High-spin

The simplest approximation to the complete problem is one based only on the electron density, called a local density approximation (LDA). For high-spin systems, this is called the local spin density approximation (LSDA). LDA calculations have been widely used for band structure calculations. Their performance is less impressive for molecular calculations, where both qualitative and quantitative errors are encountered. For example, bonds tend to be too short and too strong. In recent years, LDA, LSDA, and VWN (the Vosko, Wilks, and Nusair functional) have become synonymous in the literature. 

A spin projected result does not give the energy obtained by using a restricted open-shell calculation. This is because the unrestricted orbitals were optimized to describe the contaminated state, rather than the spin-projected state. In cases of very-high-spin contamination, the spin projection may fail, resulting in an increase in spin contamination. 

Shannon and Prewitt base their effective ionic radii on the assumption that the ionic radius of (CN 6) is 140 pm and that of (CN 6) is 133 pm. Also taken into consideration is the coordination number (CN) and electronic spin state (HS and LS, high spin and low spin) of first-row transition metal ions. These radii are empirical and include effects of covalence in specific metal-oxygen or metal-fiuorine bonds. Older crystal ionic radii were based on the radius of (CN 6) equal to 119 pm these radii are 14-18 percent larger than the effective ionic radii. 

Weak-field, high-spin Strong-field, low-spin- ... 

Figure 7.40 (a) Weak-field, high-spin and (b) strong-field, low-spin configurations in d, d, d ... 

Prussian Blue. Reaction of [Fe(CN)3] with an excess of aqueous h on(Ill) produces the finely divided, intensely blue precipitate Pmssian Blue [1403843-8] (tetrairon(Ill) tris(hexakiscyanoferrate)), Fe4[Fe(CN)3]. Pmssian Blue is identical to Turnbull s Blue, the name which originally was given to the material produced by reaction of [Fe(CN)3] with excess aqueous h on(Il). The soHd contains or has absorbed on its surface a large and variable number of water molecules, potassium ions (if present in the reaction), and h on(Ill) oxide. The h on(Il) centers are low spin and diamagnetic h on(Ill) centers are high spin. Variations of composition and properties result from variations in reaction conditions. Rapid precipitation in the presence of potassium ion affords a colloidal suspension of Pmssian Blue [25869-98-1] which has the approximate composition KFe[Fe(CN)3]. Pmssian Blue compounds are used as pigments in inks and paints and its formation on sensitized paper is utilized in the production of blueprints. 

Tris(2,4-pentanedionato)iron(III) [14024-18-1], Fe(C H202)3 or Fe(acac)3, forms mby red rhombic crystals that melt at 184°C. This high spin complex is obtained by reaction of iron(III) hydroxide and excess ligand. It is only slightly soluble in water, but is soluble in alcohol, acetone, chloroform, or benzene. The stmcture has a near-octahedral arrangement of the six oxygen atoms. Related complexes can be formed with other P-diketones by either direct synthesis or exchange of the diketone into Fe(acac)3. The complex is used as a catalyst in oxidation and polymerization reactions. 

However, high spin (P and (P species, which possess 4, 5, and 4 unpaired electrons, respectively, are labile, as are (P through (P octahedral complexes. In addition to the inert (P systems, low spin (P and (P complexes are inert to rapid substitution. The (P species are the least labile of the configurations classed as labile. 

Normally the vortex finder should extend down into the conical portion of the cyclone. It is thought that the vortex finder plays an important role in the maintenance of a stable spiraling fluid flow in the cyclone, and this makes it more difficult for the particles to leak through the boundary layer on the roof of the lid of the cyclone to the overflow tube.- Without a vortex finder, the efficiency may be reduced by 4-5%. However, an excessive long vortex finder may hinder the high spin velocity in the fluid flow and thus reduce the efficiency of the cyclone. 

Figure 19.16 The possible high-spin and low-spin configurations arising as a result of the imposition of an octahedral crystal field on a transition metal ion.

Radius depends on whether Cr(II) is low-spin (Is) or high-spin (hs). 

The most obvious features of Fig. 24.1 are the relative positions of the -t-2 oxidation states. For manganese this state, represented by the high-spin Mn cation, is much the most stable. This may be taken as an indication of the stability of the symmetrical d electron configuration. 

Aqueous solutions of salts with non-coordinating anions contain the pale-pink, [Mn(H20)6] +, ion which is one of a variety of high-spin octahedral complexes which have been... 

---