Anomalously strong effect of the ion sign on the thermochemistry of hydrogen bonded aqueous clusters of identical chemical composition

Alexey B. Nadykto; Fangqun Yu; Anas Al Natsheh

doi:10.3390/ijms10020507

Anomalously strong effect of the ion sign on the thermochemistry of hydrogen bonded aqueous clusters of identical chemical composition

Alexey B. Nadykto
, Fangqun Yu
, Anas Al Natsheh

Atmospheric Sciences Rsch Center

University at Albany

SUNY Albany
Kajaani University of Applied Sciences

Research output: Contribution to journal › Article › peer-review

9 Scopus citations

Abstract

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.

Original language	English
Pages (from-to)	507-517
Number of pages	11
Journal	International Journal of Molecular Sciences
Volume	10
Issue number	2
DOIs	https://doi.org/10.3390/ijms10020507
State	Published - Feb 2009

Keywords

Ab initio
DFT
Gibbs free energies
Hydrogen bonded complexes
Ionic clusters
Sign preference

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10.3390/ijms10020507

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title = "Anomalously strong effect of the ion sign on the thermochemistry of hydrogen bonded aqueous clusters of identical chemical composition",

abstract = "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.",

keywords = "Ab initio, DFT, Gibbs free energies, Hydrogen bonded complexes, Ionic clusters, Sign preference",

author = "Nadykto, \{Alexey B.\} and Fangqun Yu and Natsheh, \{Anas Al\}",

year = "2009",

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T1 - Anomalously strong effect of the ion sign on the thermochemistry of hydrogen bonded aqueous clusters of identical chemical composition

AU - Nadykto, Alexey B.

AU - Yu, Fangqun

AU - Natsheh, Anas Al

PY - 2009/2

Y1 - 2009/2

N2 - 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.

AB - 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.

KW - Ab initio

KW - DFT

KW - Gibbs free energies

KW - Hydrogen bonded complexes

KW - Ionic clusters

KW - Sign preference

UR - https://www.scopus.com/pages/publications/61449232546

U2 - 10.3390/ijms10020507

DO - 10.3390/ijms10020507

M3 - Article

C2 - 19333418

SN - 1661-6596

VL - 10

SP - 507

EP - 517

JO - International Journal of Molecular Sciences

JF - International Journal of Molecular Sciences

IS - 2

ER -

Anomalously strong effect of the ion sign on the thermochemistry of hydrogen bonded aqueous clusters of identical chemical composition

Abstract

Keywords

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