Issue 24, 2022

Size-dependent H and H2 formation by infrared multiple photon dissociation spectroscopy of hydrated vanadium cations, V+(H2O)n, n = 3–51

Abstract

Infrared spectra of the hydrated vanadium cation (V+(H2O)n; n = 3–51) were measured in the O–H stretching region employing infrared multiple photon dissociation (IRMPD) spectroscopy. Spectral fingerprints, along with size-dependent fragmentation channels, were observed and rationalized by comparing to spectra simulated using density functional theory. Photodissociation leading to water loss was found for cluster sizes n = 3–7, consistent with isomers featuring intact water ligands. Loss of molecular hydrogen was observed as a weak channel starting at n = 8, indicating the advent of inserted isomers, HVOH+(H2O)n−1. The majority of ions for n = 8, however, are composed of two-dimensional intact isomers, concordant with previous infrared studies on hydrated vanadium. A third channel, loss of atomic hydrogen, is observed weakly for n = 9–11, coinciding with the point at which the H and H2O calculated binding energies become energetically competitive for intact isomers. A clear and sudden spectral pattern and fragmentation channel intensity at n = 12 suggest a structural change to inserted isomers. The H2 channel intensity decreases sharply and is not observed for n = 20 and 25–51. IRMPD spectra for clusters sizes n = 15–51 are qualitatively similar indicating no significant structural changes, and are thought to be composed of inserted isomers, consistent with recent electronic spectroscopy experiments.

Graphical abstract: Size-dependent H and H2 formation by infrared multiple photon dissociation spectroscopy of hydrated vanadium cations, V+(H2O)n, n = 3–51

Supplementary files

Article information

Article type
Paper
Submitted
18 feb 2022
Accepted
06 apr 2022
First published
06 apr 2022
This article is Open Access
Creative Commons BY license

Phys. Chem. Chem. Phys., 2022,24, 14699-14708

Size-dependent H and H2 formation by infrared multiple photon dissociation spectroscopy of hydrated vanadium cations, V+(H2O)n, n = 3–51

J. Heller, E. M. Cunningham, J. C. Hartmann, C. van der Linde, M. Ončák and M. K. Beyer, Phys. Chem. Chem. Phys., 2022, 24, 14699 DOI: 10.1039/D2CP00833E

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