Lanthanide ions electron configurations

By far the most common oxidation state among the lanthanides is + 3, although some + 2 ions have also been found. - For all the + 3 cations of the lanthanides, the electron configuration is identical, namely, 4f 5d 6s . First-row transition-metal ions, on the other hand, have variable oxidation states, dependent on their propensity to attain stable, orbital configurations, ranging from + 1 to +7 oxidation states. 

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. 

The Slater—Condon integrals Ft(ff), Ft(fd), and Gj-(fd), which represent the static electron correlation within the 4f" and 4f 15d1 configurations. They are obtained from the radial wave functions R, of the 4f and 5d Kohn—Sham orbitals of the lanthanide ions.23,31... 

Table 1—Oxidation states, electronic configurations, and radii of the (III) ion of the lanthanide elements and yttrium...

The lanthanides have electrons in partly filled 4/orbitals. Many lanthanides show colors due to electron transitions involving the 4/orbitals. However, there is a considerable difference between the lanthanides and the 3d transition-metal ions. The 4/ electrons in the lanthanides are well shielded beneath an outer electron configuration, (5.v2 5p6 6s2) and are little influenced by the crystal surroundings. Hence the important optical and magnetic properties attributed to the 4/ electrons on any particular lanthanide ion are rather unvarying and do not depend significantly upon the host structure. Moreover, the energy levels are sharper than those of transition-metal ions and the spectra resemble those of free ions. 

The rare earth (RE) ions most commonly used for applications as phosphors, lasers, and amplifiers are the so-called lanthanide ions. Lanthanide ions are formed by ionization of a nnmber of atoms located in periodic table after lanthanum from the cerium atom (atomic number 58), which has an onter electronic configuration 5s 5p 5d 4f 6s, to the ytterbium atom (atomic number 70), with an outer electronic configuration 5s 5p 4f " 6s. These atoms are nsnally incorporated in crystals as divalent or trivalent cations. In trivalent ions 5d, 6s, and some 4f electrons are removed and so (RE) + ions deal with transitions between electronic energy sublevels of the 4f" electroiuc configuration. Divalent lanthanide ions contain one more f electron (for instance, the Eu + ion has the same electronic configuration as the Gd + ion, the next element in the periodic table) but, at variance with trivalent ions, they tand use to show f d interconfigurational optical transitions. This aspect leads to quite different spectroscopic properties between divalent and trivalent ions, and so we will discuss them separately. 

Trivalent lanthanide ions have an outer electronic configuration 5s 5p 4f", where n varies from 1 (Ce +) to 13 (Yb +) and indicates the number of electrons in the unfilled 4f shell. The 4f" electrons are, in fact, the valence electrons that are responsible for the optical transitions. 

Due to its 5t/-6.v- electron configuration, hafnium forms tctravalent compounds readily, although the Ilf1 ion docs not exist as such In aqueous solution except at very low pH values, Ihe common cation being HfO lor Hf OH)i ) and many of the tctravalent compounds are partly covalent. There are also less stable Hf(lll) compounds, There is close similarity in chemical properties to those of zirconium due to the similar outer electron configuration (4identical ionic radii (ZrJ is 0.80 A) the relatively low value for Hf being due lo the Lanthanide contraction. 

The variation in the heat capacity and entropy of the solid lanthanide trihalides can be described by a lattice contribution that linearly varies with atomic number within each crystallographic class of compounds, and an excess contribution that depends on the electronic configuration (crystal field) of the lanthanide ions. A distinct difference is observed between... 

The properties of the liquid lanthanide trihalides depend strongly on the atomic number of the halide. The variation in the heat capacity of the lanthanide fluorides indicates a strongly ionic behaviour of the melts with a concomittent irregular trend related to the electronic configuration of the lanthanide ions. In the lanthanide chlorides, bromides and iodides the trend becomes systematically more constant, indicating an increasing molecular nature of the melts. 

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