Other Hydrogen Bonded Systems

Hirata and Iwata, 1998, extended these studies to linear oligomers and an infinite linear hydrogen fluoride polymer. Also this study substantiates the applicability of the BLYP and B3LYP functionals, for which reasonable agreement with experiment has been found with respect to structure, binding energies and vibrational frequencies of the species explored. 

Forthe hydrogen bonded complexes (FH)2, (HC1)2, (H20)2, FH-CO, FH-OC, FH-NH3, ClH -NHj, 0H2- - -NH3, andH30+- - -H20, with binding energies ranging from 1.7 kcal/mol (FH -CO) to 32.9 kcal/mol (H30+ -H20), Tuma, Boese, and Handy, 1999, compared results of several density functional methods with high level conventional wave function based data. With the exception of the HCTH functional, all functionals were found to over- 

System Reference B3LYP B97-1 PBE1PBE BLYP PBE HTCH HTCH38 

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As for water we can expect the MVIEs for other hydrogen bonded systems in low temperature liquids to have an appreciable inverse librational contribution, and this is the case for those alcohols which have been investigated. The data on the isotopic methanols (Table 12.5) confirm this. As expected from the discussion above, the MVIE for OH/OD substitution is negative. Also the isotope effects seem to be approximately additive, MVIE(CH3/CD3) + MVIE(OH/OD) MVIE(CH3OH/CH3OD) 5.3 x 10-3 - 1.6 x 10-3 - 3.7 x 10-3 (observed = 2.9 x 10 3). 

H------0 system is transferable to all other hydrogen bond systems... 

Results for Water-Soluble Polymers and Other Hydrogen Bonding Systems... 

Klemperer. Calculations by Coulson and Robertson on other hydrogen bonding systems yielded times of -10 s. While these discrepancies between theory and experiment are probably not a record, they give one pause to wonder about the factors which determine the efficiency of the vibrational predissociation process. 

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