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Interactions between the chloride anion and aromatic molecules: infrared spectra of the Cl-_C6H5CH3, Cl-_C6H5NH2 and Cl-_C6H5OH complexes

Journal Article


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Abstract


  • The Cl --C 6H 5CH 3-Ar, Cl --C 6H 5N 3Ar, and Cl --C 6H 5OH.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 --C 6H 5NH 2 and CI 5-C 6H 5OH, the Cl - anion is attached to the substituent group by a single near-linear hydrogen bond. For Cl --C 6H 5CH 3, the Cl 5 is attached to an orifco-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 hydrogenstretching 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.

UOW Authors


  •   Bieske, Evan J. (external author)
  •   Thompson, Christopher D. (external author)
  •   Emmeluth, Corinna (external author)
  •   Poad, Berwyck L. J.

Publication Date


  • 2007

Citation


  • 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.

Scopus Eid


  • 2-s2.0-34548044266

Ro Full-text Url


  • http://ro.uow.edu.au/cgi/viewcontent.cgi?article=7972&context=scipapers

Ro Metadata Url


  • http://ro.uow.edu.au/scipapers/4629

Has Global Citation Frequency


Number Of Pages


  • 6

Start Page


  • 7322

End Page


  • 7328

Volume


  • 111

Issue


  • 31

Abstract


  • The Cl --C 6H 5CH 3-Ar, Cl --C 6H 5N 3Ar, and Cl --C 6H 5OH.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 --C 6H 5NH 2 and CI 5-C 6H 5OH, the Cl - anion is attached to the substituent group by a single near-linear hydrogen bond. For Cl --C 6H 5CH 3, the Cl 5 is attached to an orifco-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 hydrogenstretching 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.

UOW Authors


  •   Bieske, Evan J. (external author)
  •   Thompson, Christopher D. (external author)
  •   Emmeluth, Corinna (external author)
  •   Poad, Berwyck L. J.

Publication Date


  • 2007

Citation


  • 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.

Scopus Eid


  • 2-s2.0-34548044266

Ro Full-text Url


  • http://ro.uow.edu.au/cgi/viewcontent.cgi?article=7972&context=scipapers

Ro Metadata Url


  • http://ro.uow.edu.au/scipapers/4629

Has Global Citation Frequency


Number Of Pages


  • 6

Start Page


  • 7322

End Page


  • 7328

Volume


  • 111

Issue


  • 31