Issue 19, 2005

Infrared spectra of the Cl–C2H4 and Br–C2H4 anion dimers

Abstract

Infrared spectra of mass-selected Cl–C2H4 and Br–C2H4 complexes are recorded in the vicinity of the ethylene CH stretching vibrations (2700–3300 cm−1) using vibrational predissociation spectroscopy. Spectra of both complexes exhibit 6 prominent peaks in the CH stretch region. Comparison with calculated frequencies reveal that the 4 higher frequency bands are associated with CH stretching modes of the C2H4 subunit, while the 2 weaker bands are assigned as overtone or combinations bands gaining intensity through interaction with the CH stretches. Ab initio calculations at the MP2/aug-cc-pVDZ level suggest that C2H4 preferentially forms a single linear H-bond with Cl and Br although a planar bifurcated configuration lies only slightly higher in energy (by 110 and 16 cm−1, respectively). One-dimensional potential energy curves describing the in-plane intermolecular bending motion are developed which are used to determine the corresponding vibrational energies and wavefunctions. Experimental and theoretical results suggest that in their ground vibrational state the Cl-C2H4 and Br-C2H4 complexes are localized in the single H-bonded configuration, but that with the addition of modest amounts of internal energy, the in-plane bending wavefunction also has significant amplitude in the bifurcated structure.

Graphical abstract: Infrared spectra of the Cl−–C2H4 and Br−–C2H4 anion dimers

Article information

Article type
Paper
Submitted
20 Jun 2004
Accepted
05 Aug 2004
First published
26 Aug 2005

Phys. Chem. Chem. Phys., 2005,7, 3419-3425

Infrared spectra of the Cl–C2H4 and Br–C2H4 anion dimers

R. L. Wilson, Z. M. Loh, D. A. Wild, C. D. Thompson, M. D. Schuder, J. M. Lisy and E. J. Bieske, Phys. Chem. Chem. Phys., 2005, 7, 3419 DOI: 10.1039/B508731G

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