Vibrational study and spectra-structure correlations in ammonium saccharinate: Comparison with the alkali saccharinates

Panče Naumov, Gligor Jovanovski

Research output: Contribution to journalArticlepeer-review

Abstract

The FT IR spectra, at temperatures from liquid-nitrogen boiling (LNT) up to room temperature (RT), as well as the RT Raman solid-state spectra of protonated and deuterated ammonium saccharinate and of a series of alkali (Na, K, Rb, Cs) saccharinates are studied. The spectral assignments are aided with ab initio calculations on the free saccharinato anion at the HF/6-31++G(d,p) level. Attention is paid to the ND, CO and SO2 stretching regions. Correlation splitting is believed to be responsible for the presence of a v(CO) doublet. The averaged v(CO) frequency in (purely ionic) ammonium saccharinate is found to be the lowest in the so far studied saccharinates, along with the assumptions that the v(CO) frequency (or the corresponding averaged value) can have predictive value for the type of the metal-to-saccharinato ligand/ion bonding. The appreciably higher contribution of the dominating internal coordinate in the corresponding normal vibration in case of vas(SO2) than in vs(SO2) makes it suitable for spectra-structure correlations. Contrary to RT, even though no phase transitions were observed in the studied temperature range, some polycentered character is prescribed to the hydrogen bonds in which the ammonium ions of effective symmetry Cs participate at LNT. Certain structural predictions about the saccharinates of K, Rb and Cs are made.

Original languageEnglish (US)
Pages (from-to)1305-1318
Number of pages14
JournalSpectrochimica Acta - Part A: Molecular and Biomolecular Spectroscopy
Volume56
Issue number7
DOIs
StatePublished - Jun 2000

ASJC Scopus subject areas

  • Analytical Chemistry
  • Atomic and Molecular Physics, and Optics
  • Instrumentation
  • Spectroscopy

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