Interactions between halide anions and a molecular hydrophobic interface.

Interactions between halide ions (fluoride and iodide) and t-butyl alcohol (TBA) dissolved in water are probed using a recently developed hydration-shell spectroscopic technique and theoretical cluster and liquid calculations. High ignal-to-noise Raman spectroscopic measurements are combined with multivariate curve resolution (Raman-MCR) to reveal that while there is little interaction between aqueous fluoride ions and TBA, iodide ions break down the tetrahedral hydration-shell structure of TBA and produce a red-shift in its CH stretch frequency, in good agreement with the theoretical effective fragment potential (EFP) molecular dynamics simulations and hybrid quantum/EFP frequency calculations. The results imply that there is a significantly larger probability of finding iodide than fluoride in the first hydration shell of TBA, although the local iodide concentration is apparently not as high as in the surrounding bulk aqueous NaI solution.

Intermolecular interactions in complex liquids: effective fragment potential investigation of water-tert-butanol mixtures.

Structure and bonding patterns in tert-butanol (TBA)-water mixtures are investigated by using molecular dynamics simulations with the effective fragment potential (EFP) method. EFP is a model potential in which all parameters are obtained from a set of ab initio calculations on isolated fragment molecules. Mixed-basis EFP potentials (called "EFPm") for water and TBA molecules were prepared and tested in this work.