Chem. Phys. Abstract
Abstract
The solvation of an azide anion in deuterated water has been
investigated using density functional theory based
Car-Parrinello molecular dynamics calculations. The first
solvation shell of the anion was found to contain between five
and six hydrogen bonded water molecules, compared to the six and seven
waters found in analogous classical studies by empirical potentials.
The stretching modes of the azide ion in solution and in the gas phase
are both red shifted by more than 10% compared to experiment.
In agreement with inferences from experiment, the asymmetric
nu3 mode of azide in solution relaxes on a picosecond time scale. The
calculated solvent shift of this mode is about 80 cm-1,
which is somewhat greater than the measured value of the 57
cm-1.