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The overlap of "hydration cospheres" of the two cations will cause the decrease of the number of hydrogen bonds of water per cation and lead to the decrease of the solution volume, since less hydrogen bonding will result in smaller volume for water. (32) The caging effect denotes the tendency of water molecules to form cagelike structure to "hide" the hydrocarbon tails of the R4N + ion inside. When two cations approach to a suitable distance, their cage systems will tend to link up and stabilize each other, leading to a smaller total volume (see also ref 5 and 8).

SynopsisOpticid rotiilioii studies were performed on five coinpouiids coiitaiiiitig two peptide groiips. Four of the molecules were confined to restricted regions of conformational space by the presence of closed rings. Solvent and temperature were varied, and theoretical c:ttl(wlatioiis were done for each compound covering the appropriate coiiformational space. The interpretation which results is qualitatively sriccessful over the coilformational regions covered by the compounds. Quantitative correlation between theory and experiment will require compounds of high rigidity.