Proton Transfer in Strong Hydrogen Bonds Revealed by Infrared Spectra - Correlations between Structure and Spectra for the BrH : NH_3 Complex

• Authors: K. Szczepaniak , W. Person
• Languages of publication: EN

Abstracts

EN

Our scope is to achieve an understanding of the relation between the infrared spectrum and structure of a strong hydrogen-bonded complex, BrH : NH$_3$, and how and why this relationship is affected by the environment surrounding the complex. A series of DFT/B3LYP/6-31G(d,p) calculations was carried out for this system to obtain its structure and spectrum in different dielectric fields characterized by their relative permittivities. Changes in structure and spectrum (both frequencies and intensities) as the relative permittivity changes are explored. Calculations of spectra are made first under the harmonic approximation. In the next step the effect of anharmonicity was estimated for several different dielectric fields. The calculated anharmonic spectrum (for ε_r = 1.6) is compared with the experimentally observed infrared spectrum of the complex isolated in an Ar matrix at 10 K, obtained in our laboratory. The calculated frequencies and relative intensities for all normal modes agree with the corresponding experimental data surprisingly well. The potential usefulness of structure-spectra correlations is explored.

Keywords

EN

82.30.Rs; 33.20.Ea; 33.70.Fd; 31.15.Ew; 33.20.Tp

Discipline

• 82.30.Rs: Hydrogen bonding, hydrophilic effects
• 33.70.Fd: Absolute and relative line and band intensities
• 33.20.Tp: Vibrational analysis
• 33.20.Ea: Infrared spectra

• Publisher: Institute of Physics, Polish Academy of Sciences
• Journal: Acta Physica Polonica A
• Year: 2007
• Volume: 112
• Issue: S
• Pages: S-19-S-38

Dates

published

2007-12

received

2007-10-26

Contributors

author

K. Szczepaniak

• Department of Chemistry, University of Florida, P.O. Box 117200, Gainesville, Florida, 32611, USA

author

W. Person

• Department of Chemistry, University of Florida, P.O. Box 117200, Gainesville, Florida, 32611, USA

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Identifiers

DOI

10.12693/APhysPolA.112.S-19