Absorption spectra transition metal ions

A certain transition metal ion presents two optical absorption bands in a host crystal whose zero-phonon lines are at 600 nm and 700 nm, respectively. The former band has a Huang-Rhys parameter 5 = 4, while for the latter 5 = 0. Assuming coupling with a phonon of 300 cm for the two bands (a) display the 0 K absorption spectrum (absorption versus wavelength) for such a transition metal ion (b) display the emission spectra that you expect to obtain nnder excitation in both absorption bands and (c) explain how you expect these two bands to be affected by a temperature increase. 

The Orgel diagrams illustrated in figs 3.11 and 3.12 indicate that, for electronic transitions between crystal field states of highest spin-multiplicities, one absorption band only is expected in the spectra of 3d1,3d4,3d6 and 3d9 cations in octahedral coordination, whereas three bands should occur in the spectra of octahedrally coordinated 3d2, 3d3, 3d7 and 3d8 ions. Thus, if a crystal structure is known to contain cations in regular octahedral sites, the number and positions of absorption bands in a spectrum might be used to identify the presence and valence of a transition metal ion in these sites. However, this method of cation identification must be used with caution. Multiple and displaced absorption bands may occur in the spectra of transition metal ions situated in low-symmetry distorted coordination sites. 

Chapter 3 describes the theory of electronic spectra of transition metal ions. The three characteristic features of absorption bands in a spectrum are position or energy, intensity of absorption and width of the band at half peak-height. Positions of bands are commonly expressed as wavelength (micron, nanometre or angstrom) or wavenumber (cm-1) units, while absorption is usually displayed as absorbance, absorption coefficient (cm-1) or molar extinction coefficient [litre (g.ion)-1 cm-1] units. 

The valence and coordination symmetry of a transition metal ion in a crystal structure govern the relative energies and energy separations of its 3d orbitals and, hence, influence the positions of absorption bands in a crystal field spectrum. The intensities of the absorption bands depend on the valences and spin states of each cation, the centrosymmetric properties of the coordination sites, the covalency of cation-anion bonds, and next-nearest-neighbour interactions with adjacent cations. These factors may produce characteristic spectra for most transition metal ions, particularly when the cation occurs alone in a simple oxide structure. Conversely, it is sometimes possible to identify the valence of a transition metal ion and the symmetry of its coordination site from the absorption spectrum of a mineral. 

Absorption in the visible is perceived as color. A number of mechanisms exist for the creation of color in glasses. The most important commercial colored glasses contain either 3d transition metal ions or 4f rare earth (lanthanide) ions, where the coloration arises from the so-called ligand field effect. Other sources of color include the formation of metal or semi-conductor colloidal particles, optical defects induced by solarization or radiation, and charge transfer bands in the visible region of the spectrum. 

The color of cement is the result of Ught absorption in the visible part of spectrum, due to the presence of transition metal ions. 

---