ISSN:
0020-7608
Keywords:
potential functions
;
nitrate anion
;
nitrate-water interaction
;
nitrate-water cluster geometries
;
vibrational frequencies
;
Chemistry
;
Theoretical, Physical and Computational Chemistry
Source:
Wiley InterScience Backfile Collection 1832-2000
Topics:
Chemistry and Pharmacology
Notes:
The interaction between nitrate anion and water has been investigated by Hartree-Fock calculations with the 6-311+G(d, p) basis set and by B3LYP density functional calculations with the aug-cc-pVTZ basis set. It is found that the global energy minimum is a planar configuration where both hydrogen atoms of water are coordinated to two oxygen atoms of NO3- by distorted hydrogen bonds. In contrast to former studies on NO3-/H2O this configuration is found to be asymmetric at the highest theoretical level employed. The corresponding structure with C2v symmetry is a saddle point at slightly higher energy. A singly hydrogen-bonded configuration is still about 2.4 kcal/mol higher in energy. The shifts in the vibrational frequencies of water and nitrate upon complexation were calculated. A compact analytical potential function of NO3-/H2O for use in statistical thermodynamic simulations was obtained from 390 points of the energy surface and an intramolecular force field for the nitrate anion is presented. © 1998 John Wiley & Sons, Inc. Int J Quant Chem 70: 877-886, 1998
Additional Material:
5 Ill.
Type of Medium:
Electronic Resource
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