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...

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Detalles Bibliográficos
Autores principales: Nadykto, Alexey B., Yu, Fangqun, Natsheh, Anas Al
Formato: Texto
Lenguaje:English
Publicado: Molecular Diversity Preservation International (MDPI) 2009
Materias:
Communication
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC2660665/
https://www.ncbi.nlm.nih.gov/pubmed/19333418
http://dx.doi.org/10.3390/ijms10020507
Descripción
Sumario: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.

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