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Issue 31, 2017
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Fingerprints of inter- and intramolecular hydrogen bonding in saligenin–water clusters revealed by mid- and far-infrared spectroscopy

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Abstract

Saligenin (2-(hydroxymethyl)phenol) exhibits both strong and weak intramolecular electrostatic interactions. The bonds that result from these interactions compete with intermolecular hydrogen bonds once saligenin binds to one or more water molecules. Infrared (IR) ultraviolet (UV) ion-dip spectroscopy was used to study isolated saligenin–(H2O)n clusters (n = 1–3) in the far- and mid-IR regions of the spectrum. Both harmonic and anharmonic (coupled local modes and Born–Oppenheimer molecular dynamics) quantum chemical calculations were applied to assign cluster geometries to the measured spectra, and to assign vibrational modes to all spectral features measured for each cluster. The hydrated clusters with n = 1 and 2 have geometries that are quite similar to benzyl alcohol–water clusters, whereas the larger clusters with n = 3 show structures equivalent to the isolated water pentamer. Systematic shifts in the frequencies of three hydrogen bond (H-bond) deforming modes, namely OH stretching, OH torsion and H-bond stretching, were studied as a function of the hydrogen bond strength represented by either the OH bond length or the H-bond length. The shifts of the frequencies of these three modes correlate linearly to the OH length, despite both intra- and intermolecular H-bonds being included in this analysis. The OH torsion vibration displays the largest frequency shift when H-bonded, followed by the OH stretching vibrations and finally the H-bond stretching frequency. The frequency shifts of these H-bond deforming modes behave non-linearly as a function of the H-bond length, asymptotically approaching the frequency expected for the non H-bonded modes. The nonlinear behavior was quantified using exponential functions.

Graphical abstract: Fingerprints of inter- and intramolecular hydrogen bonding in saligenin–water clusters revealed by mid- and far-infrared spectroscopy

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Publication details

The article was received on 27 Mar 2017, accepted on 30 May 2017 and first published on 31 May 2017


Article type: Paper
DOI: 10.1039/C7CP01951C
Citation: Phys. Chem. Chem. Phys., 2017,19, 20343-20356
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    Fingerprints of inter- and intramolecular hydrogen bonding in saligenin–water clusters revealed by mid- and far-infrared spectroscopy

    D. J. Bakker, A. Dey, D. P. Tabor, Q. Ong, J. Mahé, M. Gaigeot, E. L. Sibert and A. M. Rijs, Phys. Chem. Chem. Phys., 2017, 19, 20343
    DOI: 10.1039/C7CP01951C

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