Water Dissociation upon Adsorption onto Free Iron Clusters Is Size Dependent.
Cationic iron clusters, produced through laser ablation and subsequently complexed with a water molecule Fen(+)-H2O (n = 6-15) are mass-selectively investigated via infrared multiple photon dissociation (IR-MPD) spectroscopy in the 300-1700 cm(-1) spectral range. The experimental data are complemented by density functional theory calculations at the OPBE/TZP level for the Fe13(+)-H2O system. The observed spectra can be explained by a mixture of clusters where for a majority water is adsorbed molecularly but for a small but significant fraction also dissociation of water molecules occurs. The bands observed at frequencies 300-700 cm(-1) exhibit regular, size-dependent frequency shifts, showing that (a) dissociation takes places on all cluster sizes and (b) the interaction of water with the cluster surface is not influenced much by the particular cluster structure. The intensity evolution of the absorption bands suggests that dissociation is increasingly probable for larger cluster sizes.
Radboud University , Institute for Molecules and Materials, FELIX Laboratory, Toernooiveld 7c, 6525 ED Nijmegen, The Netherlands.|Anton Pannekoek Institute, University of Amsterdam , Science Park 904, 1098 XH Amsterdam, The Netherlands.
Denis M
DM
Kiawi
Radboud University , Institute for Molecules and Materials, FELIX Laboratory, Toernooiveld 7c, 6525 ED Nijmegen, The Netherlands.
Valeriy
V
Chernyy
Radboud University , Institute for Molecules and Materials, FELIX Laboratory, Toernooiveld 7c, 6525 ED Nijmegen, The Netherlands.|Van 't Hoff Institute for Molecular Sciences, University of Amsterdam , Science Park 904, 1098 XH Amsterdam, The Netherlands.
Jos
J
Oomens
Van 't Hoff Institute for Molecular Sciences, University of Amsterdam , Science Park 904, 1098 XH Amsterdam, The Netherlands.
Wybren Jan
WJ
Buma
Department of Physical Chemistry, Chemistry and Chemical Engineering Research Center of Iran , P.O. Box 14335-186, Tehran, Iran.
Zahra
Z
Jamshidi
Amsterdam Center for Multiscale Modeling Section Theoretical Chemistry, VU University Amsterdam , De Boelelaan 1083, 1081 HV Amsterdam, The Netherlands.
Lucas
L
Visscher
Anton Pannekoek Institute, University of Amsterdam , Science Park 904, 1098 XH Amsterdam, The Netherlands.|SRON Netherlands, Sorbonnelaan, 3584 CA Utrecht, The Netherlands.
L B F M
LB
Waters
Radboud University , Institute for Molecules and Materials, FELIX Laboratory, Toernooiveld 7c, 6525 ED Nijmegen, The Netherlands.
Joost M
JM
Bakker