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Interactions between the chloride anion and aromatic molecules: infrared spectra of the Cl-_C6H5CH3, Cl-_C6H5NH2 and Cl-_C6H5OH complexes
Faculty of Science - Papers (Archive)
  • Corinna Emmeluth, University Of Melbourne
  • Berwyck L. J Poad, University of Wollongong
  • Christopher D Thompson, University Of Melbourne
  • Evan J Bieske, University Of Melbourne
RIS ID
72195
Publication Date
1-1-2007
Publication Details

Emmeluth, C., Poad, B. L. J., Thompson, C. D. & Bieske, E. J. (2007). Interactions between the chloride anion and aromatic molecules: infrared spectra of the Cl-_C6H5CH3, Cl-_C6H5NH2 and Cl-_C6H5OH complexes. The Journal of Physical Chemistry Part A: Molecules, Spectroscopy, Kinetics, Environment and General Theory, 111 (31), 7322-7328.

Abstract

The Cl-−C6H5CH3·Ar, Cl-−C6H5NH2·Ar, and Cl-−C6H5OH·Ar anion complexes are investigated using infrared photodissociation spectroscopy and ab initio calculations at the MP2/aug-cc-pVDZ level. The results indicate that for Cl-−C6H5NH2 and Cl-−C6H5OH, the Cl- anion is attached to the substituent group by a single near-linear hydrogen bond. For Cl-−C6H5CH3, the Cl- is attached to an ortho-hydrogen atom on the aromatic ring and to a hydrogen atom on the methyl group by a weaker hydrogen bond. The principal spectroscopic consequence of the hydrogen-bonding interaction in the three complexes is a red-shift and intensity increase for the CH, NH, and OH stretching modes. Complexities in the infrared spectra in the region of the hydrogen-bonded XH stretch band are associated with Fermi resonances between the hydrogen-stretching vibrational modes and bending overtone and combination levels. There are notable correlations between the vibrational red-shift, the elongation of the H-bonded XH group, and the proton affinity of the aromatic molecule's conjugate base.

Citation Information
Corinna Emmeluth, Berwyck L. J Poad, Christopher D Thompson and Evan J Bieske. "Interactions between the chloride anion and aromatic molecules: infrared spectra of the Cl-_C6H5CH3, Cl-_C6H5NH2 and Cl-_C6H5OH complexes" (2007) p. 7322 - 7328
Available at: http://works.bepress.com/berwyck_poad/13/