Journal
JOURNAL OF RAMAN SPECTROSCOPY
Volume 44, Issue 1, Pages 63-69Publisher
WILEY-BLACKWELL
DOI: 10.1002/jrs.4144
Keywords
osmium tetroxide; high-resolution stimulated Raman spectroscopy; tensorial formalism; isotopologues
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Funding
- Ministry of Science and Innovation [FIS2009-08069]
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We present the first high-resolution stimulated Raman study of osmium tetroxide (OsO4). Lines from the nu(1) totally symmetric stretching fundamental have been assigned. These data together with the infrared assignments of the nu(3) band previously recorded (M. Louviot et al., J. Quant. Spectrosc. Radiat. Transfer, 2012, 113, 119127) allowed a refinement of the analysis of the nu(1)/nu(3) stretching dyad. We found that the nu(1) band has an unusual positive isotopic shift of approximately 0.32 cm-1/amu, which gives further evidence that the stretching dyad should be perturbed by a complex nearby bending band polyad. This work is part of a global effort to analyze all fundamental bands of OsO4 to obtain a more precise experimental value of the ground state bond length for this heavy metal-containing molecule. The result could serve as a benchmark for high-level quantum chemistry calculations. Copyright (C) 2012 John Wiley & Sons, Ltd.
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