Modeling the hydration of mono-atomic anions from the gas phase to the bulk phase: the case of the halide ions F<sup>-</sup>, Cl<sup>-</sup>, and Br<sup>-</sup>. - Archive ouverte HAL Accéder directement au contenu
Article Dans Une Revue Journal of Chemical Physics Année : 2012

Modeling the hydration of mono-atomic anions from the gas phase to the bulk phase: the case of the halide ions F-, Cl-, and Br-.

Résumé

In this work, we investigate the hydration of the halide ions fluoride, chloride, and bromide using classical molecular dynamics simulations at the 10 ns scale and based on a polarizable force-field approach, which treats explicitly the cooperative bond character of strong hydrogen bond networks. We have carried out a thorough analysis of the ab initio data at the MP2 or CCSD(T) level concerning anion/water clusters in gas phase to adjust the force-field parameters. In particular, we consider the anion static polarizabilities computed in gas phase using large atomic basis sets including additional diffuse functions. The information extracted from trajectories in solution shows well structured first hydration shells formed of 6.7, 7.0, and 7.6 water molecules at about 2.78 Å, 3.15 Å, and 3.36 Å for fluoride, chloride, and bromide, respectively. These results are in excellent agreement with the latest neutron- and x-ray diffraction studies. In addition, our model reproduces several other properties of halide ions in solution, such as diffusion coefficients, description of hydration processes, and exchange reactions. Moreover, it is also able to reproduce the electrostatic properties of the anions in solution (in terms of anion dipole moment) as reported by recent ab initio quantum simulations. All the results show the ability of the proposed model in predicting data, as well as the need of accounting explicitly for the cooperative character of strong hydrogen bonds to reproduce ab initio potential energy surfaces in a mean square sense and to build up a reliable force field.
Fichier non déposé

Dates et versions

hal-00786658 , version 1 (09-02-2013)

Identifiants

Citer

Michael Trumm, Yansel Omar Guerrero Martínez, Florent Réal, Michel Masella, Valérie Vallet, et al.. Modeling the hydration of mono-atomic anions from the gas phase to the bulk phase: the case of the halide ions F-, Cl-, and Br-.. Journal of Chemical Physics, 2012, 136, pp.044509. ⟨10.1063/1.3678294⟩. ⟨hal-00786658⟩
91 Consultations
0 Téléchargements

Altmetric

Partager

Gmail Facebook X LinkedIn More