Tensorial properties of an electronic Raman effect of the thulium ion

1969 ◽  
Vol 47 (8) ◽  
pp. 1395-1399 ◽  
Author(s):  
J. A. Koningstein ◽  
Toa-ning Ng

The low temperature laser excited Raman spectrum of the compound thulium gallium garnet reveals the presence of an electronic transition of the thulium ion. The tensor associated with this transition can contain some asymmetry. Polarization measurements show, however, that the amount of asymmetry is too small to be detectable.

1969 ◽  
Vol 47 (24) ◽  
pp. 2879-2881 ◽  
Author(s):  
H. Fast ◽  
H. L. Welsh ◽  
D. W. Lepard

The rotational Raman spectrum of gaseous NO was photographed with a spectral resolution of ~0.3 cm−1. In longer exposures the rotational structure of the electronic transition, [Formula: see text], was also observed. It consists of O, P, Q, R, and S branches and has an intensity distribution in accordance with theory.


1987 ◽  
Vol 42 (2) ◽  
pp. 163-168 ◽  
Author(s):  
Ralf Steudel ◽  
Detlef Jensen ◽  
Bettina Plinke

Abstract The Raman spectrum of commercial "sulfur dichloride" shows strong lines due to SCl2 and S2Cl2 and weak Cl2 lines at 25 °C, but strong SCl2 and SCl4 signals at -100 °C (the latter are superimposed on the S2Cl2 lines). Thus, the intense Raman effect of SCl4 can be used to detect small amounts of chlorine in SCl2 . Mixtures of SCl2 and Cl2 (1:15) yield the Raman spectrum of SCl4 at -140 °C, while at 25 °C not trace of this compound can be detected. The spectra of SCl4 and α-SeCl4 are quite different, indicating different molecular and/or crystal structures, although ECl3 + ions (E = S, Se) are present in both cases. While Se2Cl2 dimerizes reversibly below -50 °C, S2Cl2 neither dimerizes nor isomerizes on cooling. The S2Cl2 dimer is characterized by a Raman line at 215 cm-1 the intensity of which was used to calculate an enthalpy of dimerization as of -17 kJ/mol.


1974 ◽  
Vol 52 (13) ◽  
pp. 1185-1188 ◽  
Author(s):  
R. W. Ward ◽  
P. W. Whippey

Measurements of the low temperature luminescent spectra of CaF2:Er3+ have revealed a vibronic sideband associated with the Er3+ electronic transition at 5512 Å. The phonon frequencies observed are shown to be related to the single phonon density of states of CaF2.


2013 ◽  
Vol 77 (4) ◽  
pp. 453-465 ◽  
Author(s):  
A. R. Kampf ◽  
S. J. Mills ◽  
B. P. Nash ◽  
R. M. Housley ◽  
G. R. Rossman ◽  
...  

AbstractCamaronesite (IMA 2012-094), [Fe3+(H2O)2(PO3OH)]2(SO4)·1–2H2O, is a new mineral from near the village of Cuya in the Camarones Valley, Arica Province, Chile. The mineral is a low-temperature, secondary mineral occurring in a sulfate assemblage with anhydrite, botryogen, chalcanthite, copiapite, halotrichite, hexahydrite, hydroniumjarosite, pyrite, römerite, rozenite and szomolnokite. Lavender-coloured crystals up to several mm across form dense intergrowths. More rarely crystals occur as drusy aggregates of tablets up to 0.5 mm in diameter and 0.02 mm thick. Tablets are flattened on {001} and exhibit the forms {001}, {104}, {015} and {018}. The mineral is transparent with white streak and vitreous lustre. The Mohs hardness is 2½, the tenacity is brittle and the fracture is irregular, conchoidal and stepped. Camaronesite has one perfect cleavage on {001}. The measured and calculated densities are 2.43(1) and 2.383 g/cm3, respectively. The mineral is optically uniaxial (+) with ω = 1.612(1) and ε = 1.621(1) (white light). The pleochroism is O (pale lavender) > E (colourless). Electron-microprobe analyses provided Fe2O331.84, P2O529.22, SO315.74, H2O 23.94 (based on O analyses), total 100.74 wt.%. The empirical formula (based on 2 P a.p.f.u.) is: Fe1.94(PO3OH)2(S0.96O4)(H2O)4·1.46H2O. The mineral is slowly soluble in concentrated HCl and extremely slowly soluble in concentrated H2SO4. Camaronesite is trigonal, R32, with cell parameters:a = 9.0833(5), c = 42.944(3) Å, V = 3068.5(3) Å3 and Z = 9. The eight strongest lines in the X-ray powder diffraction pattern are [dobs Å (I)(hkl)]: 7.74(45)(101), 7.415(100)(012), 4.545(72)(110), 4.426(26)(018), 3.862(32)(021,202,116), 3.298(93)(027,119), 3.179(25)(208) and 2.818(25)(1·1·12,125). In the structure of camaronesite (R1 = 2.28% for 1138 Fo > 4σF), three types of Fe octahedra are linked by corner sharing with (PO3OH) tetrahedra to form polyhedral layers perpendicular to c with composition [Fe3+(H2O)2(PO3OH)]. Two such layers are joined through SO4 tetrahedra (in two half-occupied orientations) to form thick slabs of composition [Fe3+(H2O)2(PO3OH)]2(SO4). Between the slabs are partially occupied H2O groups. The only linkages between the slabs are hydrogen bonds. The most distinctive component in the structure consists of two Fe octahedra linked to one another by three PO4 tetrahedra yielding an [Fe2(PO4)3] unit. This unit is also the key component in the sodium super-ionic conductor (NASICON) structure and has been referred to as the lantern unit. The polyhedral layers in the structure of camaronesite are similar to those in the structure of taranakite. The Raman spectrum exhibits peaks consistent with sulfate, phosphate, water and OH groups.


2001 ◽  
Vol 34 (4) ◽  
pp. 437-442 ◽  
Author(s):  
Chan Jin ◽  
Chaozhong Zhao

1978 ◽  
Vol 59 (1) ◽  
pp. 10-13 ◽  
Author(s):  
Marcia L.A. Temperini ◽  
O. Sala ◽  
H.J. Bernstein

Using a non-luminescent crystal of rock-salt, a quartz spectrograph with a fine slit, and the 2536.5 A resonance radiations of mercury arc as exciter, the Raman effect in rock-salt has been studied. The spectrum exhibits nine distinct Raman lines with frequency shifts 135, 184, 202, 235, 258, 278, 314, 323 and 350 cm. -1 . The frequency shifts 235 and 184 cm. -1 representing conspicuous lines in the Raman spectrum agree as nearly as could be expected with the position of the two subsidiary infra-red absorption maxima observed by Barnes & Czerny with thin films of rock-salt. The principal infra-red absorption frequency of 163 cm. -1 is inactive in the Raman effect, but its octave is represented. The nature of the Raman spectrum to be expected is deduced on the basis of a theory due to Tamm, as also on the basis of another due to Fermi, the vibration spectrum of the rock-salt lattice being taken to be that worked out by Kellermann on the basis of the Born lattice dynamics. The results are altogether of a different nature from those actually observed experimentally in the present investigation. The conclusion is thus reached that the Born lattice dynamics does not correctly picture the vibration spectrum of the rock-salt lattice. On the other hand the observed facts, both in respect of Raman effect and infra-red absorption, fit into the theoretical picture provided by the dynamics of crystal lattices recently worked out by Sir C. V. Raman.


When the Raman effect was first discovered, it was believed that every line in the Raman spectrum referred to some characteristic vibration of the scatter­ing molecule. Later the tendency was to regard the lines as due to transitions between states of vibration of the molecule, so that the energies corresponded not to energies of vibration directly, but to differences in the energy of vibra­tion of two different modes. It is now realised that the infra-red spectrum of a substance and the Raman spectrum which it scatters give complementary information. Certain modes of vibration are represented solely in the infra­red spectrum, others are found only in the Raman spectrum, while others may appear in both spectra. Quite early a rough criterion on the basis of symmetry was put forward by Schaefer, for the determination of whether or not a particular vibration was to be expected in the Raman effect. Recently a selection rule has been formulated by Placzek; no vibration will appear as a fundamental in the Raman effect if it is such that any symmetrical operation upon it can change the signs of the displacements of the normal co-ordinates, without altering the energy. It is clear that a knowledge of the normal modes of vibration of the molecule under discussion must precede the application of any such rule, and it is the purpose of the present communication to discuss the normal modes of vibration of the carbonate and nitrate ions. In 1929 the writer showed that it was possible to obtain Raman spectra from powdered crystals, and the discovery was made when using powdered crystals of potassium nitrate. The method was applied first to carbonates and nitrates, so it became of interest to attempt to fix the structure of the anions of these salts by means of the Raman spectra combined with the infra-red data. In what follows the carbonate ion will first be dealt with in some detail, and then the nitrate ion can be treated summarily owing to the similarity of structure of the two ions.


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