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AbstractAbstract
[en] Hydrogen bonds in solid hydrates provide the possibility to essentially study the role of the proton acceptors. Hydrogen bond distances and water stretching frequencies, in particular ν (OD) frequencies of isotopically dilute HOD molecules, are most frequently used for a structural and spectroscopic characterization, respectively. Frequency-distance correlations are commonly used to visualize and analyse the experimental data. In a previous survey on 0-H ... Y hydrogen bonds in solids hydrates, because of the lack of suitable spectroscopic data, 0-H ... F type hydrogen bonds had to be omitted. The aim of this thesis was to close this obvious gap and to improve the statistical significance of the data for the other halogenides. Low temperature vibrational spectra (IR and Raman) of isotopically dilute samples of a number of fluorides, chlorides and bromides, with known structures, were measured and the uncoupled ν(OD) frequencies were assigned to distinct 0-H ... Y groups. Correlation curves were calculated using functions of the type ν(OD) = 2727 - A*exp(-B*R(O...Y)); the resulting standard deviations measured 42 cm-1(F: 30 experimental points), 15 cm-1 (Cl: 31 points) and 27 cm-1 (Br: 23 points). For O-H...F, CI, Br hydrogen bonds it was possible to establish a generalized correlation function by replacing the physically meaningless A and B parameters by the electonegativities (χ(Y)) and the Ahrens ionic radii (r(Y)) of the acceptors: ν(OD)=2727-212*exp(1.658*χ(Y)-2.578)-(1.4+r(Y)-R).This correlation function is also appropriate for 0-H-.-0, S, Se hydrogen bonds, provided slightly modified ionic radii are used. In all cases the deviations from the original correlation curves are negligible. Attempts to interpret the scattering of points within the correlation plots on the basis of varying bond valences at the acceptor atoms remained without success. (author)
Original Title
Schwingungsspektroskopische Untersuchungen von Hydraten anorganischer Halogenide
Primary Subject
Source
Jun 1995; 163 p; Available from Univ. Wien Bibliothek, Dr. Karl Lueger-Ring 1, 1010 Wien (AT); Reference number: D29484; Thesis (Dr. rer.nat.)
Record Type
Miscellaneous
Literature Type
Thesis/Dissertation
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