ISSN:
1572-8897
Source:
Springer Online Journal Archives 1860-2000
Topics:
Chemistry and Pharmacology
,
Mathematics
Notes:
Abstract A perturbation theoretical method is proposed that allows determination of the function describing the dependence of the intramolecular XH(D) potential on the hydrogen bond strength. Treating the XH(D) oscillators as mixed cubic–quartic oscillators in which the stretch–stretch couplings of the ν(X–H(D)) mode with the internal modes of the radical X may be neglected, and introducing the hydrogen bonding influence through the changes in the harmonic diagonal force constants (as proposed by Sceats and Rice [41]), it is possible to extract the analytical form of the function $$k_{rr} = f\left( {R_{X \ldots Y} } \right)$$ ) from the experimental $$\tilde v_{XH(D)} $$ versus $$R_{X \ldots Y} $$ correlations. The other parameters obtained by the empirical correlations, within this model, also have an exact physical meaning. The method is applicable to weak hydrogen bonds as well as to hydrogen bonds of intermediate strength, and, strictly speaking, to linear X– $$X - H(D) \ldots Y$$ systems. However, extension to arbitrary geometry may be easily done.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1023/A:1019110717451
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