A Coupled Car-Parrinello Molecular Dynamics and EXAFS Data Analysis Investigation of Aqueous Co2+
- 10 November 2006
- journal article
- research article
- Published by American Chemical Society (ACS) in The Journal of Physical Chemistry A
- Vol. 110 (48), 13081-13088
- https://doi.org/10.1021/jp064688z
Abstract
We have studied the microscopic solvation structure of Co2+ in liquid water by means of density functional theory (DFT)-based Car−Parrinello molecular dynamics (CPMD) simulations and extended X-ray absorption fine structure (EXAFS) data analysis. The effect of the number of explicit water molecules in the simulation box on the first and second hydration shell structures has been considered. Classical molecular dynamics simulations, using an effective two-body potential for Co2+−water interactions, were also performed to show box size effects in a larger range. We have found that the number of explicit solvent molecules has a marginal role on the first solvation shell structural parameters, whereas larger boxes may be necessary to provide a better description of the second solvation shell. Car−Parrinello simulations were determined to provide a reliable description of structural and dynamical properties of Co2+ in liquid water. In particular, they seem to describe both the first and second hydration shells correctly. The EXAFS signal was reconstructed from Car−Parrinello simulations. Good agreement between the theoretical and experimental signals was observed, thus strengthening the microscopic picture of the Co2+ solvation properties obtained using first-principle simulations.This publication has 72 references indexed in Scilit:
- Density-functional theory-based molecular simulation study of liquid methanolThe Journal of Chemical Physics, 2004
- Characterization of dynamics and reactivities of solvated ions byab initiosimulationsJournal of Computational Chemistry, 2003
- Rate and Mechanisms for Water Exchange around Li+(aq) from MD SimulationsThe Journal of Physical Chemistry B, 2003
- Reaction Path Sampling of the Reaction between Iron(II) and Hydrogen Peroxide in Aqueous SolutionThe Journal of Physical Chemistry A, 2002
- Electronic properties of hard and soft ions in solution: Aqueous Na+ and Ag+ comparedThe Journal of Chemical Physics, 2001
- The solvation of Na+ in water: First-principles simulationsThe Journal of Chemical Physics, 2000
- Assessment of the validity of intermolecular potential models used in molecular dynamics simulations by extended x-ray absorption fine structure spectroscopy: A case study of Sr2+ in methanol solutionThe Journal of Chemical Physics, 1998
- Application of x-ray absorption spectroscopy to the studies of structure and bonding of metal complexes in solutionAccounts of Chemical Research, 1986
- Absolute energy calibration of X-ray radiation from synchrotron sourcesJournal of Applied Crystallography, 1985
- Hydration and complex formation study on concentrated MCl2 solutions [M=Co(II), Ni(II), Cu(II)] by x-ray diffraction techniqueThe Journal of Chemical Physics, 1981