title: Structure and Dynamics of Ferrocyanide and Ferricyanide Anions in Water and Heavy Water: An Insight by MD Simulations and 2D IR Spectroscopy.
abstract: Combined computational and experimental techniques were employed to investigate at the microscopic level the structural and dynamic properties of ferro- and ferricyanide ions in aqueous solution. The characterization of the structural patterns and multiscale dynamics taking place within the first solvation spheres in water and heavy water solvents was first achieved through extensive molecular dynamics simulations, performed with refined force fields, specifically parametrized for the cyanide ions under investigation. The information gained about the solute-solvent interactions is then validated through the successful comparison of computed and measured waiting-time-dependent 2D IR spectra. The vibrational patterns resulting from 2D IR measurements were rationalized in terms of the interaction between the ion and the neighboring water molecules described by simulation. It was found that, within the first solvation sphere, the stronger interactions of the solvent with the ferro species are responsible for a delay in the relaxation dynamics, which becomes more and more evident on longer time scales.
authors.affiliation: Istituto di Chimica dei Composti OrganoMetallici (ICCOM-CNR) , National Research Council (CNR), Area della Ricerca, Via G. Moruzzi 1, I-56124 Pisa, Italy.
authors.forename: Giacomo
authors.initials: G
authors.lastname: Prampolini
authors.affiliation: Beijing National Laboratory for Molecular Sciences, Molecular Reaction Dynamics Laboratory, Institute of Chemistry, The Chinese Academy of Sciences , Beijing, P. R. China 100190.
authors.forename: Pengyun
authors.initials: P
authors.lastname: Yu
authors.affiliation: Istituto di Chimica dei Composti OrganoMetallici (ICCOM-CNR) , National Research Council (CNR), Area della Ricerca, Via G. Moruzzi 1, I-56124 Pisa, Italy.
authors.forename: Silvia
authors.initials: S
authors.lastname: Pizzanelli
authors.affiliation: Dipartimento di Chimica e Chimica Industriale, Università di Pisa , Via Risorgimento 35, I-56126 Pisa, Italy.
authors.forename: Ivo
authors.initials: I
authors.lastname: Cacelli
authors.affiliation: Beijing National Laboratory for Molecular Sciences, Molecular Reaction Dynamics Laboratory, Institute of Chemistry, The Chinese Academy of Sciences , Beijing, P. R. China 100190.
authors.forename: Fan
authors.initials: F
authors.lastname: Yang
authors.affiliation: Beijing National Laboratory for Molecular Sciences, Molecular Reaction Dynamics Laboratory, Institute of Chemistry, The Chinese Academy of Sciences , Beijing, P. R. China 100190.
authors.forename: Juan
authors.initials: J
authors.lastname: Zhao
authors.affiliation: Beijing National Laboratory for Molecular Sciences, Molecular Reaction Dynamics Laboratory, Institute of Chemistry, The Chinese Academy of Sciences , Beijing, P. R. China 100190.
authors.forename: Jianping
authors.initials: J
authors.lastname: Wang