A Raman and resonance Raman study of polybromide anions and a study of the temperature dependence of the Raman-active phonons of tetrabutylaminonium tribromide |
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| Institution: | 1. Center of Functional Nano-Ceramics, National University of Science and Technology “MISiS”, Moscow, 119049, Russia;2. Institute of Structural Macrokinetics and Material Science, Russian Academy of Sciences, Chernogolovka, Moscow, 142432, Russia;3. Department of Chemical and Biomolecular Engineering, University of Notre Dame, Notre Dame, 46556, Indiana, USA;1. Boreskov Institute of Catalysis SB RAS, Lavrentieva Ave., 5, Novosibirsk, 630090, Russia;2. Novosibirsk State University, Pirogova Str., 2, Novosibirsk, 630090, Russia;1. College of Chemistry, Beijing Normal University, Beijing 100875, China;2. Analytical and Testing Center, Beijing Normal University, China;3. Key Laboratory of Theoretical and Computational Photochemistry, Ministry of Education, College of Chemistry, Beijing Normal University, Beijing 100875, China;1. Faculty of Chemistry, University of Warsaw, Pasteura 1, 02-093 Warsaw, Poland;2. Department of Pharmacogenomics, Faculty of Pharmacy, Medical University, 02-097 Warsaw, Poland |
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| Abstract: | Raman and resonance spectroscopy are shown to be capable of characterizing the tribromide and pentabromide anions and interstitial dibromine. The anions have Raman-active phonons which display a broad maximum in their excitation profiles at 600 nm, whereas interstitial bromine has a maximum in its excitation profile shifted towards the blue.Large shifts in band wavenumber are observed for the symmetric and asymmetric bromine stretching vibrations in tribromide salts with different cations. The bromine stretch force constants for the tribromide anions, for dibromine and for the recently reported decabromide dianion, have been shown to obey the relationship, k=0.01r−6.7.The Raman-active phonons of tetrabutylammonium tribromide have been studied as a function of temperature, from 10 to 300 K. No first order phase changes were observed and remarkably small coefficients (∂ν/∂T)P, were measured for both the internal and the external modes. |
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