A quantum molecular dynamics study of the properties of NO+(H2O)n clusters

The structures and dynamics of NO+(H2O)n, with n=1,2,3, have been studied using first principles Born–Oppenheimer molecular dynamics (BOMD) performed in the framework of density functional theory (DFT) with a generalized gradient approximation (GGA). The ground-state structure of NO+(H2O), in which a relatively weak bond connects NO+ and H2O, is shown to be floppy along certain degrees of freedom. When a second water molecule is added, a new solvation shell is formed via a hydrogen bond. Our investigations indicate that a third water molecule attaches to the first water molecule and completes the second solvation shell. The hydration energies are found to be 1.31, 0.87, and 0.77 eV for n=1,2,3, respectively. The vibrational spectra at room temperature are calculated for NO+, and all three hydrated clusters. Compared to an isolated NO+ ion, a redshift of 120–200 cm−1 is observed for the N–O vibrational mode in NO+(H2O)n. For n=2, new peaks, identified as O–H stretches of the first H2O molecule, appear belo...

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