Infrared spectroscopy of anionic hydrated fluorobenzenes

Journal Article · Fri Sep 21 04:00:00 EDT 2007 · Journal of Chemical Physics

DOI:https://doi.org/10.1063/1.2768348· OSTI ID:21024186

Schneider, Holger; Vogelhuber, Kristen M; Weber, J Mathias ^[1]

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1. JILA, NIST, and Department of Chemistry and Biochemistry, University of Colorado, Boulder, Colorado 80309 (United States)

We investigate the structural motifs of anionic hydrated fluorobenzenes by infrared photodissociation spectroscopy and density functional theory. Our calculations show that all fluorobenzene anions under investigation are strongly distorted from the neutral planar molecular geometries. In the anions, different F atoms are no longer equivalent, providing structurally different binding sites for water molecules and giving rise to a multitude of low-lying isomers. The absorption bands for hexa- and pentafluorobenzene show that only one isomer for the respective monohydrate complexes is populated in our experiment. For C{sub 6}F{sub 6}{sup -}{center_dot}H{sub 2}O, we can assign these bands to an isomer where water forms a weak double ionic hydrogen bond with two F atoms in the ion, in accord with the results of Bowen et al. [J. Chem. Phys. 127, 014312 (2007), following paper.] The spectroscopic motif of the binary complexes changes slightly with decreasing fluorination of the aromatic anion. For dihydrated hexafluorobenzene anions, several isomers are populated in our experiments, some of which may be due to hydrogen bonding between water molecules.

• OSTI ID: 21024186
• Journal Information: Journal of Chemical Physics, Journal Name: Journal of Chemical Physics Journal Issue: 11 Vol. 127; ISSN JCPSA6; ISSN 0021-9606
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
ABSORPTION SPECTROSCOPY
ANIONS
COMPLEXES
DENSITY FUNCTIONAL METHOD
DISSOCIATION
FLUORINATED AROMATIC HYDROCARBONS
FLUORINATION
HYDROGEN
INFRARED SPECTRA
ISOMERS
MOLECULAR STRUCTURE
PHOTOLYSIS