Cluster models of aqueous Na ~+ and Cl ~+ in sea water/ice

摘要

In this article, we present finite cluster models of aqueous solutes NaCl(H _2O) _(10), NaCl(H _2O) _5, and (H _2O) _6 in terms of molecular geometry and vibrational spectra for interpretation of experimental infrared spectra of NaCl brine solutions. The quantum chemistry program GAMESS is used to optimize the model clusters to a local minimum energy gradient of less than 5.0d-6 hartrees/bohr with B3LYP in a gaussian basis of 6-31G(d,p). Harmonic frequencies are computed for comparison with the infrared spectra measured by attenuated total reflection of a temperature-controlled Ge plate under a layer of cold brine solution. Themotivation for this research is to understand the mechanism by which freezing seawater excludes halide ions (mainly Cl -) and why the O-H stretching region of the spectra changes with temperature. Frost flowers, sea ice, and snow in marine environments contain concentrated halides in liquid brine at their surfaces which lead to catalytic destruction of low-altitude ozone in the polar regions of the Earth.