{\mathrm{ex1}}=\{(\sqrt{2},\mathrm{},0),(\sqrt{2},\mathrm{},0)\}$$
(5.3)
(of course, this ensemble is not unique in averaging to $`\rho _{\mathrm{ex1}}`$). The ellipses corresponding to the pair (5.3) are identical apart from their senses of rotation, which are opposite.

$`\rho _{\mathrm{ex1}}`$ is an example of a coherence matrix with $`\mathrm{N}\mathbf{=}0\mathbf{,}`$ although its $`𝐌`$ is not isotropic; that is, the shape of the inertia ellipsoid is not constrained by the direction of the orientation vector. More surprising, perhaps, is that the converse is true - the inertia ellipse may be isotropic yet $`\mathrm{N}`$ takes on the maximum value allowed by (4.2), for example

$$\rho _{\mathrm{ex2}}=\frac{1}{3}\left(\begin{array}{ccc}1& \mathrm{}& 0\\ \mathrm{}& 1& 0\\ 0& 0& 1\end{array}\right),$$
(5.4)
which is the sum of $`\rho _{\mathrm{un}}`$ and a completely antisymmetric matrix (which is not a density matrix). An ensemble which corresponds to $`\rho _{\mathrm{ex2}}`$ is the pair of states with equal weight

$$_{\mathrm{ex2}}=\{(1,\mathrm{},1),(1,\mathrm{},1)\}.$$
(5.5)
The ellipses represented here share their minor axis (in the $`y`$-direction) and have orthogonal major axes. They both have the same shape (eccentricity $`1/\sqrt{2}`$), which geometrically implies that their total moment of inertia is isotropic (higher averages than quadratic are not isotropic). This pair of ellipses, along with the spherical inertia ellipsoid and orientation vector, are shown in figure 2.

Both $`\rho _{\mathrm{ex1}}`$ and $`\rho _{\mathrm{ex2}}`$ have the same eigenvalues $`2/3,1/3,0`$ (equivalently, the same unitary invariants $`\mathrm{tr}\rho ,\mathrm{tr}\rho ^2,det\rho `$); however, the two ensembles (5.3), (5.5) are clearly not the same: the ellipses in the two ensembles have the same shape (eccentricity $`1/\sqrt{2}`$), but the orientations in space are different, and there is no obvious physical transformation between the two sets of states.

In general, the minimum number of states in an ensemble required to specify $`\rho `$ is three, and in fact, the (complex) eigenvectors of $`\rho `$ suffice, as in (3.10). In this case, the eigenvectors make up the ensemble, the probability weighting for each being the corresponding eigenvalue. Since $`\rho _{\mathrm{ex1}},\rho _{\mathrm{ex2}}`$ each have one zero eigenvalue, an ensemble consisting only of two states is sufficient for these examples (the states in $`_{\mathrm{ex1}},_{\mathrm{ex2}}`$ are linear combinations of the eigenvectors, and are not orthogonal).

## 6 Discussion

Interfering nonparaxial polarization fields in three dimensions are more complicated than their paraxial counterparts, and their analysis involves subtle geometric reasoning . Most importantly, the Poincaré sphere description breaks down for polarization states in three dimensions, because it cannot account for the direction of the ellipse normal $`\mathrm{N}\mathbf{;}`$ the appropriate nonparaxial analogue of the Poincaré sphere is the *Majorana sphere*, which involves the symmetric product of two unit vectors, which describe the geometry of the nonparaxial polarization ellipse . These two vectors have a complicated expression in terms of the pure field state $`\mathrm{E}\mathbf{.}`$

It would be of interest to find the relationship between the $`3\times 3`$ coherence matrix and ensembles defined in terms of the Majorana sphere; a natural physical case would be when the $`E_x,E_y,E_z`$ field components are gaussian distributed (for example black body radiation). In this case, for a given $`\rho `$ the distribution on the Majorana sphere would be unique and related to other gaussian Majorana statistics . The analogous $`2\times 2`$ distributions on the surface of the Poincaré sphere have a rather simple form . Given the analytical complications of the Majorana sphere, it is unlikely that the $`3\times 3`$ calculations will be straightforward, and it is unclear whether the geometric interpretation presented here would be helpful in this problem.

As described in section 3, there is no unique direction, or set of directions, associated with propagation for a general $`3\times 3`$ $`\rho ,`$ and therefore, unlike the $`2\times 2`$ case, there is no physical interpretation of $`3\times 3`$ unitary transformations using conventional optical elements. Despite this lack of propagation information, a natural application of the 3-dimensional coherence matrix is in scattering theory, since a scatterer, such as a Rayleigh particle, responds only to the statistical $`\mathrm{E}`$ field at its position, i.e. the coherence matrix. It is therefore possible that classic problems such as atmospheric radiative transfer  may be analysed using the $`3\times 3`$ coherence matrix.

A natural experimental situation in which the nonparaxial coherence matrix is relevant is in the optical near field, for which measurements of the 3-dimensional field are possible  (of course the theory is not restricted to optical frequencies). The geometric interpretation should provide insight into the ensemble of polarization ellipses which gives rise to a measured $`3\times 3`$ coherence matrix.

## Acknowledgements

I am grateful to Michael Berry and John Hannay for useful discussions, and Girish Agarwal for pointing out to me the connection with density matrices in atomic physics. This work was supported by the Leverhulme Trust.

## References


text:
# An efficient control of Curie temperature 𝑇_𝐶 in Ni-Mn-Ga alloys

## Abstract

We have studied the influence of alloying with a fourth element on the temperature of ferromagnetic ordering $`T_C`$ in Ni-Mn-Ga Heusler alloys. It is found that $`T_C`$ increases or decreases, depending on the substitution. The increase of $`T_C`$ is observed when Ni is substituted by either Fe or Co. On the contrary, the substitution of Mn for V or Ga for In strongly reduces $`T_C`$.

Ni-Mn-Ga alloys attract a considerable attention due to the phenomenon of a large magnetic-field-induced strain observed in the ferromagnetic state at temperatures below martensitic transformation temperature $`M_s`$. The practical importance of this phenomenon has stimulated an intensive study of composition dependence of the martensitic transformation temperature. The experimental results obtained have shown that $`M_s`$ is very sensitive to the chemical composition and is observed in a wide temperature interval, ranging from $`<4`$ K up to over 600 K c-1995 . Contrary to $`M_s`$, Curie temperature $`T_C`$ of Ni-Mn-Ga alloys was found to be less compositional dependent. Based on the published experimental results it can be concluded that the highest $`T_C380`$ K is observed in the stoichiometric Ni2MnGa. A decrease of $`T_C`$ in alloys with a deficiency in Mn, which possesses a magnetic moment of $`4\mu _\mathrm{B}`$, is due to the dilution of the magnetic subsystem. For the alloys with Mn excess, it was suggested that the decrease in $`T_C`$ is accounted for by antiferromagnetic coupling of the extra Mn atoms e-2002 . Since large magnetic-field-induced strains are observed only in the ferromagnetic state, an efficient control of the ferromagnetic ordering temperature is of importance for realization of this effect in a large temperature interval. For this aim we studied the influence of Fe, Co, V, and In on Curie temperature of Ni-Mn-Ga alloys.

Polycrystalline ingots of Ni-Mn-Ga with addition of Fe, Co, V, and In were prepared by a conventional arc-melting method in argon atmosphere. The ingots were homogenized at 1050 K for nine days and quenched in ice water. Samples for low-field magnetic measurements were cut from the middle part of the ingots. Curie temperature was determined as a minimum on the temperature derivative of magnetization curve, $`dM/dT`$ (Fig. 1).

Nominal composition and Curie temperature $`T_C`$ of the samples studied is listed in Table 1. It is evident from these data that substitution of Ga for In or Mn for V results in decrease of $`T_C`$. Especially pronounced decrease of $`T_C`$ is observed in the case when Mn atoms, at which magnetic moment is localized, are substituted for V atoms. This is accounted for by the dilution of the magnetic subsystem. In the case of substitution of Ga for In, the decrease of $`T_C`$ is presumably due to an increase of crystal lattice parameter, induced by In which has a larger atomic radius than Ga.

Magnetization measurements of two series of samples where Ni was substituted for Co or Fe showed that Curie temperature increases with increasing Co (or Fe) content (Table 1). In these alloys Mn content remains constant (21 at.% for Co-containing samples and 20 at.% for Fe-containing samples) and, therefore, the Mn magnetic subsystem is supposed to be not influenced by these substitutions. The observed increase of $`T_C`$ in the Co- and Fe-containing samples implies that the magnetic properties of Ni-Mn-Ga should be considered taking into account small magnetic moments located on Ni atoms w-z  and their coupling with magnetic moments of Mn atoms. For example, the increase in $`T_C`$ in these alloys can be accounted for by a stronger Co-Mn (Fe-Mn) exchange interaction as compared to the Ni-Mn one. Besides this scenario, the enhancement of $`T_C`$ in Ni-Mn-Ga by addition of Co or Fe could be explained assuming a noncollinear magnetic configuration of magnetic moments in the ternary Ni2MnGa Heusler compound. In a recent theoretical consideration of magnetic properties of Ni2MnGa and Ni2MnAl Enkovaara et. al. e-2003  suggested that lowering of the total energy at a large spiral wave vector is due to Ni and, therefore Ni significantly affects $`T_C`$ in these alloys. The authors suggested that Curie temperature in Ni2MnGa could be increased by a substitution of the Ni sites. Note also that this suggestion is in accordance with an empirical observation that Curie temperature of Co2MnZ or Cu2MnZ (Z is a non-transition element) alloys is higher than $`T_C`$ in corresponding Ni2MnZ alloys w-z . Our experimental data, however, are not sufficient to make an unambiguous conclusion about the mechanism responsible for the increase of $`T_C`$ and therefore this effect needs further investigation.