In:
Physical Chemistry Chemical Physics, Royal Society of Chemistry (RSC), Vol. 24, No. 24 ( 2022), p. 14699-14708
Abstract:
Infrared spectra of the hydrated vanadium cation (V + (H 2 O) 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 + (H 2 O) 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 H 2 O 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 H 2 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.
Type of Medium:
Online Resource
ISSN:
1463-9076
,
1463-9084
Language:
English
Publisher:
Royal Society of Chemistry (RSC)
Publication Date:
2022
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1476283-3
detail.hit.zdb_id:
1476244-4
detail.hit.zdb_id:
1460656-2
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