Artículo
Collecting high-order interactions in an effective pairwise intermolecular potential using the hydrated ion concept: The hydration of Cf3+
Autor/es | Galbis Fuster, Elsa
Hernández Cobos, Jorge Rodríguez Pappalardo, Rafael Sánchez Marcos, Enrique |
Departamento | Universidad de Sevilla. Departamento de Química Orgánica y Farmacéutica |
Fecha de publicación | 2014 |
Fecha de depósito | 2016-10-03 |
Publicado en |
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Resumen | This work proposes a new methodology to build interaction potentials between a highly charged metal cation and water molecules. These potentials, which can be used in classical computer simu- lations, have been fitted to ... This work proposes a new methodology to build interaction potentials between a highly charged metal cation and water molecules. These potentials, which can be used in classical computer simu- lations, have been fitted to reproduce quantum mechanical interaction energies (MP2 and BP86) for a wide range of [M(H2O)n]m+(H2O)l clusters (n going from 6 to 10 and l from 0 to 18). A flexible and polarizable water shell model (Mobile Charge Density of Harmonic Oscillator) has been coupled to the cation-water potential. The simultaneous consideration of poly-hydrated clusters and the polarizability of the interacting particles allows the inclusion of the most important many-body effects in the new polarizable potential. Applications have been centered on the californium, Cf(III) the heaviest actinoid experimentally studied in solution. Two different strategies to select a set of about 2000 structures which are used for the potential building were checked. Monte Carlo simulations of Cf(III)+500 H2O for three of the intermolecular potentials predict an aquaion structure with coordination number close to 8 and average RCf–O in the range 2.43–2.48 Å, whereas the fourth one is closer to 9 with RCf–O = 2.54 Å. Simulated EXAFS spectra derived from the structural Monte Carlo distribution compares fairly well with the available experimental spectrum for the simulations bearing 8 water molecules. An angular distribution similar to that of a square antiprism is found for the octa-coordination. |
Agencias financiadoras | Ministerio de Ciencia e Innovación (MICIN). España |
Identificador del proyecto | CTQ2011-25932 |
Cita | Galbis Fuster, E., Hernández Cobos, J., Rodríguez Pappalardo, R. y Sánchez Marcos, E. (2014). Collecting high-order interactions in an effective pairwise intermolecular potential using the hydrated ion concept: The hydration of Cf3+. Journal of Chemical Physics, 140 (21), 214104. |
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