Computational Investigation of the Solvation of Nitric Acid: Formation of the NO3- and H3O+ Ion Pair

Autor:	J. B. Wright, Jill R. Scott
Rok vydání:	2004
Předmět:	chemistry.chemical_compound Crystallography chemistry Hydrogen bond Nitric acid Computational chemistry Binding energy Potential energy surface Solvation Molecule Physical and Theoretical Chemistry Basis set Transition state
Zdroj:	The Journal of Physical Chemistry A. 108:10578-10585
ISSN:	1520-5215 1089-5639
DOI:	10.1021/jp047633a
Popis:	MP2 and B3LYP calculations were performed to investigate complexes of nitric acid with water using the 6?311++G(2d,p) basis set were used to determine optimized geometries and binding energies for HNO3···nH2O systems (n = 1–4). The structures for the global minima for n = 1–4 have homodromic rings formed by successive hydrogen bonds. The potential energy surface for the HNO3···nH2O clusters is quite shallow. The first stable ion-pair configuration is obtain for a HNO3···4H2O complex. The ion-pair, H3O+—NO3-, is separated by the three H2O molecules forming an Eigen-ion (H9O4+) type structure. The transition states and activation barriers for n = 1–4 were also determined. The zero-point corrected transition-state barrier for the ion-pair is only 0.5 kcal/mol. Larger HNO3···nH2O clusters (n up to 32) were also determined to be dominated by the ion-pair motif.
Databáze:	OpenAIRE
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