Acetonitrile/sulfuric acid/water clusters: A matrix isolation infrared and computational study

Mark Rozenberg, Aharon Loewenschuss*, Claus J. Nielsen

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

3 Scopus citations

Abstract

In continuation of our studies of sulfuric acid H-bonded complexes of atmospheric relevance we report the infrared spectra of the matrix isolated complexes formed between acetonitrile (CD3CN) and sulfuric acid. Due to the “free” electron pair on its nitrogen, acetonitrile is of basic nature and a formation of the relatively strong intermolecular O–H⋯N hydrogen bond with sulfuric acid may be expected. However, the matrix isolation spectra of this system are complicated by the inevitable presence of water in the vapor and in the matrix. We identify the spectral signatures of the binary 1:1 CD3CN*H2SO4 and triple 1:1:1 CD3CN*H2O*H2SO4 H-bonded complexes. The infrared matrix isolation spectra are accompanied by quantum mechanical studies of relevant model H-complexes. By its red shift from the position of the “free” v(OH) band of sulfuric acid and by the calculated H-bond length of the R(O–H⋯N) hydrogen bond it is concluded that the acetonitrile/sulfuric acid interaction energy is considerably higher than that of acetonitrile/water on the one hand and significantly lower than the sulfuric acid/water interaction, on the other.

Original languageEnglish
Article number126948
JournalJournal of Molecular Structure
Volume1199
DOIs
StatePublished - 5 Jan 2020

Bibliographical note

Publisher Copyright:
© 2019

Keywords

  • FTIR spectroscopy
  • H-bonding
  • Sulfuric acid H-Bonded complexes

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