Anomalously Strong Effect of the Ion Sign on the Thermochemistry of Hydrogen Bonded Aqueous Clusters of Identical Chemical Composition

International Journal of Molecular Sciences

Alexey B. Nadykto¹  Fangqun Yu¹ 

[1] Atmospheric Sciences Research Center, State University of New York at Albany, 251 Fuller Rd., Albany 12203, NY, USA

关键词: Ionic clusters;    DFT;    ab initio;    sign preference;    Gibbs free energies;    hydrogen bonded complexes;   

DOI  :  10.3390/ijms10020507

来源: mdpi

【 摘 要 】

The sign preference of hydrogen bonded aqueous ionic clusters X±(H₂O)_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.

【 授权许可】

CC BY   
© 2009 by the authors; licensee Molecular Diversity Preservation International, Basel, Switzerland.