1. Ab initlo molecular dynamics and quasichemical study of H+(aq).
- Author
-
Asthagiri, D., Pratt, L. R., and Kress, J. D.
- Subjects
PROTONS ,SOLUTION (Chemistry) ,THERMODYNAMICS ,ATOMS ,PARTICLES (Nuclear physics) ,CONSTITUTION of matter - Abstract
The excess proton in water, H
+ (aq), plays a fundamental role in aqueous solution chemistry. Its solution thermodynamic properties are essential to molecular descriptions of that chemistry and for validation of dynamical calculations. Within the quasichemical theory of solutions those thermodynamic properties are conditional on recognizing underlying solution structures. The quasichemical treatment identifies H3 O+ and H2 O5 + as natural inner- shell complexes, corresponding to the cases of n = 1, 2 water molecule ligands, respectively, of a distinguished H+ ion. A quantum-mechanical treatment of the inner-shell complex with both a dielectric continuum and a classical molecular dynamics treatment of the outer-shell contribution identifies the latter case (the Zundel complex) as the more numerous species. Ab initlo molecular dynamics simulations, with two different electron density functionals, suggest a preponderance of Zundel-like structures, but a symmetrical ideal Zundel cation is not observed. [ABSTRACT FROM AUTHOR]- Published
- 2005
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