The vibrational spectra of sulfate ions in alkali halide crystals |
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| Affiliation: | 1. University of Zielona Góra, Institute of Physics, Division of Spectroscopy of Functional Materials, 4a Szafrana Str., 65-516 Zielona Góra, Poland;2. Vlokh Institute of Physical Optics, Sector of Spectroscopy, 23 Dragomanov Str., 79-005 Lviv, Ukraine;3. Institute of Low Temperatures and Structure Research of the Polish Academy of Sciences, Department of Spectroscopy of Laser Materials, 2 Okólna Str., 50-422 Wrocław, Poland;1. College of Chemistry and Materials Science, Sichuan Normal University, Chengdu 610068, China;2. Department of Basic Education,Dazhou Vocational and Technical College, Dazhou 635001, China;3. Clean Energy Materials and Engineering Center, School of Microelectronics and Solid-state Electronics, University of Electric Science and Technology of China, Chengdu 611731, China;1. Institute of Chemistry, Tyumen State University, Tyumen 625003, Russia;2. Department of General and Special Chemistry, Industrial University of Tyumen, Tyumen 625000, Russia;3. Laboratory of Coherent Optics, Kirensky Institute of Physics Federal Research Center KSC SB RAS, Krasnoyarsk 660036, Russia;4. Institute of Nanotechnology, Spectroscopy and Quantum Chemistry, Siberian Federal University, Krasnoyarsk 660041, Russia;5. Laboratory of Optical Materials and Structures, Institute of Semiconductor Physics, SB RAS, Novosibirsk 630090, Russia;6. Laboratory of Semiconductor and Dielectric Materials, Novosibirsk State University, Novosibirsk 630090, Russia;7. Laboratory of Molecular Spectroscopy, Kirensky Institute of Physics Federal Research Center KSC SB RAS, Krasnoyarsk 660036, Russia;8. Laboratory of Crystal Physics, Kirensky Institute of Physics, Federal Research Center KSC SB RAS, Krasnoyarsk 660036, Russia;9. Siberian Federal University, Krasnoyarsk 660041, Russia;10. Department of Physics, Far Eastern State Transport University, Khabarovsk 680021, Russia;1. College of Chemistry and Chemical Engineering, Henan Polytechnic University, Jiaozuo, Henan 454000, China;2. Personnel Department, Henan Polytechnic University, Jiaozuo, Henan 454000, China |
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| Abstract: | Single crystals of KCl and KBr grown from melts doped with magnesium, calcium, barium and lead sulfates at about 0.1 mole per cent have been examined in the fundamental vibrational region of the sulfate ion with an infrared grating spectrometer at 35 and −190°C. Some samples employed sulfate enriched in 34S to about 45 per cent. Except in the case of magnesium, the infrared absorption spectra can be interpreted on the basis of C2v symmetry arising from the perturbation of the sulfate Td symmetry by an adjacent divalent cation, i.e. the barium, calcium and lead ions form ion pairs with the sulfate within the alkali halide lattice.The triply degenerate SO stretching and bending modes are split into three unequal components; the observed frequencies in the stretching region are in reasonable quantitative agreement with values calculated on the basis of changes in the bond stretching force constants induced by the adjacent excess positive charge of the metal ions; such changes are calculated to be of the order of Δf = 1 mdynÅ compared with observed values ranging from 0.6 to 0.9 mdynÅ. |
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