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Hydrogen bonds are one of the most enigmatic intermolecular interactions where the strength of interaction depends very intimately on the local environment of the bonded atoms. One can change the entire nature of the interactions by changing its local environment. Many of the enzymatic reactions work by this above-mentioned mechanism. Hence, it is important to understand how changes in the local environment can modify hydrogen bonds. In line with this, complete structural and vibrational investigations on ammonium ion substituted potassium dihydrogen phosphate mixed crystals K0.988(NH4)0.012H2PO4 and (K0.956(NH4)0.044H2PO4) are performed. The behaviour of O–H–O hydrogen bond in these crystals is very sensitive to changes in the local environment. A small change in the concentration of K+ ion has an observable effect on hydrogen bond geometry and hence on the double-well potential energy contour for these bonds. The dynamics of H atom depends on the potential barrier height. It changes gradually with decreasing temperature from predominantly inter-well to completely intra-well dynamics with an intermediate precursor region, where inter-well and intra-well dynamics are important. [ABSTRACT FROM AUTHOR]

The structure of the mixed crystal [K1− x(NH4) x]3H(SO4)2 as obtained from single-crystal neutron diffraction is compared with the previously reported room-temperature neutron structure of crystalline K3H(SO4)2. The two structures are very similar, as indicated by the high value of their isostructurality index (94.8%). It was found that the replacement of even a small amount (3%) of K+ with NH4+ has a significant influence on the short strong hydrogen bond connecting the two SO42− ions. Earlier optical measurements had revealed that the kinetics of the superionic transition in the solid solution [K1− x(NH4) x]3H(SO4)2 are much faster than in K3H(SO4)2; this reported difference in the kinetics of the superionic phase transition in this class of crystal is explained on the basis of the difference in strength of the hydrogen-bond interactions in the two structures. [ABSTRACT FROM AUTHOR]

Molar volumes of a wide series of Schiff bases and their structural analogs, such as N-benzyl-ideneaniline N-oxides and azo compounds, in infinitely dilute solutions were determined. Analysis of the obtained values in terms of the additivity scheme showed that molecular fragments and substituting groups in these compounds are strongly solvated by solvent molecules, which leads to deviation of most molecules from the planar arrangement of the aryl moieties and bridging groups. Most compounds in which H-chelate rings are formed due to intramolecular hydrogen bonding are characterized by contraction of molar volumes, indicating their entropy stabilization in solution via release of solvent molecules from the solvate shell upon chelation. Methods for the determination of dipole moments and Kerr constants in solution can be simplified to a considerable extent for those compounds for which the additivity scheme was applied to calculate the molar volumes. [ABSTRACT FROM AUTHOR]