Mr. Waterland et al., Symmetry breaking effects in NO3-: Raman spectra of nitrate salts and ab initio resonance Raman spectra of nitrate-water complexes, J CHEM PHYS, 114(14), 2001, pp. 6249-6258
Ground-state structures and vibrational frequencies are calculated for comp
lexes of the nitrate anion with one and two water molecules at the ab initi
o Hartree-Fock level with a basis set including diffuse and polarization fu
nctions. Two local minimum geometries are found for each complex. Calculati
ons of the electronically excited states at the CIS level are then used to
find the forces on each of the atoms upon vertical excitation to the two lo
west-lying (near-degenerate) strongly allowed electronic transitions. These
forces are converted to gradients of the excited-state potential surfaces
along the ground-state normal modes and compared with the parameters obtain
ed previously from empirical simulations of the experimental resonance Rama
n intensities of NO3- in dilute aqueous solution. The calculations on two-w
ater clusters agree well with the experimental excited-state geometry chang
es along the totally symmetric N-O stretch. The calculations underestimate
the frequency splitting of the antisymmetric stretching vibration (degenera
te in the isolated D-3h ion) and the resonance Raman intensity in this mode
, suggesting that bulk solvent polarization enhances the asymmetry of the l
ocal environment for NO3- in water. Comparison of the ground-state vibratio
nal frequency splitting of the antisymmetric stretch with the corresponding
values for the nitrate ion in salts having known crystal structures sugges
ts that the rms difference among the three N-O bond lengths for nitrate ani
on in water probably exceeds 0.01 A. (C) 2001 American Institute of Physics
.