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# Structure of the icosahedral Ti-Zr-Ni quasicrystal

## I Introduction

Quasicrystals are solids that combine long-range translational order with rotational symmetries that forbid periodic translational symmetry. To understand the physical properties of quasicrystals, and in particular, the conditions under which nature prefers quasiperiodic to periodic order, it is necessary to determine their atomic structure. The aperiodic nature of quasicrystals requires new methods for structural analysis. In spite of significant progress in recent years, the complete atomic structure of quasicrystals still remains an unsettled question. Boudard and de Boissieu (1999)

The purpose of this paper is to determine the atomic structure of the thermodynamically stable icosahedral TiZrNi quasicrystal ($`i`$-TiZrNi). Although this material is the best-ordered among the known Ti-based quasicrystals, only polycrystalline samples with small grain sizes are available, which limits the information available from diffraction experiments. Therefore this paper develops a new method for structural analysis, based on the real-space structure description, whereby (several kinds of) tiles fill space and each kind of tile receives an identical “decoration” by atomic species, just as unit cells do in ordinary crystallography.

The known quasicrystal structures fall into two main types. Henley and Elser (1986) In a Frank-Kasper type structure, neighboring atoms always form tetrahedra, and the constituent species divide into “small” atoms (with icosahedral coordination) or “large” atoms (with coordination number up to 16). In an Al-transition metal (Al-TM) structure, the transition metals are commonly surrounded by an icosahedron of Al, and Al atoms often form octahedra. In either type, icosahedral quasicrystals (and closely similar crystalline phases called “approximants”) may be built from large ($``$50 atom) clusters with icosahedral symmetry: the “Bergman cluster” Bergman et al. (1957) in the Frank-Kasper case, or the “Mackay icosahedron” Elser and Henley (1985) in the Al-TM case. The Ti-based class of quasicrystals appears to fall on the borderline between the two main types Henley and Elser (1986); thus, though $`i`$-TiMn and $`i`$-TiCr fall in the Al-TM class, our subject $`i`$-TiZrNi is of the Frank-Kasper type. In developing its structural model, we will take advantage of structural relationships to both the $`i`$-AlMnSi and the Frank-Kasper quasicrystals.

### I.1 Methods of Structural Investigation

Many thermodynamically stable quasicrystals such as $`i`$-AlCuFe Tsai et al. (1987), $`i`$-AlPdMn Tsai et al. (1990), and $`d`$-AlNiCo Ritsch et al. (1996) within the Al-TM metal class, $`i`$-AlCuLi and $`i`$-MgZnRE (RE=rare earth) Niikura et al. (1994); Tsai et al. (1994) in the Frank-Kasper class, as well as the new binary quasicrystal $`i`$-CdYb Tsai et al. (2000), can be grown as single grains up to several millimeter size, which allows the measurement of single crystal diffraction data. (Of those mentioned, all except $`i`$-AlCuLi also exhibit long-range order, i.e., instrumentally sharp Bragg peaks.) Using a variety of procedures Steurer and Haibach (1999); Boudard and de Boissieu (1999); Elser (1999), atomic structures have been refined for many of these quasicrystals, such as $`i`$-AlCuLi de Boissieu et al. (1991); Yamamoto (1992); Qiu and Jaric (1995), $`i`$-AlCuFe Cornier-Quiquandon et al. (1991); Katz and Gratias (1993); Cockayne et al. (1993) and $`i`$-AlPdMn Boudard et al. (1991); Janot et al. (1992); de Boissieu et al. (1994).

All these structures were parametrized as cuts by a three-dimensional hyperplane through a density in a six-dimensional hyperspace. Bak (1986); Gratias et al. (1988); Janot et al. (1989a) The difficulty with the six-dimensional approach is that only an average structure can be determined and disorder in the quasicrystal can not be treated appropriately. This, combined with experimental limitations such as truncation effects, usually produces a small number of spurious atoms with unphysical coordination numbers or small interatomic separations in structural models. A purely crystallographic approach alone might, therefore, not be able to fix all the positions and chemical identities of the atoms in quasicrystalline structures. It is furthermore infeasible for quasicrystalline alloys with small grain sizes for which only powder diffraction data are available.

Additional experimental and theoretical data, such as structural information from related approximant phases and results from total energy calculations, can be helpful in the development of realistic structure models for quasicrystals. To incorporate this information a real space approach is desirable. Henley et al. (2000); Mihalkovič et al. (1996) A common real space approach to the structure of quasicrystals is the tiling decoration. One splits the structural analysis into two parts: (1) the problem of the determination of the correct tiling geometry, and (2) the atomic decoration of the tiles. An advantage of the decoration viewpoint is different calculations (ab initio LDA, pair-potentials, diffraction simulation) may be performed using periodic tilings (”approximants”) with larger or smaller unit cells, depending on the calculation’s computational burden, and the results can be compared or combined in a systematic fashion.

The first tiling-decoration approaches were based on similarities to periodic crystalline structures. Elser and Henley (1985); Henley and Elser (1986) In later work energetic considerations were taken into account. Examples of such investigations are the work by Krajči and Hafner who investigated the structure of the $`i`$-AlMgZn quasicrystal using a decoration of the three-dimensional Penrose tiling and pair potentials based on the pseudopotential theory. Krajči and Hafner (1992) Windisch et al. studied the atomic and electronic structure and the lattice dynamics of $`i`$-AlCuLi using molecular dynamics simulations and density-functional calculations of decorated Penrose and canonical cell tilings. Windisch et al. (1994a, b) The structure of the (metastable) $`i`$-AlMn quasicrystal has been studied by Mihalkovič et al. using canonical cell tiling decorations and pairpotentials. Mihalkovič et al. (1996); Mihalkovic et al. (1996) Recently Mihalkovič et al. investigated the structure of decagonal AlCoNi using Monte-Carlo calculations with tile updates. Mihalkovič et al. (2001)

All these investigations are based on the energetics of structural models and do not incorporate diffraction data into the modeling process. To derive a reliable structural model of a quasicrystal, a combination of the crystallographic approach based on diffraction data with information from total energy calculations and relaxation studies is highly desirable. In this paper we present the first study combining a least-squares refinement of X-ray and neutron diffraction data with structural information obtained from ab initio relaxations for approximant structures.

### I.2 The Ti-Zr-Ni quasicrystal

Few studies have been performed for quasicrystalline alloys with grain sizes so small that only powder diffraction data are available. Early work was devoted to the metastable system $`i`$-AlMnSi. Cahn et al. (1988); Janot et al. (1989b); Duneau and Oguey (1989) Another class of such quasicrystals are the Ti-based icosahedral alloys. As early as 1985, Zhang et al. Zhang et al. (1985) discovered a metastable icosahedral phase in Ti-Ni-V. In the following years, further icosahedral phases in Ti-based alloys containing other 3d transition metals such as V, Cr, Mn, Fe, Co and Ni were found. Dong et al. (1986); Kelton et al. (1988); Dunlap et al. (1988); Holzer et al. (1989); Kelton and Zhang (1990); Zhang and Kelton (1991); Libbert and Kelton (1995) However, no stable quasicrystalline phase of this class has been discovered yet. Investigations of projection-based models of the structure of the Ti-Mn quasicrystal by Phillips et al. using tight-binding recursion and pair-potential based energy calculations Phillips et al. (1991, 1992) showed that the Mackay clusters form the backbone of the structure. Furthermore small additions of Si and O, which are crucial for the formation of the Ti-Cr and Ti-Mn quasicrystal Zhang and Kelton (1990); Libbert and Kelton (1995), were found to energetically stabilize the structure. Hennig and Teichler (1997)

In this work the experimentally well-studied icosahedral Ti-Zr-Ni quasicrystal is considered. As early as 1990, Molokanov and Chebotnikov Molokanov and Chebotnikov (1990) discovered a metastable icosahedral phase in Ti-Zr-Ni and in 1997 a thermodynamically stable icosahedral Ti-Zr-Ni phase was discovered by Kelton et al. Kelton et al. (1997) The $`i`$-TiZrNi quasicrystal is formed by either rapid quenching or solid state transformation at temperatures of $`500^\mathrm{o}`$C to $`600^\mathrm{o}`$C, generally leading to a fine microstructure of quasicrystal and crystal phases. The icosahedral phase is rather disordered with a coherence length of about 350 Å, resulting in a small number of measurable structure factors. Therefore, an atomic structure determination by diffraction experiments alone is impossible. Consequently little is known about the atomic structure of $`i`$-TiZrNi.

There is hope of obtaining information on the atomic arrangement in $`i`$-TiZrNi by studying the structure of related periodic “approximants”, meaning crystal structures whose unit cells are fragments of some quasicrystal. There are several competing periodic phases known in the Ti-Zr-Ni phase diagram. Besides the binary phases $`\alpha `$-TiZr, $`\delta `$-Ti2Ni Yurko et al. (1959) and $`l`$-Zr2Ni Kirkpatrick et al. (1962), there are two ternary phases; a cubic Frank-Kasper type structure ($`W`$-phase) and a hexagonal Laves type phase $`\lambda `$-TiZrNi. Molokanov et al. (1989) The structures of the $`W`$-TiZrNi phase, which can be interpreted as a Fibonacci 1/1 approximant of $`i`$-TiZrNi, and of the $`\lambda `$-TiZrNi phases were determined by a Rietveld refinement using X-ray diffraction and neutron scattering data. Structural details were confirmed by ab initio calculations. Kim et al. (1998); Hennig et al. (2000); Majzoub et al. (2001) The $`W`$-TiZrNi phase is closely related to the quasicrystal phase. Kim et al. (1997); Hennig et al. (2000) They both form at similar compositions and temperature ranges and grow with a coherent crystallographic orientation. EXAFS studies indicate a similar local structure in both phases. Sadoc et al. (2000) The presence of a reversible phase transformation between the icosahedral phase and the $`W`$-phase at about $`600^{}`$C indicates that $`i`$-TiZrNi is a low-temperature phase, in contrast to most other quasicrystals. Davis et al. (2000) This opens the exciting possibility that an (aperiodic) $`i`$-TiZrNi quasicrystal, or a very similar large-cell crystal, could be a ground state phase.

### I.3 Contents of this paper

The goal of our work is to model the ideal structure of the $`i`$-TiZrNi quasicrystal. The energetic stability and electronic structure of approximants to the $`i`$-TiZrNi quasicrystals, as well as the competing phases, are the topics of a subsequent paper. In this paper we present a structural analysis of $`i`$-TiZrNi based on a new method, combining powder diffraction data and information from ab initio calculations in form of a constrained least-squares analysis. In Section II the initial decoration model is derived. We base our structure on the canonical cell tiling geometry, which is introduced in Section II.2. As our starting point an initial atomic decoration of the canonical cells is determined from the atomic structure of the 1/1 approximant $`W`$-TiZrNi (Sec. II.3). The following Section III on the optimization of the decoration model is the core of the paper. The constrained least-squares method of refinement is introduced. This approach incorporates structural information from ab initio relaxations as constraints into a least squares refinement of the diffraction data. The resulting structure can be understood as a simple decoration model. This and further details of the structural model, which are important for comparisons to experimental data such as EXAFS measurements, are discussed in Section IV.

## II First decoration model

In this section we derive the initial decoration model. The underlying tiling geometry of our model is given by the canonical cell tilings. The canonical cell tilings provide a tiling model with a high packing fraction of icosahedral clusters. The location of the atomic sites decorating the canonical cells in our model are based on structural features of the $`W`$-phase.

### II.1 Structure of the $`W`$-phase

The $`W`$-TiZrNi phase is a periodic crystalline phase closely related to the icosahedral quasicrystal. Its composition Ti50Zr35Ni15 is close to the composition of the quasicrystal Ti41.5Zr41.5Ni17 and it grows with a coherent crystallographic orientation with respect to the quasicrystalline phase. The structure of the $`W`$-phase was determined using X-ray diffraction and neutron scattering data and confirmed by ab initio calculations. Kim et al. (1998); Hennig et al. (2000)

It consists of a body centered cubic packing of icosahedral Bergman clusters connected by a few “glue” sites (see Table 1). The Bergman cluster as shown in Figure 1 is composed of a central Ni atom surrounded by a small icosahedron of 12 Ti atoms. A second icosahedron is formed by placing 12 Ni atoms directly outside the vertices of the small icosahedron. Finally 20 Zr atoms are placed on the faces of the large icosahedron. The remaining 36 “glue” sites consist of 24 Ti atoms, forming a hexagon that separates the Bergman clusters along the threefold $`111`$ directions, and 12 Ti and Zr atoms, forming a rhombus that divides the Bergman clusters along the twofold $`100`$ directions. The structural analysis and ab initio calculations revealed that chemical disorder in the $`W`$-phase is abundant only between the chemically similar Ti and Zr atoms on the “glue” sites but no disorder is found on the cluster sites. Hennig et al. (2000)

The atomic structure of the $`W`$-phase is similar to the structure of the Frank-Kasper phases $`\mathrm{Al}_{40}\mathrm{Mg}_{40}\mathrm{Zn}_{20}`$ Bergman et al. (1957) and $`\mathrm{Al}_{56}\mathrm{Li}_{32}\mathrm{Cu}_{12}`$ Audier et al. (1988). The $`W`$-TiZrNi structure differs from these in (i) the occupation of the central site of the Bergman cluster, which is empty in the cases of Al-Mg-Zn and Al-Li-Cu, and (ii) the chemical disorder, which occurs between the smaller components Al and Zn or Cu in Al-Mg-Zn and Al-Li-Cu respectively and between the larger components Ti and Zr in the case of Ti-Zr-Ni. Furthermore, the analysis for $`i`$-TiZrNi showed chemical ordering on the sites of the Bergman cluster.

### II.2 Canonical cell tiling

In modeling the quasicrystal structure the canonical-cell tiling (CCT) model is used. Henley (1991) The packing rules permit periodic, random and in principle quasiperiodic tilings, although no rule for a quasiperiodic tiling has been found yet. Henley (1991); Mihalkovič et al. (1996) A large number of periodic approximants structures, ranging from a 1/1 up to a 31/24 approximant, are known for this tiling. In order to use the CCT’s for a structural description of quasicrystals and for a refinement of decoration models to experimental diffraction data, predictions for the structure factors of the icosahedral structure are needed (see App. A and B).

Canonical cell tilings consist of four kinds of disjoint cells denoted $`A`$, $`B`$, $`C`$ and $`D`$. Their nodes are joined by two types of linkages, $`b`$ and $`c`$ bonds, which run in twofold and threefold symmetry directions respectively (see Fig. 2). There are three different kind of cell faces. The $`X`$ face has the shape of an isosceles triangle formed by one $`b`$ bond and two $`c`$ bonds, the $`Y`$ face with a shape of an equilateral triangle is formed by three $`c`$ bonds and finally the rectangular $`Z`$ face is formed by two $`b`$ bonds and two $`c`$ bonds.

The simplest quasiperiodic tiling with icosahedral symmetry is the Penrose tiling. Its tiles are the prolate rhombohedron ($`PR`$) and oblate rhombohedron ($`OR`$); their edges have the length $`a_q`$ and run into fivefold symmetry directions. The CCT can uniquely be decomposed into $`PR`$’s, $`OR`$’s and rhombic dodecahedra consisting of two $`PR`$ and two $`OR`$Henley (1991); Mihalkovič et al. (1996) A rhombic dodecahedron is assigned to each $`b`$ bond and a $`PR`$ to each $`c`$ bond. They are called $`RD`$ and $`PR_c`$ respectively (see Fig. 3). They both connect nodes of the CCT.

Each triangular $`Y`$ face is pierced by another kind of $`PR`$, which we will call $`PR_Y`$. It is useful to divide these $`PR_Y`$ into two subclasses, called $`PR_Y(C)`$ and $`PR_Y(D)`$ according to whether it lies mostly in a $`C`$ or $`D`$ cell respectively. Each $`D`$ cell contains three more $`PR`$’s, called $`PR_D`$. Finally, each $`Z`$ face contains an $`OR`$. This decomposition of the CCT facilitates the description of the decoration model in the following section.

### II.3 Decoration description

We now derive the initial decoration sites for the canonical cell tiles from the structure of the $`W`$-phase. As our starting point we require that our decoration model reproduces the features of the $`W`$-TiZrNi structure wherever possible.

The structure of the $`W`$-phase corresponds to a Fibonacci 1/1 approximant. In the canonical cell tiling description the 1/1 approximant is given by an $`A_6`$ tiling. The decoration of the $`A`$-cell is thus completely determined by the $`W`$-phase. The nodes of the $`A_6`$ tiling correspond to the center of the Bergman cluster in the $`W`$-phase. Thus every node of the CCT will be occupied by a two-shell Bergman cluster and the atomic configuration surrounding the twofold ($`b`$) and threefold ($`c`$) linkages will be the same as in the $`W`$-phase. This already accounts for over 80% of the atoms in decoration of large tilings. We then extend our decoration model to the interior of the larger $`B`$, $`C`$ and $`D`$ cells using the structure of $`W`$-TiZrNi as a guide.

We use the decomposition of the larger canonical cell tiles into prolate and oblate rhombohedron as well as the rhombic dodecahedron to describe their decoration. Since the $`A_6`$ tiling can be decomposed into $`PR_c`$’s and $`RD`$’s, their atomic decoration is determined by the atomic structure of the 1/1 approximant (see Fig. 4). Simply to limit the number of free parameters, it is assumed that the decoration sites of the $`PR_Y(C)`$, $`PR_Y(D)`$ and $`PR_D`$ are the same as for the $`PR_c`$. As for the $`OR`$, its face decoration is forced by the need to adjoin with the other tiles and it has no space for additional interior atoms (see Fig. 4). It is noted here that the site list is the same as for the Henley-Elser decoration of Al-Mg-Zn. Henley and Elser (1986)

After defining the general sites of the decoration model, the nomenclature for the different sites, necessary for a description of the chemical decoration, is introduced. From the $`W`$-phase we derived four general types of decoration sites for the Amman tiles. These are the vertices and the mid-edge sites of the Amman tiles, the two diagonal sites of the $`PR`$, and the sites inside of the $`RD`$. We denote these four kinds of sites by the letters $`\alpha `$, $`\beta `$, $`\gamma `$ and $`\delta `$ respectively (see Fig. 4). Any further differentiation of the sites is indicated by a subscript. The physical significance is that identically labeled sites have the same coordinates and occupations in the decoration model.

The center and the second shell icosahedron of the Bergman cluster decorate vertices of the Amman tiles; these are denoted $`\alpha _1`$ and $`\alpha _2`$ respectively. The sites of the first shell of the Bergman cluster are equivalent to edge centers of the Amman tiles and are denoted by $`\beta _1`$. The $`PR_c`$ has six mid-edge $`\beta _2`$ sites on the plane bisecting its long axis. The two atomic sites on the long axis of the $`PR_c`$ which, furthermore, also decorate the faces of the large icosahedron of the Bergman cluster, are denoted by $`\gamma _1`$. The same $`\gamma _1`$ site also appears in the interior of the $`RD`$. There are four additional sites in the interior of the $`RD`$ on the plane bisecting its long axis. These four sites form a rhombus. The sites on its short axis are denoted by $`\delta _1`$ and the sites on its long axis by $`\delta _2`$. All of the decoration sites discussed up to now were directly derived from the structure of the $`W`$-phase.

For the $`B`$, $`C`$ and $`D`$ cell we assume that the local structure is similar, with the decoration of the nodes and the $`b`$ and $`c`$ bonds the same as derived from the $`W`$-phase. There are additional sites which need to be specified for the $`B`$, $`C`$ and $`D`$ cell. These are the sites connected to the $`PR_Y(C)`$, the $`PR_Y(D)`$, the $`PR_D`$ and the $`OR`$. The acute vertex of the $`PR_Y`$ closest to the $`Y`$ face, the three mid-edges sites adjacent to this vertex and the adjacent site on the threefold axis are not already determined by adjacent tiles. These sites are called $`\alpha _3`$, $`\beta _3`$ and $`\gamma _2`$ respectively (see Fig. 5(a)). For the $`PR_Y(D)`$, a number of sites inside the $`D`$ cell must be specified. Starting from the acute vertex away from the $`Y`$ face, the three mid-edge sites $`\beta _5`$, the three vertices $`\alpha _4`$, and the ring of six mid-edge sites $`\beta _6`$ need to be specified. Furthermore, the site along the diagonal that is adjacent to the acute vertex that is away from the $`Y`$ face is denoted by $`\gamma _3`$ (see Fig. 5(c)). For the $`OR`$, the mid-edge sites are labeled $`\beta _4`$ (see Fig. 5(d)). Along the diagonal of the $`PR_D`$, the site away from the node of the $`D`$ cell is called $`\gamma _4`$. The six mid-edge sites on the plane bisecting the $`PR_D`$ are denoted $`\beta _7`$ (see Fig. 5(b)).

## III Structural Refinement

In this section the decoration model for $`i`$-TiZrNi is optimized using a constrained least-squares analysis of diffraction data incorporating results from ab initio calculations. In this approach, the optimization of the structural model is split into two steps. In the first step, the chemical decoration of the atomic sites is refined by X-ray and neutron diffraction data while the site positions are kept fixed. The atomic positions are then optimized in a second step by ab initio relaxations of the resulting atomic decoration for periodic tilings. These relaxed atomic positions are then used as a constraint to the refinement of the diffraction data.

### III.1 Diffraction data

The sample preparation and the data acquisition was performed by E. H. Majzoub; details can be found in References \[Majzoub, 2000; Majzoub et al., 2000\]. The composition of the sample is (Ti41.5Zr41.5Ni17)98Pb2. The Pb was used, since it was assumed to accumulate in the grain boundaries due to its low solubility in the Ti-Zr-Ni phases. The regions to which the Pb segregates are liquid during the annealing, allowing for faster diffusion of the transition metals, thus enhancing the formation of larger quasicrystalline grains with longer coherence length. The samples were arc-melted from the pure materials under an argon atmosphere and then annealed at $`600^{}`$C for 7 days under vacuum. The X-ray diffraction pattern was measured using Cu-Kα radiation. Neutron powder diffraction data for the sample was obtained at the University of Missouri Research Reactor in collaboration with W. B. Yelon. The neutron wavelength was 1.7675Å.

The uncorrected structure factors were obtained from the powder diffraction data by performing a least-squares fit of the data to a Gaussian peak profile,

$$I(\theta )=I_b+I_0\frac{1}{\sqrt{2\pi }\sigma }\mathrm{exp}\left(\frac{(\theta \theta _0)^2}{2\sigma ^2}\right),$$
(1)
where the peak is centered at $`\theta _0`$ and has a width of $`\sigma `$. The integrated intensity is given by $`I_0`$. Any peak broadening related to the diffractometer or the coherence length of the sample is absorbed in the width, $`\sigma `$, of the Gaussian peak profile. The data were fitted in a small interval of $`\mathrm{\Delta }\theta 1^{}\mathrm{}2^{}`$ around the center of each peak. The dependence of the results on the choice of the size of this interval was accounted for by the estimated errors, which reflect the range over which the fit parameters varied when the size of the interval over which the fit was performed was slightly changed. The background was fitted using a single parameter, $`I_b`$. Out of the 31 peaks for the neutron diffraction data, 24 peaks were indexed to the icosahedral phase and 7 were indexed to the $`\delta `$-Ti2Ni secondary phase. For the X-ray data, 18 structure factors were obtained. Three of the peaks belonged to the $`\delta `$-Ti2Ni secondary phase and 15 to the icosahedral quasicrystal.

Overall, the number of measured structure factors is rather small. Furthermore, since only powder diffraction data is available for the $`i`$-TiZrNi quasicrystal, a few of the measured structure factors were superpositions of crystallographically inequivalent reflections, further exacerbating a structural analysis. In the following two sections the initial decoration model for canonical cell tilings is refined to the measured structure factors constraining the atomic positions by ab initio relaxations.

### III.2 Calculating the structure factors

A least-squares analysis for the chemical decoration of the sites of the structure model to the X-ray diffraction and neutron scattering data from icosahedral Ti41.5Zr41.5Ni17 was performed. As a good approximation of the quasiperiodic tiling, a cubic 8/5 CCT approximant with 576 nodes forming 1320 $`A`$, 576 $`BC`$ and 136 $`D`$ cells containing 52392 atoms per unit cell and with a lattice constant of 98Å was used. Mihalkovič and Mrafko (1993) For the 8/5 approximant, the distribution of the complementary coordinates of the nodes has a small variance. It is thus reasonable to assume that this tiling is a good approximant to the hypothetical quasiperiodic canonical cell tiling. The decorations of the 8/5 canonical cell tiling were constructed using the *Canonical Cell Tiling Package – “There are the atoms”* by Mihalkovič. Mihalkovič (2000)

The icosahedral structure factor, $`F_{\mathrm{ico}}(𝐪)`$, is approximated by averaging over the amplitudes, $`F_{\mathrm{app}}(𝐪_𝐚)`$, of all the Bragg peaks in the approximant that map onto a single orbit of icosahedral peaks given by the wave vector, $`𝐪`$,

$$F_{\mathrm{ico}}(𝐪)=\frac{1}{M_{\mathrm{ico}}(𝐪)}\underset{a}{}M_{\mathrm{app}}(𝐪_a)F_{\mathrm{app}}(𝐪_a).$$
(2)
Each corresponding orbit of reflections in the approximant is represented by a wave vector, $`𝐪_a`$, and has the multiplicity $`M_{\mathrm{app}}`$. $`M_{\mathrm{ico}}`$ is the multiplicity of the icosahedral orbit. The average is taken over amplitudes instead of intensities requiring the correct choice of phases of the structure factors. It is therefore necessary to center the approximant structure in six dimensional space. Details of this and a discussion of the differences between averaging over amplitudes and intensities can be found in Appendices A and B.

The X-ray and neutron diffraction data were taken at room temperature. To account for thermal motion which decreases the structure factor, $`F_{\mathrm{ico}}(𝐪)`$, for large momentum, $`q`$, an isotropic Debye-Waller factor is used,

$$f_{\mathrm{DW}}^s(q)=\mathrm{exp}\left(\frac{B_{\mathrm{iso}}^s}{8\pi ^2}q^2\right).$$
(3)
Due to the small number of measured structure factors, only a single thermal parameter, $`B_{\mathrm{iso}}^s`$ with $`s\{\mathrm{Ti},\mathrm{Zr},\mathrm{Ni}\}`$, for each atomic species was used. The X-ray form factors, $`f_s(q)`$, and the neutron scattering lengths, $`f_s`$, were taken from Reference \[ITC, 1992\].

Altogether the icosahedral structure factors, $`F_{\mathrm{ico}}`$, needed for the refinement are given by

$$F_{\mathrm{ico}}(𝐪)=\underset{l,s}{}c_s(l)f_{\mathrm{DW}}^s(q)f_s(q)\underset{a}{}\frac{M_{\mathrm{app}}(𝐪_a)}{M_{\mathrm{ico}}(𝐪)}\underset{j_l}{}e^{i𝐪_a𝐫_j}.$$
(4)
The first sum is over all classes, $`l`$, of distinct sites of the decoration model. The second sum is over the three different atomic species, $`s\{\mathrm{Ti},\mathrm{Zr},\mathrm{Ni}\}`$, decorating these classes of sites with concentrations, $`c_s(l)`$. The third summation is over the orbits of the approximant structure represented by the wave vector, $`𝐪_a`$, which correspond to the icosahedral wave vector, $`𝐪`$. Finally the last summation is taken over the individual atomic site, $`𝐫_j`$, belonging to the set of sites, $`_l`$, of the site class, $`l`$.

### III.3 Constrained least-squares refinement

Before we can compare the experimental peak intensities to the calculated structure factors, several correction factors have to be taken into account. For both, the X-ray and the neutron diffraction data, the intensities must be corrected by the Lorentz factor, $`\mathrm{sec}\theta \mathrm{cosec}^2\theta `$. Furthermore for the X-rays, the intensities are modified by the polarization, $`P`$, of the beam as described by the Thomson formula

$$\frac{1+P\mathrm{cos}^2(2\theta )}{1+P}.$$
(5)
Since the X-ray beam was unpolarized, $`P=1`$ is used. Overall the estimated intensity of a reflection is given by

$$I_{\mathrm{ico}}(q)=\frac{1+P\mathrm{cos}^2(2\theta )}{(1+P)(\mathrm{cos}\theta \mathrm{sin}^2\theta )}\left|F_{\mathrm{ico}}(q)\right|^2$$
(6)
for X-ray diffraction and by

$$I_{\mathrm{ico}}(q)=\mathrm{sec}\theta \mathrm{cosec}^2\theta \left|F_{\mathrm{ico}}(q)\right|^2$$
(7)
for neutron scattering.

Since the positions of the atoms are kept fixed in the refinement, the last two summations in Equation (4) over the atomic sites of each class with identical atomic decoration and over the orbits of wave vectors for the approximant are performed beforehand for all necessary values of $`𝐪_{\mathrm{ico}}`$. The total structure factor for each $`𝐪`$ was then obtained by summing over these partial structure factors multiplied by the average form factor or scattering length, $`f_s(q)`$, and the average Debye-Waller factor of the atoms decorating the site. The corrected intensity, $`I_{\mathrm{ico}}`$, is then obtained from the calculated structure factor, $`F_{\mathrm{ico}}`$, using Equations 6 or 7 respectively.

From the calculated intensities, the residuals $`R`$ and $`R_w`$ as well as the reduced $`\chi ^2`$ are obtained, providing a standard measure of how well the calculated data matches the observed one. The residuals are defined as

$$R=\frac{_q\left|\sqrt{I_{\mathrm{exp}}(q)}\sqrt{I_{\mathrm{ico}}(q)}\right|}{_q\sqrt{I_{\mathrm{exp}}(q)}}$$
(8)
and

$$R_w=\sqrt{\frac{_qw(q)\left(\sqrt{I_{\mathrm{exp}}(q)}\sqrt{I_{\mathrm{ico}}(q)}\right)^2}{_qw(q)I_{\mathrm{exp}}(q)}}$$
(9)
where the sums are over all observed and calculated intensities, $`I_{\mathrm{exp}}`$ and $`I_{\mathrm{ico}}`$ respectively. The weights $`w`$ are given by the uncertainty of the measured intensities where $`w=1/\sigma _I^2`$. The “goodness” of the fit is given by the reduced $`\chi ^2`$,

$$\chi ^2=\frac{_qw(q)\left(\sqrt{I_{\mathrm{exp}}(q)}\sqrt{I_{\mathrm{ico}}(q)}\right)^2}{NN_p},$$
(10)
where $`N`$ is the total number of reflections and $`N_p`$ is the number of estimated parameters.

Since the number of measured reflections is rather small, additional measured quantities such as the composition of the structure can be incorporated as constraints to the refinement and to limit the parameter space. The composition of the refined structure, $`c_i`$, was constrained by a penalty function,

$$\underset{i\{\mathrm{Ti},\mathrm{Zr},\mathrm{Ni}\}}{}\left(c_ic_i^o\right)^2/\sigma _c^2.$$
(11)
In order to ensure that the composition of the refined structure, $`c_i`$, does not deviate by more than a few percent from the nominal experimental value, $`c_i^o`$, a value of $`\sigma _c=0.02`$ was used. The $`\chi ^2`$ was then minimized by varying the chemical decoration of the sites using Powell’s conjugate direction method. Press et al. (1993)

The chemical decoration of the ideal atomic sites is refined with respect to the structure factors of 38 reflections for $`i`$-TiZrNi, 15 X-ray and 23 neutron diffraction structure factors. The maximum number of different sites of the decoration model is 18. The decoration of the sites in the $`W`$-phase structure was used for the initial configuration, i.e. $`\alpha `$ sites were decorated with Ni, $`\beta `$ sites with Ti and $`\gamma `$ and $`\delta `$ sites with Zr. The chemical decoration on each of these site classes was allowed to vary between two components, either Ti and Zr or Ti and Ni. About a dozen different starting configurations were used. The majority of the optimization runs resulted in the same final concentrations and gave the lowest observed $`\chi ^2`$. However, as common in optimization problems, we cannot guarantee to have found the global minimum. During the refinement classes of sites which showed similar chemical occupancies were combined into a single class. The final number of independent classes of sites was six. This, and the three thermal parameters yield a total of nine estimated parameters.

The refinement using the initial decoration sites yielded for the residuals, $`R`$, of the structure factors 11.5% for X-ray, 6.1% for neutron and 6.9% combined. The weighted residuals, $`R_w`$, are 15.7% for X-ray, 4.6% for neutron and 5.7% combined. The reduced $`\chi ^2`$ is 1.8 indicating crystallographic significance for the fit. The thermal parameters for Ti and Zr, $`B_{\mathrm{iso}}^{\mathrm{Ti}}=1.1`$Å2 and $`B_{\mathrm{iso}}^{\mathrm{Zr}}=1.2`$Å2, are comparable to values found in the $`\delta `$-(Ti,Zr)2Ni alloys. Mackay et al. (1994) The thermal parameter for Ni, $`B_{\mathrm{iso}}^{\mathrm{Ni}}=2.3`$Å2, is about a factor two larger than the value found in $`\delta `$-(Ti,Zr)2Ni. This could reflect static disorder on some of the Ni sites.

### III.4 Ab initio relaxations

So far we have only refined the chemical decoration of the ideal sites of the canonical cell tiling. In the next step we perform ab initio relaxations for the resulting structure to investigate the site positions. The ab initio calculations were performed with VASP Kresse and Furthmüller (1996a, b); Kresse and Hafner (1993), which is a density functional code using a plane-wave basis and ultrasoft Vanderbilt-type pseudopotentials Vanderbilt (1990); Kresse and Hafner (1994). Atomic-level forces are calculated and relaxations with a conjugate gradient method are performed. Ab initio calculations are computationally very expensive. Thus, only calculations for small systems with up to a few hundred atoms are feasible on current computers. Therefore, ab initio relaxations only for the small periodic tilings of the canonical cells were performed. The tilings used were the $`A_6`$, the $`B_2C_2`$ and the $`D_2`$ tiling. Henley (1991)

As a starting configuration, the results from the analysis of the diffraction data were used. The chemical order was idealized by placing only the majority species on each site. The calculations were performed using the generalized gradient approximation by Perdew and Wang Perdew and Wang (1992), and a plane-wave kinetic-energy cutoff of $`E_{cut}=302.0`$eV was chosen to ensure convergence. The pseudopotentials for Ti and Zr describe, besides the usual outer shell states, also the 3p and 4p states, respectively, as valence states. Due to the size of the quasicrystal-like tiling structures a check of the convergence with the number of k-points was not always possible due to computational limitation. Therefore the k-point mesh was chosen as large as possible, i.e. $`3\times 3\times 3`$ for the $`A_6`$ tiling, $`2\times 2\times 2`$ for the $`B_2C_2`$ tiling and $`1\times 1\times 1`$ for the $`D_2`$ tiling, corresponding to 4, 2 and 1 $`𝐤`$-points in the irreducible part of the Brillouin zone respectively. The positions of the atoms, as well as the shape and volume of the unit cells, were relaxed until the total electronic energy change was smaller than $`1`$meV. This corresponds to atomic-level forces $`F_{max}0.02`$eV/Å.

The atomic positions after the ab initio relaxation were remarkably close for all three tilings to the ideal atomic positions, such as the corners, mid-edges etc. of the decorated tiles, with average displacements smaller than 0.13 Å (see Table 2).

The resulting atomic positions from the relaxation calculations were then symmetrized. This involves mapping the relaxed positions back onto their canonical orbit and calculating the average canonical coordinates of equivalent atoms. Mihalkovič (2000); Mihalkovic et al. (1996) The deviations of the relaxed atomic positions from their canonical coordinates are in general rather small with an average deviation of $`0.07`$Å. The largest deviation occurs for the $`\beta _4`$ site, where the relaxed positions deviates by $`0.19`$Å in the $`D_2`$ and by $`0.05`$Å in the $`B_2C_2`$ cell. In fact, the deviations in both cells have almost opposite directions.

The symmetrized positions are used as an input for fitting the site chemistry to the diffraction data. This process can, in principle, be repeated until convergence is achieved. In our case, since no significant changes in the decoration were observed, the optimization was already converged after the refinement of the relaxed atomic positions.

Using the relaxed positions, the residuals, $`R`$, of the structure factors decrease to 10.8% for X-ray, 5.1% for neutron and 5.9% combined. The weighted residuals, $`R_w`$, are 15.0% for X-ray, 4.0% for neutron and 5.1% combined. The reduced $`\chi ^2`$ is 1.4, indicating a good agreement between the calculated and measured structure factors (see Fig. 6). Overall, the relaxed positions lead to a better agreement with the diffraction data than the unrelaxed positions.

The resulting chemical decoration is given in Table 3. The thermal parameter decreases for Ti to 0.3Å2, for Zr to 1.0Å2 and it is unchanged for Ni. The chemical decorations on the sites change by less than 5%, with the exception of site $`\gamma _2`$, where the probability of finding Ti increases by 10%, and the site $`\alpha _4`$, that is now only occupied by Ni. The stoichiometry changes by less than 0.5%. The composition of the refined structure Ti41Zr40Ni19 agrees with the nominal composition Ti41.5Zr41.5Ni17 to within 2%.

This is the first refinement that systematically combines diffraction data and structural energies. Since the powder diffraction data for $`i`$-TiZrNi are not available for sufficiently high momentum $`q`$ to usefully constrain the coordinates the atomic positions were fixed to the results from ab inito relaxations. If better data were available for this quasicrystal, positional information would be available from the diffraction data as well. The relaxed atomic positions lead to an improved agreement between the calculated and measured structure factors. This illustrates that results from ab initio relaxations can successfully be incorporated as constraints into structural refinements.

## IV Structural features of the quasicrystal

In this section we discuss some details of the resulting structural model for $`i`$-TiZrNi using the large 8/5 approximant and compare to the structure of the $`W`$-phase. Results for pair correlation functions, coordination numbers and local atomic environments, which are important for comparisons to experimental data such as EXAFS, are given in Tables 4 and 5 as well as Figure 7.

Figure 7 shows the partial pair-distribution functions for the 1/1 approximant phase, $`W`$-TiZrNi, and the 8/5-approximant. Tables 4 and 5 list the numbers and average distances of nearest neighbors in both structures. The pair-correlation functions for the $`W`$-phase and the quasicrystal resemble another, corresponding to the similar local atomic structures of both phases. While the $`W`$-phase has no Ni-Ni nearest neighbors at all, the number of Ni-Ni neighbor pairs in the quasicrystal is rather small. Chemical disorder was found only on a small number of sites, apparently localized to the glue region between the Bergman cluster, similar to the $`W`$-TiZrNi approximant (see Tab. 1). Results of recent investigations of the local atomic structure of the $`W`$-phase and the quasicrystal by EXAFS measurements Sadoc et al. (2000) are consistent with the pair-distribution functions of the structural model developed here.

The features of the decoration model of the quasicrystal can be understood by the energetics of the interactions between the constituents. Ti and Zr atoms are completely miscible and exhibit a zero heat of mixing. Ti and Ni as well as Zr and Ni, on the other hand, have a strongly negative heat of mixing, indicating strong attractive interactions between these pairs. Thus, it is energetically favorable for all the Ni atoms to be surrounded by Ti or Zr. This explains why, in the structure of the 1/1 approximant and the quasicrystal, hardly any Ni-Ni bonds occur. Since Zr is slightly larger than Ti it is no surprise that Zr occupies the more open sites of the structure given by the interior of the $`PR`$ and $`RD`$.

The refined structure of the quasicrystal is very similar to the structure of the 1/1 approximant phase, $`W`$-TiZrNi. The atomic sites for the structure model of the quasicrystal are based on the $`W`$-phase structure. The refined decoration of these sites is the same in most cases. However, the $`\delta _1`$ and $`\delta _2`$ sites along the $`b`$ bond are occupied by Zr only in the quasicrystal, while in the $`W`$-phase chemical disorder occurs between Ti and Zr. Overall, the amount of chemical disorder in the quasicrystal appears to be of the same order or even slightly less than in the $`W`$-phase. Considering the apparent disorder in the powder diffraction patterns, the lack of chemical disorder on most sites of the structural model of the quasicrystal seems surprising at first and might be fortuitous. However, it is noted, that the quasicrystal forms at low temperatures, possibly reducing the amount of entropic disorder. We speculate, that an (aperiodic) $`i`$-TiZrNi quasicrystal, or a very similar large-cell crystal, could be a ground state phase. This idea is investigated in a subsequent paper.

## V Conclusion

We have developed the first realistic structural model for the icosahedral Ti-Zr-Ni quasicrystal. Our model is based on atomic decorations of the canonical cell tilings. For the structural refinement a new method of constrained least squares analysis is used, combining X-ray and neutron diffraction data with results from ab initio relaxations. The refined structural model exhibits only small amounts of chemical disorder between Ti and Zr.

This structural model should be helpful for a better understanding and interpretation of experimental data such as, for example, EXAFS data, pcT-isotherms, relations to crystalline phases and the ternary phase diagram. Furthermore this model will enable us to investigate the possibility of $`i`$-TiZrNi as a ground state quasicrystal.

###### Acknowledgements.

The work at Washington University was supported by the National Science Foundation (NSF) under grants DMR 97-05202 and DMR 00-72787. Work at Cornell made use of the Cornell Center for Materials Research Computing Facilities, supported through the National Science Foundation MRSEC program (DMR-0079992). C.L.H. was supported by the Department of Energy (DOE) grant DE-FG02-89ER-45405. R.G.H. was partially supported by NSF grant DMR-0080766 and by DOE grant DE-FG02-99ER45795. We thank Alex Quandt and Jeff Neaton for discussions about the VASP code, Marek Mihalkovič for the code to decorate canonical cell tilings and E. H. Majzoub for providing us with the X-ray and neutron diffraction data.

## Appendix A Diffraction from Approximants

In this Appendix a method is presented for the calculation of the structure factors of the icosahedral quasicrystal from large cubic approximants.

Assuming that the local structure of the approximant closely resembles the structure of the quasicrystals, the quasicrystal structure factors can be approximated by the structure factors of a large periodic approximant. However, a direct comparison of the structure factors of the approximant to measured structure factors of the icosahedral phase is not possible due to the different symmetries of the structures. This leads to different multiplicities of corresponding reflections for both structures and a splitting of orbits of icosahedral reflections in the case of the approximant. The problem is further complicated by the fact that the Bragg reflections of the quasicrystal form a dense set, which is not the case for the periodic approximants. Inequivalent low intensity reflections, therefore, can become degenerate in the approximant. The problem of degenerate reflections in the approximant becomes increasingly important in smaller approximants. Since, for structural investigations only Bragg reflections with intensities above a threshold are used, the degeneracy problem can be avoided by using a large enough approximant.

The six dimensional representation of icosahedral quasicrystals enables one to relate their diffraction patterns to the diffraction patterns of their related crystalline approximants. The reciprocal lattice (RL) of the approximant is obtained when the golden mean, $`\tau `$, which appears in the icosahedral basis of the physical space, is replaced by the rational number $`\tau _n=f_{n+1}/f_n`$. The mapping of the icosahedral RL to the cubic RL is induced by keeping the same six indices but using the rationally related basis vectors. Every icosahedral reciprocal lattice vector (RLV) maps to a unique cubic RLV. The maximum cubic subgroup of the icosahedral symmetry group, $`m\overline{3}\overline{5}`$, is given by $`m3`$. While the order of the icosahedral group is 120, the order of the cubic subgroup is only 24. Thus, the image of one orbit of equivalent icosahedral reflections is the union of up to five cubic orbits. Although an icosahedral RLV vector does not map to a cubic RLV in the same direction, any icosahedral RLV in a given fundamental domain of the cubic group maps to a cubic RLV in the same fundamental domain. Thus, to get the standard representative cubic RLV’s corresponding to one icosahedral RLV orbit, we only need to check the images of all icosahedral RLV’s in that orbit whose orientations fall in the standard principal triangle of the cubic group.

The calculation of the structure factors for the icosahedral phase from the cubic approximant proceeds in two steps. First, for every orbit of icosahedral reflections with complementary components smaller than some cutoff, $`Q_{\mathrm{max}}^{}`$, the multiplicity, $`M_{\mathrm{ico}}`$, is determined by analyzing if the representing RLV points into any high-symmetry direction of the icosahedral point group. The icosahedral RLV’s of the orbit which fall into the fundamental domain of the cubic point group are determined. Depending on the multiplicity of the icosahedral orbit this results in a set of up to five RLV’s. For each of these icosahedral RLV, the corresponding cubic RLV in the approximant is determined by the projection method, where the golden mean, $`\tau `$, in the basis vectors of the physical space is replaced by the rational approximant, $`\tau _n`$. The multiplicity, $`M_\mathrm{a}`$, of the orbit represented by each of the cubic RLV’s is calculated by analyzing if the cubic RLV points into any high-symmetry direction of the cubic point group.

In the second step, to approximate the structure factor of the icosahedral RLV, the structure factors of the corresponding cubic RLV’s of the periodic approximant are calculated and averaged. This average could be taken over either the amplitudes or the intensities of the structure factors. While for reflections with a high intensity, both methods of averaging result in nearly the same values, for low intensity reflections the right choice of averaging is more important. Since all the cubic approximants are centrosymmetric, the structures can be centered such that the phases of the structure factors are either 0 or $`\pi `$, resulting in a plus or minus sign for the structure factors. The correct centering of the approximant structures involves a shift in the six-dimensional space. The 1/1 approximant structure requires no shift. For the cubic 2/1, 3/2, 8/5 and 13/8 approximants of the canonical cell tiling, the six-dimensional centering vector is given by $`\frac{1}{2}(1,0,1,1,0,0)`$. These approximants have the symmetry group $`Pa\overline{3}`$. That means that there is one 3-fold axis which passes through the node at the origin in real space. That 3-fold axis is chosen to be in the cubic $`(111)`$ direction which corresponds to the six-dimensional vector $`(1,0,1,1,0,0)`$.

For reflections with nearly vanishing intensity, the splitting of the reflection in the approximant leads to a distribution of structure factors around zero. An averaging over intensities would lead to a positive value, while for averaging over amplitudes the resulting value is closer to zero and provides a better approximation. In this work, the icosahedral structure factor is estimated by averaging over the amplitudes of the corresponding structure factors of a large cubic approximant (see Eqs. (2) and (4)). In order for the approximated structure factors to closely resemble the icosahedral structure factors, the atomic structure of the approximant has to resemble the structure of the icosahedral phase closely, which is more likely the case for larger approximants.

## Appendix B Averaging over Amplitudes or Intensities

To compare the accuracy of the prediction of the structure factors from averaging over amplitudes and over intensities the method is applied to the Penrose tiling, since for the ideal quasiperiodic Penrose tiling, the structure factors can be easily calculated by Fourier transformation of the acceptance domain. If the vertices of the Penrose tiling are identical scatterers, the structure factors of the ideal quasiperiodic Penrose tiling are determined by the Fourier transformation of the triacontahedral acceptance domain. Elser (1986)

In Figure 8 the structure factors for the ideal quasiperiodic Penrose tiling are compared to the estimated values from the cubic Penrose 1/1 and 3/2 approximant structures. While for the 1/1 approximant the structure factors deviate strongly at lower intensities, already for the 3/2 approximants the estimated structure factors closely resemble the icosahedral structure factors over about three orders of magnitude. Averaging over amplitudes instead of intensities leads to significant improvements in the case of the 1/1 approximant, but only minor changes for the 3/2 approximant. It is noted here, that the Penrose tiling decorated with unit scatterers on the vertices is likely to oversimplify the problem and that in more realistically decorated structures, larger deviations could occur.


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# Reply to “Comment on ‘Magnetic field effects on neutron diffraction in the antiferromagnetic phase of 𝑈𝑃𝑡₃’ ”

Present address: \]Department of Physics and Astronomy, Clemson University, Clemson SC 29634

## Abstract

Fåk, van Dijk and Wills (FDW) question our interpretation of elastic neutron-scattering experiments in the antiferromagnetic phase of UPt3. They state that our analysis is incorrect because we average over magnetic structures that are disallowed by symmetry. We disagree with FDW and reply to their criticism below. FDW also point out that we have mistaken the magnetic field direction in the experiment reported in Ref. dij98, . We correct this error and note that our previous conclusion is also valid for the correct field orientation.

We disagree with the claim of Fåk, et al.Fåk et al. (2002) that our analysis of elastic neutron-scattering experiments in the antiferromagnetic (AFM) phase of UPt3 is incorrect because we average over magnetic structures that belong to different irreducible representations of the crystallographic space group. Classification of magnetic structures and magnetic phase transitions on the basis of irreducible representations of the space group and time-inversion neglects the fundamental role that exchange interactions play in magnetic phase transitions. Dzyaloshinskii (1964); Andreev and Marchenko (1976, 1980); Toledano and Toledano (1987) Exchange interactions are invariant under continuous rotations of all the moments, and typically dominate the anisotropy energies that couple the atomic moments to the lattice. Classification of magnetic structures based on the exchange group accounts for the wide variety of magnetic structures that are observed in magnetic materials. The Shubnikov classification, which does not take into account the higher symmetry of the exchange interactions, disallows some of these structures.Andreev and Marchenko (1980)

Thus, for a magnetic instability driven by exchange interactions the primary irreducible representation is based on the combined group of continuous rotations in spin space, the crystallographic space-group and time-reversal, $`𝖦_{\text{ex}}`$. The irreducible representations of the exchange group combine several irreducible representations of the space group.Izy91  Thus, not only are magnetic structures corresponding to irreducible representations of the space group allowed. On the contrary, structures that are a combination of irreducible representations of the space group, but belong to one exchange representation, are also possible magnetic structures. Many examples of magnetic structures with these type of “mixed space-group representations” mixed  are described in the literature.oles76 ; Toledano and Toledano (1987)

In most materials the magnetically ordered phase is defined by one irreducible representation of the space group due to the anisotropy energies which resolve (at least partially) orientational degeneracies within the exchange representation. anisotropy  However, since the anisotropy terms are relatively weak, the energy splitting of differently oriented magnetic states are small. Thus, magnetic domain structures, including their response to magnetic fields, should be analyzed using the degenerate, or nearly degenerate, states within the full exchange multiplet. We believe this is the correct approach to understanding the magnetism and to analyze the possible magnetic structures in the heavy fermion compound UPt3.

In our analysis, we considered a general model for UPt3 compatible with the available data.Moreno and Sauls (2001) We selected one irreducible representation of $`𝖦_{\text{ex}}`$ that is consistent with elastic neutron scattering data in zero field. If we neglect the spin-lattice couplings then only the relative orientations of the atomic moments in the magnetic unit cell are fixed by the primary irreducible representation. Anisotropy energies are also included to resolve, or partially resolve, the degeneracies of the exchange representation.

Neutron scattering and X-ray experiments in UPt3 show AFM order with propagation vector $`\stackrel{}{q}_1=\stackrel{}{a}_1^{}/2`$.3arms  The magnetic U ions occupy two symmetry equivalent positions in the unit cell. The magnetic representation has 6 dimensions (3 times the number of magnetic ions). Until very recently, the crystal structure of UPt3 was thought to be hexagonal with space group $`D_{6h}^4`$. However, a recent X-ray diffraction experiment revealed a lower trigonal symmetry with space group $`D_{3d}^3`$. Walko et al. (2001) In either case, the magnetic representation can be decomposed in six one-dimensional representations. Three of these correspond to FM alignment of the ions in the unit cell; the other three representations correspond to AFM alignments. The alignment of the magnetization or sub-lattice magnetization may be along the $`\widehat{x}`$, $`\widehat{y}`$ or $`\widehat{z}`$ axes. However, these six structures are connected with only two exchange representations corresponding to FM or AFM alignment in the unit cell. Table 1 shows the irreducible representations and basis functions of the crystallographic space groups $`D_{6h}^4`$ and $`D_{3d}^3`$ grouped by their corresponding exchange multiplets.

Our study is based on a free energy functional (Eq. 9 of Ref. Moreno and Sauls, 2001) which includes the exchange, anisotropy and Zeeman energies. First, a uniaxial anisotropy term (not shown in Eq. 9 of Ref. Moreno and Sauls, 2001) restricts the order parameter to the basal plane. In addition, the in-plane (hexagonal) anisotropy energy favors alignment of the moments along any of the three directions perpendicular to the hexagonal lattice vectors. Note that the form of the anisotropy energy is the same for either $`D_{6h}^4`$ and $`D_{3d}^3`$ symmetry groups. The effect of a magnetic field on the AFM order is included through the Zeeman coupling to the atomic moments, which in general mixes different nearly degenerate representations of the space group within the exchange multiplet.Moriya  The competition between the anisotropy energy and the Zeeman coupling induces hexagonal modulations of the upper critical field as a function of the orientation of the field in the basal plane at the transition to the superconducting phase.Keller et al. (1994); Sauls (1996) The in-plane anisotropy energy is small, since a large in-plane anisotropy energy would produce an orthorhombic modulation of the upper critical field, which is not observed. Higher order anisotropy terms example  which might resolve the remaining degeneracy and thus favor alignment of the moments along the propagation vector of the magnetic order would be extremely small. Therefore, the three structures shown in Fig. 1 of Ref. Moreno and Sauls, 2001 are degenerate, or quasi-degenerate, and certainly should be considered in the analysis of the magnetic structure and neutron scattering in the presence of an in-plane magnetic field. Thus, in our analysis we consider the possibility of degenerate, or nearly degenerate, magnetic structures by making an average over different distributions of domains. We also presented results and predictions for the single magnetic structure with the magnetization parallel to the propagation vector. The authors of the comment seem to have overlooked this prediction, which if we had confined our analysis to a single representation of the space group, as Fåk, et al. advocate, would be the only relevant structure.

We did mistake the magnetic field direction in the experiment reported in Ref. dij98, . In the correct geometry of that experiment the field was along the reciprocal lattice direction \[-1,2,0\]. The ratios reported in Eq. 5 of Ref. Moreno and Sauls, 2001, and in the paragraph that follows that equation, should be modified as follows. When only domain “1” is populated we have $`r=1`$. For a crystal with equally populated magnetic domains, the correct ratio between the scattering rate at high field and zero field is

$`r={\displaystyle \frac{1(0.441\mathrm{cos}(\theta _H+\pi /2))^2}{1(0.441\mathrm{cos}(\theta ))^2}}=0.89.`$ (1)
Our previous conclusion, stated for the incorrect field orientation, is unchanged for the correct field orientation; it is not possible based on existing data to conclude whether or not the U moments rotate with the field, because of the small change in intensity that is expected for this Bragg peak and the large error bars that are reported for the intensity. We also concluded that, in order to understand UPt3 magnetism in the presence of magnetic field or under pressure, systematic, zero-field measurements of the intensity of a number of magnetic peaks in the same single crystal, such as those reported in Ref. Goldman et al., 1986, need to be carried out. Furthermore, our hypothesis that intrinsic stacking faults pin the AFM domain walls in the ab-plane and fix the spatial distribution of domains with different propagation vectors has been recently reinforced. For uniaxial pressures applied to the basal plane a significant increase in the magnetic intensity has been reported van Dijk et al. (2001) in contrast with the relatively small change in a magnetic field.lus96a ; dij98  Pinning by intrinsic stacking faults may help explain this difference, since the applied magnetic field leaves the distribution of regions with different propagation vectors unaltered. However, uniaxial pressure likely disturbs the configuration of stacking faults leading to a stronger effect on the magnetic structure.

In conclusion, our analysis of the neutron scattering data is based on a sound theoretical model for possible magnetic structures in UPt3, which is more general than would be allowed based on a single irreducible representation of the space group. The relative importance of exchange interactions leads naturally to mixed irreducible representations of the crystal space group, which are relevant because they are energetically allowed.


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# Is it 𝑒 or is it 𝑐? Experimental Tests of Varying Alpha

\[

## Abstract

Is the recent evidence for a time-varying fine structure ’constant’ $`\alpha `$ to be interpreted as a varying $`e`$, $`c`$, $`\mathrm{}`$, or a combination thereof? We consider the simplest varying electric charge and varying speed of light theories (VSL) and prove that for the same type of dark matter they predict opposite senses of variation in $`\alpha `$ over cosmological times. We also show that unlike varying $`e`$ theories, VSL theories do not predict violations of the weak equivalence principle (WEP). Varying $`e`$ theories which explain astronomical inferences of varying $`\alpha `$ predict WEP violations only an order of magnitude smaller than existing Eötvös experiment limits but could be decisively tested by STEP. We finally exhibit a set of atomic-clock and related experiments for which all (hyperbolic) varying $`\alpha `$ theories predict non-null results. They provide independent tests of the recent astronomical evidence.

\]

The possibility that the fine structure constant $`\alpha e^2/\mathrm{}c`$ might be a dynamical variable has attracted considerable attention following the observations of Webb et al . These observations use a powerful new many-multiplet technique to extract a larger fraction of the information encoded in quasar (QSO) absorption spectra at medium redshift than traditional doublet studies. They study energy differences between relativistic transitions to many different ground states and compare observations with laboratory measurements and many-body computations. The continuing trend of these results is that the value of $`\alpha `$ was lower in the past, with $`\mathrm{\Delta }\alpha /\alpha =0.72\pm 0.18\times 10^5`$ for $`z0.53.5.`$

It is clear that such a discovery, if correct, has important implications for the foundations of physics, but pinpointing the precise conclusions to be drawn is more controversial. While it is reassuring that $`\alpha `$ was lower rather than higher in the past, so that QED remains perturbative, the full implications for unification are still unclear , and we shall not discuss them further here. These results also raise the question: which of $`e`$, $`\mathrm{}`$ and $`c`$ might be responsible for any observed change in $`\alpha `$ and what operational meaning should be attributed to such a determination? Undoubtedly, in the sense of , one has to make an operationally “meaningless” choice of which dimensional constant is to become a dynamical variable. Yet, in practice this choice is never arbitrary; it is clearly dictated by simplicity once the detailed dynamics of the theory have been established. Here, we argue that the dynamics have unambiguous observational implications: a combination of experiment and simplicity therefore selects one member of a dimensionless combination ($`\alpha `$) of dimensional constants ($`e`$, $`\mathrm{}`$ and $`c`$) to which we should preferentially ascribe its space-time variation. We will present a number of clear experimental tests which can distinguish rival theories of $`\alpha `$ variation which are expressed through explicit change in $`e`$ or $`c`$. Existing theories will be used as examples.

Several theoretical contexts for the Webb et al results have been explored. Sandvik, Magueijo and Barrow  have recently proposed a varying electric charge theory (BSBM), inspired by an earlier construction of Bekenstein . A supersymmetric version of this theory was created in . Various dilatonic alternatives, in which all coupling constants vary as a function of a single field, may also be considered (including dilaton couplings to the cosmological constant ). Other candidates to explain variations in $`\alpha `$ are the varying speed of light (VSL) theories , which also offer an alternative to inflation for solving cosmological problems. As archetypal examples we take the BSBM theory  and the VSL theory presented in . By introducing an appropriate change of units we can turn VSL into a constant $`c`$ theory, but the dynamics will then look unnecessarily complicated; likewise BSBM can be rephrased as a constant $`e`$, varying $`c`$ theory, with a concomitant increase in complexity. This is why we say that BSBM is a varying $`e`$ theory while the theory in  is a VSL theory: dynamics fixes the choice. Crucially, the dynamics also have unambiguous observational implications. We will show that with standard dark matter VSL predicts an increasing $`\alpha `$, as a function of cosmological time. By contrast, BSBM predicts a decreasing $`\alpha `$, a conclusion which can only be reversed by a different choice of dark matter composition, as explained in . This is a striking difference, but pending the determination of the nature of the dark matter one can use both BSBM and VSL to fit the Webb et al results. The same remark applies to other cosmological tests, such as constraints arising from the cosmic microwave background (CMB) and Big Bang Nucleosynthesis (BBN) .

However, BSBM and VSL theories also make different predictions regarding spatial variations in $`\alpha `$ near massive objects. Due to these variations all changing-$`\alpha `$ theories predict a ’fifth force’ effect , but we will see that the exact details can distinguish between BSBM and VSL. In BSBM theory the fifth force induces an anomalous acceleration which, unlike gravity, depends on the material composition of the test particle and so violates the weak equivalence principle (WEP). The VSL theories, on the other hand, are consistent with the WEP, as first noted by Moffat.

The exact level of WEP violation predicted by BSBM depends upon an unsolved problem in nuclear and hadronic physics: how much of the mass-energy of nuclei is of electrostatic nature? As yet, there is no reliable answer to this question  but we can still estimate the magnitude of WEP violation, which reveals that the BSBM theory is marginally consistent with current Eötvös experiments. However, the next generation of WEP tests, such as the STEP project , will easily be sensitive enough to detect violations of the WEP as predicted by BSBM even by the most conservative estimates. Should violations be observed, it should be seen as a success for varying $`e`$ theories. If not, then we must narrow our interest to VSL theories in order to accommodate observational signals of varying $`\alpha `$. Thus, space experiments such as STEP can provide an independent experimental test of any astronomical evidence for varying $`\alpha `$, and decide between a varying $`e`$ or $`c`$ interpretation.

We start by describing briefly the two theories to be used as exemplars. In the BSBM varying $`\alpha `$ theory, the quantities $`c`$ and $`\mathrm{}`$ are taken to be constant, while $`e`$ varies as a function of a real scalar field $`\psi ,`$ with $`e=e_0e^\psi `$. As shown in , it is possible to rewrite this theory in such a way that $`\psi `$ only couples to the free electromagnetic lagrangian $`_{em}`$. The field tensor $`f_{\mu \nu }=_\mu a_\nu _\nu a_\mu `$ and the covariant derivatives $`D_\mu =_\mu +ie_0a_\mu `$ then do not contain $`\psi `$, and the action takes the form:

$$S=d^4x\sqrt{g}\left(_g+_{mat}+_\psi +_{em}e^{2\psi }\right),$$
(1)
where $`_\psi =\frac{\omega }{2}_\mu \psi ^\mu \psi `$, $`_{em}=\frac{1}{4}f_{\mu \nu }f^{\mu \nu }`$, and $`_{mat}`$ (the lagrangian of all matter fields apart from $`_{em}`$) does not depend on $`\psi `$. The gravitational lagrangian is the usual $`_g=\frac{1}{16\pi G}R`$, with $`R`$ the curvature scalar.

In contrast, the covariant VSL theory proposed in  assumes that $`c`$ varies, and builds the simplest dynamics on this premise, which is equivalent to a choice of a system of units. It assumes that $`c=c_0e^\chi `$ (with $`\chi `$ another real scalar field) and that the full matter Lagrangian $`_M`$ does not contain $`\chi `$. Up to a free parameter, $`q`$, this assumption fixes how all matter couplings scale with $`c`$; in particular, one has for all interactions $`i`$ associated with gauge charges $`e_i`$ that $`\alpha _ie_i\mathrm{}cc^q`$. The action is

$$S=d^4x\sqrt{g}\left(_g+_\chi +_Me^{b\chi }\right),$$
(2)
with $`_\chi =\frac{\omega }{2}_\mu \chi ^\mu \chi `$, and $`_g`$ is as given above. It was shown in  that only when $`b+q0`$ can these theories be conformally mapped into dilaton theories, and into Brans-Dicke theories only when $`q=0`$ . This theory has an obvious novelty when compared to BSBM: all $`\alpha _i`$ are variable. However, recent cosmological variations in non-electromagnetic $`\alpha _i`$ are beyond the reach of current direct astrophysical observations. Hence for the purpose of this Letter we shall ignore their consequences.

Varying the action with respect to the metric leads to straightforward generalizations of Einstein’s equations . Variation with respect to the new scalar fields leads to dynamical equations for $`\alpha `$. For small variations, $`\delta \alpha /\alpha 1,`$ these are:

$$\mathrm{}\frac{\delta \alpha }{\alpha }=\frac{4}{\omega }_{em}$$
(3)
for BSBM, and

$$\mathrm{}\frac{\delta \alpha }{\alpha }=\frac{bq}{\omega }_M$$
(4)
for VSL. In both cases the right-hand side is zero for relativistic matter, predicting negligible variations in $`\alpha `$ during the radiation-dominated cosmological epoch. Two striking differences appear in the matter epoch, when the RHS becomes non-negligible, in both the coupling parameters and the driving source $``$. The requirement that the fields $`\chi `$ and $`\psi `$ have a positive definite energy forces $`\omega >0`$. This fixes the sign of the coupling for BSBM ($`4/\omega `$) but not for VSL ($`bq/\omega `$). The source $``$ is also different for each theory and is parameterized by different ratios determined by the dark matter: $`\zeta =_{em}/\rho `$ for BSBM, and $`\xi =_M/\rho `$ for VSL.

The value of $`\zeta `$ for baryonic and dark matter has been disputed . It is the difference between the percentage of mass in electrostatic and magnetostatic forms. As explained in , we can at most estimate this quantity for neutrons and protons, with $`\zeta _n\zeta _p10^4`$. We may expect that for baryonic matter $`\zeta 10^4`$, with composition-dependent variations of the same order. The value of $`\zeta `$ for the dark matter, for all we know, could be anything between -1 and 1. Superconducting cosmic strings, or magnetic monopoles, display a negative $`\zeta `$, unlike more conventional dark matter. On the other hand it was argued in  that the value of $`\xi `$ (characterizing the VSL dynamics in the matter epoch) is $`1`$ for all non-relativistic matter. This is equivalent to requiring that non-relativistic matter is dominated by its potential energy (including rest mass) rather than by its kinetic energy $`T`$. We shall use this fact in the rest of the paper although it is not essential for most of what follows.

It is clear that the only way to obtain a cosmologically increasing $`\alpha `$ in BSBM is with $`\zeta <0`$, i.e with unusual dark matter, in which magnetic energy dominates over electrostatic energy. In  we showed that fitting the Webb et al results requires $`\zeta _m/\omega =2\pm 1\times 10^4`$, where $`\zeta _m`$ is weighted by the necessary fractions of dark and baryonic matter. On the other hand VSL theory fits the Webb et al results with $`bq/\omega =8\times 10^4`$, for all types of dark matter. Hence, if we were to determine that $`\zeta >0`$ for the dark matter in the universe, we could experimentally rule out BSBM but not VSL. This is just one way in which the question in the title of this paper could be answered.

However, pending identifying the dark matter, we may still answer this question by looking at spatial variations in $`\alpha `$. In all causal varying-$`\alpha `$ theories defined by a wave equation the observed redshift dependence of $`\alpha `$ requires there also to be spatial variations near compact massive bodies . The relevant equations may be obtained by dropping the time dependence in (3) and (4). Then, a linearized spherically symmetric solution in the vicinity of an object with mass $`M_s`$ and $`\zeta =\zeta _s`$ is

$$\frac{\delta \alpha }{\alpha }=\frac{\zeta _s}{\omega }\frac{M_s}{\pi r}2\times 10^4\frac{\zeta _s}{\zeta _m}\frac{M_s}{\pi r}$$
(5)
for BSBM

$$\frac{\delta \alpha }{\alpha }=\frac{bq}{\omega }\frac{M_s}{4\pi r}2\times 10^4\frac{M_s}{\pi r}.$$
(6)
for VSL. We note that the level of spatial variations in BSBM, given , depends on the nature of the dark matter (the ratio $`\zeta _s/\zeta _m`$), whereas for VSL it does not. In VSL, $`\alpha `$ increases near compact objects (with decreasing $`c`$ if $`q<0`$, with increasing $`c`$ if $`q>0`$) but in BSBM $`\alpha `$ decreases (since $`\zeta _m<0`$ and $`\zeta _s>0`$). In VSL theories, near a black hole $`\alpha `$ could become much larger than 1, so that electromagnetism would become non-perturbative with dramatic consequences for the physics of black holes. In BSBM precisely the opposite happens: electromagnetism switches off.

Spatial variations lead to a number of observable effects which sharply distinguish between VSL and BSBM. Most obviously $`\alpha `$ could be measured in absorption lines from compact objects, as explained in . More subtly, alpha gradients induce a ’fifth force’ effect. In order to compute this force one must model $`\zeta `$ or $`\xi `$ for test bodies. In BSBM the test-particle lagrangian may be split as $`_t=_m+e^{2\psi }_{em}`$. Variation with respect to the metric leads to a similar split of the stress-energy tensor, producing an energy density of the form $`\rho ((1\zeta _t)+\zeta _te^{2\psi }),`$ and so a mass of $`m((1\zeta _t)+\zeta _te^{2\psi }),`$ (assuming electric fields dominate). In order to preserve their ratios of $`\zeta _t=_{em}/\rho `$ test particles may thus be represented by

$$(y)=𝑑\tau m((1\zeta _t)\zeta _te^{2\psi })[g_{\mu \nu }\dot{x}^\mu \dot{x}^\nu ]^{\frac{1}{2}}\frac{\delta (xy)}{\sqrt{g}}$$
(7)
where over-dots are derivatives with respect to the proper time $`\tau `$. This leads to equations of motion:

$$\ddot{x}^\mu +\mathrm{\Gamma }_{\alpha \beta }^\mu \dot{x}^\alpha \dot{x}^\beta +\frac{2\zeta _te^{2\psi }}{(1\zeta _t)\zeta _te^{2\psi }}^\mu \psi =0$$
(8)
which in the non-relativistic limit (with $`\zeta _t1`$) reduce to

$$\frac{d^2x^i}{dt^2}=_i\varphi 2\zeta _t_i\psi ,$$
(9)
where $`\varphi `$ is the gravitational potential. Thus we predict an anomalous acceleration:

$$a=\frac{M_s}{r^2}\left(1+\frac{\zeta _s\zeta _t}{\omega \pi }\right)$$
(10)
Violations of the WEP occur because $`\zeta _t`$ is substance dependent. For two test bodies with $`\zeta _1`$ and $`\zeta _2`$ the Eötvös parameter is:

$$\eta \frac{2|a_1a_2|}{a_1+a_2}=\frac{\zeta _s|\zeta _1\zeta _2|}{\omega \pi }.$$
(11)
This can be written more conveniently as the product of the following 3 factors:

$$\eta =\left(\frac{\zeta _E|\zeta _1\zeta _2|}{\pi \zeta _p}\right)\left(\frac{\zeta _p}{\zeta _m}\right)\left(\frac{\zeta _m}{\omega }\right).$$
(12)
The last factor is the coupling that determines cosmological time variations in $`\alpha `$, and using the results is best fitted to be $`\zeta _m/\omega 10^4`$. If we take $`\zeta _n\zeta _p|\zeta _p\zeta _n|=𝒪(10^4)`$ then for typical substances the first factor is $`10^5`$. Hence, we need $`\zeta _m=𝒪(1)`$ to produce $`\eta =𝒪(10^{13}),`$just an order of magnitude below existing experimental bounds.

In contrast to this VSL theories predict that for all test particles

$$(y)=𝑑\tau me^{b\chi }[g_{\mu \nu }\dot{x}^\mu \dot{x}^\nu ]^{\frac{1}{2}}\frac{\delta (xy)}{\sqrt{g}},$$
(13)
where we have assumed $`\xi =1`$. This leads to an anomalous acceleration of equal magnitude for all test particles, so that there are no WEP violations. This new acceleration does imply corrections to the standard tests of general relativity, such as the precession of Mercury’s perihelion, light deflection and radar echo time-delay . These were studied in  and impose the undemanding constraint of $`b^2/\omega <10^2`$ . Therefore we conclude that an increase of about an order of magnitude in the experimental sensitivity to non-zero $`\eta `$ would decide between the BSBM and VSL theories.

Webb et al  caution that their results might be due to some uninvestigated systematic effect. For this reason it is important to seek independent observational verification. Direct measurement of WEP violations at the predicted level could be seen as a direct confirmation of the source of the astronomical results. Spatial fluctuations in $`\alpha `$ could also be directly mapped from spectroscopy of lines formed in very compact objects or their accretion disks . But more realistically we note that Earth-based atomic-clock experiments could also measure these fluctuations. Atomic clocks tick at a rate $`\tau ^1(E_e\alpha ^2)/\mathrm{}`$, where $`E_e`$ is the electron rest energy. Hence atomic-clock experiments able to measure gravitational redshifts will suffer from an extra effect: in BSBM theories these clocks tick slower in gravitational wells, with $`\tau 1/\alpha ^2`$, whereas in VSL $`\tau 1/c^{2q+1}1/\alpha ^{2+1/q}`$. Any hyperbolic varying-$`\alpha `$ theory explaining  should predict a similar effect.

In general, any gravitational-redshift experiment should be sensitive to a varying $`\alpha `$. For example, the Pound-Rebka-Snyder experiment uses the Mössbauer effect to produce a narrow resonance line from $`\gamma `$-ray photons emitted by radioactive isotopes. The effect has been used to observe gravitational redshifts, but the emitted photon’s energy also depends upon $`\alpha `$. For small variations in $`\alpha `$ the energy shift is $`\delta E/E=C\delta \alpha /\alpha `$ with $`C`$ of order 1 (but not very well known). A similar effect will occur in experiments using Rydberg lines, with a shift in wavelength $`\delta \lambda /\lambda =2(\delta \alpha /\alpha )`$ (for both VSL and BSBM theories). Once the photon is emitted, varying-$`\alpha `$ theories predict no extra redshift for free-flying photons (since $`=0`$ for photons). However, the observed gravitational redshift of frequencies takes the form $`\delta \nu /\nu =(1+\alpha _{PPN})\delta \varphi `$, with a non-zero PPN parameter $`\alpha _{PPN}`$ induced at emission. Using (5) we find that for BSBM theory $`\alpha _{PPN}=2\zeta _s/(\pi \omega )`$, with the quasar data  then implying that $`\alpha _{PPN}10^8`$. For VSL theory care must be taken, because $`\delta \lambda /\lambda `$, $`\delta \nu /\nu `$ and $`\delta E/E`$ are distinct quantities. Defining $`\alpha _{PPN}`$ in terms of frequency in the conventional way and using (6) we have that $`\alpha _{PPN}(2+q^1)bq/(4\pi \omega )(2+q^1)10^5`$. Hence BSBM theory predicts a stronger redshift than general relativity, with corrections of order $`10^8`$. If $`q1,`$ VSL theory predicts a weaker redshift effect with corrections of order $`10^5`$; but this conclusion is changed if $`q1/2`$. Both BSBM and VSL theories are consistent with the current bound of $`\alpha _{PPN}<10^4`$ . Any causal varying-$`\alpha `$ theory should predict a non-zero correction to the relativistic redshift formulae.

In summary, we have explained how a combination of experiment and common sense may distinguish a varying $`c`$ from a varying $`e`$. Using only minimal versions of such theories, we have shown how they can be distinguished by weak equivalence principle violations, by the type of dark matter required to give the variations inferred from quasar observations, and by gravitational-redshift experiments. In non-minimal varying-$`e`$ and -$`c`$ theories, the distinguishing observational signatures should be even more obvious. For instance, if Lorentz invariance were found to be broken, , then a varying-$`c`$ theory would provide a better framework for expressing variations in $`\alpha `$.

Finally, we note that the experiments proposed in this paper are by no means the only discriminators between varying-$`e`$ and -$`c`$ expressions of a varying $`\alpha `$. In  the authors examined black hole thermodynamics, by changing the values of $`e`$ and $`c`$ in their description of black hole thermodynamics (which, however, may be too simplistic ). In this context they found that interpreting a varying $`\alpha `$ as varying $`e`$ or $`c`$ leads to opposite black-hole dynamics, with a varying-$`e`$ contradicting the second law of thermodynamics. In principle one could test whether or not black hole areas always increase with time in the next generation of gravitational-wave observatories. Like the various experiments described in this paper, this is experimentally unambiguous, since the ratio of two areas is dimensionless.

Acknowledgements HBS thanks the Research Council of Norway for financial support. We thank S. Alexander, P. Davies, T. Davis, G. Dvali, J. Moffat, D. Mota, M. Murphy, K. Olive, M. Pospelov, G. Shore, J. Webb and M. Zaldarriaga for discussions.