Structural, dynamical, and transport ...
Type de document :
Compte-rendu et recension critique d'ouvrage
DOI :
Titre :
Structural, dynamical, and transport properties of the hydrated halides: How do At<sup>-</sup> bulk properties compare with those of the other halides, from F<sup>-</sup> to I<sup>-</sup>?
Auteur(s) :
Réal, Florent [Auteur]
Physico-Chimie Moléculaire Théorique [PCMT]
Severo Pereira Gomes, Andre [Auteur]
Physico-Chimie Moléculaire Théorique [PCMT]
Guerrero Martínez, Yansel Omar [Auteur]
Physico-Chimie Moléculaire Théorique [PCMT]
Galland, Nicolas [Auteur]
Chimie Et Interdisciplinarité : Synthèse, Analyse, Modélisation [CEISAM]
Vallet, Valérie [Auteur]
Physico-Chimie Moléculaire Théorique [PCMT]
Masella, Michel [Auteur]
Institut de Biologie et de Technologies de Saclay [IBITECS]
Ayed, Tarah [Auteur]
Chimie Et Interdisciplinarité : Synthèse, Analyse, Modélisation [CEISAM]
Physico-Chimie Moléculaire Théorique [PCMT]
Severo Pereira Gomes, Andre [Auteur]
Physico-Chimie Moléculaire Théorique [PCMT]
Guerrero Martínez, Yansel Omar [Auteur]
Physico-Chimie Moléculaire Théorique [PCMT]
Galland, Nicolas [Auteur]
Chimie Et Interdisciplinarité : Synthèse, Analyse, Modélisation [CEISAM]
Vallet, Valérie [Auteur]
Physico-Chimie Moléculaire Théorique [PCMT]
Masella, Michel [Auteur]
Institut de Biologie et de Technologies de Saclay [IBITECS]
Ayed, Tarah [Auteur]
Chimie Et Interdisciplinarité : Synthèse, Analyse, Modélisation [CEISAM]
Titre de la revue :
The Journal of Chemical Physics
Pagination :
124513
Éditeur :
American Institute of Physics
Date de publication :
2016-03-28
ISSN :
0021-9606
Discipline(s) HAL :
Physique [physics]/Physique [physics]/Chimie-Physique [physics.chem-ph]
Résumé en anglais : [en]
The properties of halides from the lightest, Fuoride (F<sup>-</sup>), to the heaviest, astatide (At<sup>-</sup>), have been studied in water using a polarizable force-field approach based on molecular dynamics (MD) ...
Lire la suite >The properties of halides from the lightest, Fuoride (F<sup>-</sup>), to the heaviest, astatide (At<sup>-</sup>), have been studied in water using a polarizable force-field approach based on molecular dynamics (MD) simulations at the 10 ns scale. The selected force-field explicitly treats the cooperativity within the halide-water hydrogen bond networks. The force- eld parameters have been adjusted to ab initio data on anion/water clusters computed at the relativistic Möller-Plesset second-order perturbation theory level of theory. The anion static polarizabilities of the two heaviest halides, I<sup>-</sup> and At<sup>-</sup>, were computed in the gas phase using large and diffuse atomic basis sets, and taking into account both electron correlation and spin-orbit coupling within a four-component framework. Our MD simulation results show the solvation properties of I<sup>-</sup> and At<sup>-</sup> in aqueous phase to be very close. For instance, their first hydration shells are structured and encompass 9.2 and 9.1 water molecules at about 3.70 ± 0.05 Å, respectively. These values have to be compared to the F<sup>-</sup>, Cl<sup>-</sup>, and Br<sup>-</sup> ones, i.e., 6.3, 8.4, and 9.0 water molecules at 2.74, 3.38, and 3.55 Å, respectively. Moreover our computations predict the solvation free energy of At<sup>-</sup> in liquid water at ambient conditions to be 68 kcal mol<sup>-1</sup>, a value also close the I<sup>-</sup> one, about 70 kcal mol<sup>-1</sup>. In all, our simulation results for I<sup>-</sup> are in excellent agreement with the latest neutron- and X-ray diffraction studies. Those for the At<sup>-</sup> ion are predictive, as no theoretical or experimental data are available to date.Lire moins >
Lire la suite >The properties of halides from the lightest, Fuoride (F<sup>-</sup>), to the heaviest, astatide (At<sup>-</sup>), have been studied in water using a polarizable force-field approach based on molecular dynamics (MD) simulations at the 10 ns scale. The selected force-field explicitly treats the cooperativity within the halide-water hydrogen bond networks. The force- eld parameters have been adjusted to ab initio data on anion/water clusters computed at the relativistic Möller-Plesset second-order perturbation theory level of theory. The anion static polarizabilities of the two heaviest halides, I<sup>-</sup> and At<sup>-</sup>, were computed in the gas phase using large and diffuse atomic basis sets, and taking into account both electron correlation and spin-orbit coupling within a four-component framework. Our MD simulation results show the solvation properties of I<sup>-</sup> and At<sup>-</sup> in aqueous phase to be very close. For instance, their first hydration shells are structured and encompass 9.2 and 9.1 water molecules at about 3.70 ± 0.05 Å, respectively. These values have to be compared to the F<sup>-</sup>, Cl<sup>-</sup>, and Br<sup>-</sup> ones, i.e., 6.3, 8.4, and 9.0 water molecules at 2.74, 3.38, and 3.55 Å, respectively. Moreover our computations predict the solvation free energy of At<sup>-</sup> in liquid water at ambient conditions to be 68 kcal mol<sup>-1</sup>, a value also close the I<sup>-</sup> one, about 70 kcal mol<sup>-1</sup>. In all, our simulation results for I<sup>-</sup> are in excellent agreement with the latest neutron- and X-ray diffraction studies. Those for the At<sup>-</sup> ion are predictive, as no theoretical or experimental data are available to date.Lire moins >
Langue :
Anglais
Vulgarisation :
Non
Projet ANR :
Source :