Actinide crystal structure

Table 5.16. Actinides crystal structures, lattice parameters of their allotropes, calculated densities.

Actinide crystal structures are more complicated and diversified than the corresponding lanthanide metal structures. Information about the crystal stmctures of the actinide metals is given in Table IV. 

In the previous section we have already illustrated the complex magnetic structures that often exist in cubic NaCl-type actinide compounds. Not surprisingly, when we consider more complex actinide crystal structures the magnetic structures can become even more complicated. So many uranium compounds are now being synthesized and examined that it is impossible to cover all these studies in one review. 

Table 8. Properties and Crystal Structure Data for Important Actinide Binary Compounds...

Crystal Structure and Ionic Radii. Crystal stmcture data have provided the basis for the ionic radii (coordination number = CN = 6), which are summarized in Table 9 (13,14,17). For both and ions there is an actinide contraction, analogous to the lanthanide contraction, with increasing positive charge on the nucleus. 

The crystal structures of the borides of the rare earth metals (M g) are describedand phase equilibria in ternary and higher order systems containing rare earths and B, including information on structures, magnetic and electrical properties as well as low-T phase equilibria, are available. Phase equilibria and crystal structure in binary and ternary systems containing an actinide metal and B are... 

Hexaborides of a CaBg type are formed by K, the alkaline earths, Y and the larger lanthanides, as well as Th and some actinides ". The crystal structure of these compounds with cubic symmetry (Pm3m, O, ) (see Fig. 1) is characterized by a three-dimensional skeleton of Bg boron octahedra, the interstices of which are filled by metal atoms. The connection between two octahedra is by a B—B bond of length 1.66 X 10 pm, whereas the B—B bond lengths in one octahedron are 1.76 X 10 pm. ... 

Remarks on the crystal chemistry of the alloys of the 3rd group metals. A large number of intermediate phases have been identified in the binary alloys formed by the rare earth metals and actinides with several elements. A short illustrative list is shown in Tables 5.19 and 5.20. Compounds of a few selected rare earth metals and actinides have been considered in order to show some frequent stoichiometries and crystal structure types. The existence of a number of analogies among the different metals considered and the formation of some isostructural series of compounds may be noticed. 

Perovskites, 27 358 band structure, 38 131-132 crystal structure, 38 123-125 Perovskite-type oxides see also specific lanthanum-based catalysts actinide storage in radioactive waste, 36 315-316... 

Table XI gives the room-temperature, atmospheric pressure crystal structures, densities, and atomic volumes, along with the melting points and standard enthalpies of vaporization (cohesive energies), for the actinide metals. These particular physical properties have been chosen as those of concern to the preparative chemist who wishes to prepare an actinide metal and then characterize it via X-ray powder diffraction. The numerical values have been selected from the literature by the authors.

Actinide metal Crystal structure Density (g/cm ) Atomic volume (A ) Melting point (K) Enthalpy of vaporization AH, g (kJ/mol)... 

Crystallographic data (.continued) for transition metal tetrafluorides, 27 98 for transition metal trifluorides, 27 92 Crystallographic disorder, nitrosyl groups, 34 304-305 Crystallography fuscoredoxin, 47 380 prismane protein, 47 232-233 Rieske and Rieske-type proteins, 47 92-109 Crystal radii, of various ions, 2 7 Crystals, 39 402 Crystal structure actinide metals, 31 36 copper-cobalt supetoxide dismutases, 45 ... 

Considerations on the crystal structures and other physical properties of the light actinides have triggered a large effort in quantum calculations for the wave functions of the outer electrons of actinides, including in atoms as well as in solids. 

V. Crystal Structures and Thermodynamic Properties of Simple Actinide Binary 106... 

The higher actinide metals americium, curium, berkelium and californium have - at normal pressure - again the common structure dhcp and are in this respect similar to some of the lanthanide metals. In fact, the theoretical calculations and certain experimental observations show that in these actinide metals, 5 f electrons are localized, as are the 4f electrons in the lanthanide metals. More detailed considerations on the possible correlations between electronic and crystal structure are found in. ... 

Figure 5 gives the variation of the atomic volume in the actinide series, for the room temperature crystal structures as well as for the ccp and bcc high temperature allotropes, which exist for a number of actinides. The graph is based on the lattice parameters of Table 1, which includes also recent results. The marked dip in the curve from Th to Am illustrates the shrinkage of interactinide distance which is linked to the itinerancy of the 5f electrons in this part of the actinide series. 

Fig. 5. Atomic volume of the actinide metals room temperature crystal structures O high temperature ccp aUotropes at room temperature -I- high temperature bcc allot-ropes at high temperature...

This treatment aiming to evaluate thermodynamically the orbital character of the bond in actinide metals, follows closely the general features illustrated above and has a particular value inasmuch as it is accompanied by a fairly comprehensive survey of the chemical and physical properties of actinide metals known at that time. In it, the metallic radius and the crystal structures are taken as valence indicators AH nd Tm as the bonding indicators . The metallic valence, however, is not taken as constant throughout the actinide series, but rather allowed to vary. The particular choices are justified by physical and chemical arguments, which are taken in support of the hypothesis chosen. 

From a thermodynamic viewpoint, we may imagine that, in an actinide metal, the model of the solid in which completely itinerant and bonding 5 f electrons exist and that in which the same electrons are localized, constitute the descriptions of two thermodynamic phases. The 5f-itinerant and the 5 f-localized phases may therefore have different crystal properties a different metallic volume, a different crystal structure. The system will choose that phase which, at a particular T and p (since we are dealing with metals, the system will have only one component) has the lower Gibbs free-energy. A phase transition will occur then the fugacity in the two possible phases is equal e.g. the pressure. To treat the transition, therefore, the free energies and the pressures of the two phases have to be compared. We recall that ... 

---