Anomalously strong effect of the ion sign on the thermochemistry of hydrogen bonded aqueous clusters of identical chemical composition.
The sign preference of hydrogen bonded aqueous ionic clusters X+/-(H(2)O)(i) (n =1-5, X = F; Cl; Br) has been investigated using the Density Functional Theory and ab initio MP2 method. The present study indicates the anomalously large difference in formation free energies between cations and anions of identical chemical composition. The effect of vibrational anharmonicity on stepwise Gibbs free energy changes has been investigated, and possible uncertainties associated with the harmonic treatment of vibrational spectra have been discussed.
Nadykto
Alexey B
AB
Atmospheric Sciences Research Center, State University of New York at Albany, 251 Fuller Rd., Albany 12203, NY, USA.
Yu
Fangqun
F
Atmospheric Sciences Research Center, State University of New York at Albany, 251 Fuller Rd., Albany 12203, NY, USA.
Al Natsheh
Anas
A
Kajaani University of Applied Sciences, Kuntokatu 5, 87101 Kajaani, Finland.