Lanthanide configurations

One of the first uses that Racah (1942b) put his W function to was the calculation of the term energies of the lanthanide configuration f. The limitations of Slater s diagonal-sum method were mentioned in section 3.1. Racah neatly circumvented the problem of satisfying the Pauli exclusion principle by introducing spin-up and spin-down spaces. Two electrons are put in the first space (space A, say) and the remaining electron is put in the second (space B). Thus... 

These ideas can be readily extended to include the lanthanide configurations 4f or, for that matter, the general configuration 1 Racah credited Bacher and Goudsmit (1934) for realizing that two-electron excitations from / can be represented by two-electron operators within to second order in perturbation theory. To show how this can come about in detail, Racah introduced the single-electron tensor operators zffH ) that convert a state of to one of As such,... 

FIGURE 16 Energy difference v- ii (in eV per lanthanide ion) between the tetravalent and trivalent lanthanide configurations in dioxides (solid circles) and A-type (hexagonal) sesquioxides (open squares). 

Group III with electronic configuration 5s 4d . The principal ore is gadolinite (a silicate also containing lanthanides). Y2O3 containing Eu is used as a red phosphor in colour television. Yttrium iron garnets are used as microwave filters. 

Table 3. Electronic Configurations for Gaseous Atoms of Lanthanide and Actinide Elements...

Absorption and Fluorescence Spectra. The absorption spectra of actinide and lanthanide ions in aqueous solution and in crystalline form contain narrow bands in the visible, near-ultraviolet, and near-infrared regions of the spectmm (13,14,17,24). Much evidence indicates that these bands arise from electronic transitions within the and bf shells in which the Af and hf configurations are preserved in the upper and lower states for a particular ion. 

Although rare-earth ions are mosdy trivalent, lanthanides can exist in the divalent or tetravalent state when the electronic configuration is close to the stable empty, half-fUed, or completely fiUed sheUs. Thus samarium, europium, thuUum, and ytterbium can exist as divalent cations in certain environments. On the other hand, tetravalent cerium, praseodymium, and terbium are found, even as oxides where trivalent and tetravalent states often coexist. The stabili2ation of the different valence states for particular rare earths is sometimes used for separation from the other trivalent lanthanides. The chemicals properties of the di- and tetravalent ions are significantly different. 

Applications Linked to Physical Properties. Apphcations involving physical properties use high purity (>99.99%) lanthanides and exploit the elements specific electronic configuration. 

Uranium is the fourth element of the actinide (SJ series. In the actinide series the electrons are more effectively shielded by the Is and 7p electrons relative to the 4f electrons (shielded by 6s, 6p) in the lanthanide (4p series. Thus, there is a greater spatial extension of 5f orbitals for actinides than 4f orbitals for lanthanides. This results in a small energy difference between and 5/ 6d7s electronic configurations, and a wider range of oxidation states is... 

Cerous salts in general are colorless because Ce " has no absorption bands in the visible. Trivalent cerium, however, is one of the few lanthanide ions in which parity-allowed transitions between 4f and Sd configurations can take place and as a result Ce(III) compounds absorb in the ultraviolet region just outside the visible. 

There is no single best form of the periodic table since the choice depends on the purpose for which the table is used. Some forms emphasize chemical relations and valence, whereas others stress the electronic configuration of the elements or the dependence of the periods on the shells and subshells of the atomic structure. The most convenient form for our purpose is the so-called long form with separate panels for the lanthanide and actinide elements (see inside front cover). There has been a lively debate during the past decade as to the best numbering system to be used for the individual... 

Figure 30.3 Variation with atomic number of some properties of La and the lanthanides A, the third ionization energy (fa) B, the sum of the first three ionization energies ( /) C, the enthalpy of hydration of the gaseous trivalent ions (—A/Zhyd)- The irregular variations in I3 and /, which refer to redox processes, should be contrasted with the smooth variation in A/Zhyd, for which the 4f configuration of Ln is unaltered.

Electronic absorption spectra are produced when electromagnetic radiation promotes the ions from their ground state to excited states. For the lanthanides the most common of such transitions involve excited states which are either components of the ground term or else belong to excited terms which arise from the same 4f" configuration as the ground term. In either case the transitions therefore involve only a redistribution of electrons within the 4f orbitals (i.e. f—>f transitions) and so are orbitally forbidden just like d—>d transitions. In the case of the latter the rule is partially relaxed by a mechanism which depends on the effect of the crystal field in distorting the symmetry of the metal ion. However, it has already been pointed out that crystal field effects are very much smaller in the case of ions and they... 

The reason usually cited for the great similarity in the properties of the lanthanides is that they have similar electronic configurations in the outermost 6s and 5d orbitals. This occurs because, at this point in the periodic table, the added electrons begin to enter 4f orbitals which are fairly deep inside the atom. These orbitals are screened quite well from the outside by outer electrons, so changing the number of 4/electrons has almost no effect on the chemical properties of the atom. The added electrons do not become valence electrons in a chemical sense—neither are they readily shared nor are they readily removed. 

THE ELECTRON CONFIGURATIONS OF GASEOUS ACTINIDE AND LANTHANIDE ATOMS... 

Lanthanide elements, 411, 389 contraction, 413 electron configurations, 415 occurrence and preparation, 413 oxidation numbers, 414 properties, 412 Lanthanum... 

Wilson JA (1977) A Generalized Configuration - Dependent Band Model for Lanthanide Compounds and Conditions for Interconfiguration Fluctuations. 32 57-91 Wilson MR (1999) Atomistic Simulations of Liquid Crystals. 94 41-64 Winkler H, see Trautwein AX (1991) 78 1-96... 

Desimoni et al. [101] further investigated the influence of the variation of the lanthanide and of the PyBOx ligand (bearing a Pr- or Ph-substituent with the same configuration) on the enantioselectivity of the Diels-Alder test... 

Fig. 1.1 (a) The ionization enthalpies of dipositive lanthanide ions with configurations of the type [Xe]4f" (upper plot left-hand axis), (b) The standard Gibbs energy change of reaction 1 (lower plot right-hand axis estimated value ... 

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