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Title: Electron-driven ionization of large methanol clusters in helium nanodroplets
Authors: Goulart, Marcelo
Bartl, Peter
Mauracher, Andreas
Zappa, Fabio
Ellis, Andrew M.
Scheier, Paul
First Published: 23-Jan-2013
Publisher: Royal Society of Chemistry
Citation: Physical Chemistry Chemical Physics, 2013, 15 (10), pp. 3577-3582
Abstract: The electron-driven ionization of helium droplets doped with pure methanol and ethanol clusters has been investigated for the first time using high resolution mass spectrometry. Large clusters are readily accessible by this route, with up to 100 alcohol molecules seen in the present study. The mass spectra for the doped helium droplets show many similarities with previous gas phase mass spectrometric studies of methanol and ethanol clusters. Thus the dominant ion products, at least for small clusters, are the protonated species H[superscript +](CH[subscript 3]OH)[subscript n] and H[superscript +](C[subscript 2]H[subscript 5]OH)[subscript n]. Likewise intra-cluster reaction is observed to produce H[superscript +](H[subscript 2]O)(CH[subscript 3]OH)[subscript n] and H[superscript +](H[subscript 2]O)(C[subscript 2]H[subscript 5]OH)[subscript n] ions. However, in helium droplets the observation of consecutive intra-cluster reactions is seen with product molecules containing up to five water molecules. The evidence points towards the proton locating on H[subscript 2]O to form H[subscript 3]O[superscript +], rather than the alcohol, despite the higher proton affinity of the latter. The behaviour of the H[superscript +](H[subscript 2]O)[subscript m](ROH)[subscript n] ion signals as a function of cluster size is consistent with the most stable cluster structures arising from a central H[subscript 3]O[superscript +] ion surrounded by two or more complete five-membered rings with the constituents held in place by hydrogen bonds.
DOI Link: 10.1039/c3cp43826k
ISSN: 1463-9076
eISSN: 1463-9084
Version: Publisher Version
Status: Peer-reviewed
Type: Journal Article
Rights: Copyright © 2013, Royal Society of Chemistry. Deposited with reference to the publisher’s archiving policy available on the SHERPA/RoMEO website.
Appears in Collections:Published Articles, Dept. of Chemistry

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