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Register a new userConjugation in hydrogen-bonded systems
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Yulia V. Novakovskaya
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Analysis of the electron density distribution in clusters composed of hydrogen fluoride, water, and ammonia molecules, especially within the hydrogen-bond domains, reveals the existence of both sigma- and pi-binding between molecules. The sigma-kind density distribution determines the mutual orientation of molecules. A pi-system may be delocalized conjugated, which provides additional stabilization of molecular clusters. In those clusters where the sequence of hydrogen bonds is not planar, a peculiar kind of pi-conjugation exists. HF anion and H5O2 cation are characterized by quasi-triple bonds between the electronegative atoms. The most long-lived species stabilized by delocalized pi-binding are rings and open or closed hoops composed of fused rings. It is conjugated pi-system that determines cooperativity phenomenon.
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During compression of a water dimer calculated with high-precision first-principles methods, the trends of H-bond and O-H bond lengths show quantum effect of the electronic structure. We found that the H-bond length keeps decreasing, while the O-H bond length increases up to the stable point and decreases beyond it when the water dimer is further compressed. The remarkable properties are different from those observed in most previous researches which can be understood and extrapolated through classical simulation. The observations can be explained by the decrease in orbital overlap and change in the exchange repulsion interaction between water monomers. The dominant interaction between water monomers changes from electrostatic interaction to exchange repulsion at the turning point of the O-H bond length when the O...O distance is decreased. These findings highlight the quantum effect on the hydrogen bond in extreme conditions and play an important role in the recognition of the hydrogen bond structure and mechanism.
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