Infrared Spectra and Ab Initio Calculations for the F-−(CH4)n (n = 1−8) Anion Clusters

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dc.contributor.author Loh, Zoë
dc.contributor.author Wilson, R. L.
dc.contributor.author Gordon, Mark
dc.contributor.author Wild, D. A.
dc.contributor.author Bieske, Evan
dc.contributor.author Lisy, J. M.
dc.contributor.author Njegic, Bosiljka
dc.contributor.author Gordon, Mark
dc.contributor.department Chemistry
dc.date 2018-02-17T08:22:30.000
dc.date.accessioned 2020-06-30T01:20:28Z
dc.date.available 2020-06-30T01:20:28Z
dc.date.copyright Sun Jan 01 00:00:00 UTC 2006
dc.date.issued 2006-12-01
dc.description.abstract <p>Infrared spectra of mass-selected F-−(CH4)<em>n</em> (<em>n</em> = 1−8) clusters are recorded in the CH stretching region (2500−3100 cm-1). Spectra for the <em>n</em> = 1−3 clusters are interpreted with the aid of ab initio calculations at the MP2/6-311++G(2df 2p) level, which suggest that the CH4ligands bind to F- by equivalent, linear hydrogen bonds. Anharmonic frequencies for CH4 and F-−CH4 are determined using the vibrational self-consistent field method with second-order perturbation theory correction. The <em>n</em> = 1 complex is predicted to have a <em>C</em>3<em>v</em> structure with a single CH group hydrogen bonded to F-. Its spectrum exhibits a parallel band associated with a stretching vibration of the hydrogen-bonded CH group that is red-shifted by 380 cm-1 from the ν1 band of free CH4 and a perpendicular band associated with the asymmetric stretching motion of the nonbonded CH groups, slightly red-shifted from the ν3 band of free CH4. As <em>n</em>increases, additional vibrational bands appear as a result of Fermi resonances between the hydrogen-bonded CH stretching vibrational mode and the 2ν4 overtone and ν2 + ν4combination levels of the methane solvent molecules. For clusters with <em>n</em> ≤ 8, it appears that the CH4 molecules are accommodated in the first solvation shell, each being attached to the F- anion by equivalent hydrogen bonds.</p>
dc.description.comments <p>Reprinted (adapted) with permission from <em>Journal of Physical Chemistry A</em> 110 (20060: 13736, doi:<a href="http://dx.doi.org/10.1021/jp0654112" target="_blank">10.1021/jp0654112</a>. Copyright 2006 American Chemical Society.</p>
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dc.identifier archive/lib.dr.iastate.edu/chem_pubs/475/
dc.identifier.articleid 1489
dc.identifier.contextkey 7935849
dc.identifier.s3bucket isulib-bepress-aws-west
dc.identifier.submissionpath chem_pubs/475
dc.identifier.uri https://dr.lib.iastate.edu/handle/20.500.12876/14937
dc.language.iso en
dc.source.bitstream archive/lib.dr.iastate.edu/chem_pubs/475/0-L_2006_Gordon_InfraredSpectra.pdf|||Sat Jan 15 00:25:55 UTC 2022
dc.source.bitstream archive/lib.dr.iastate.edu/chem_pubs/475/2006_Gordon_InfraredSpectra.pdf|||Sat Jan 15 00:25:57 UTC 2022
dc.source.uri 10.1021/jp0654112
dc.subject.disciplines Chemistry
dc.title Infrared Spectra and Ab Initio Calculations for the F-−(CH4)n (n = 1−8) Anion Clusters
dc.type article
dc.type.genre article
dspace.entity.type Publication
relation.isAuthorOfPublication 1a5927c0-5a5f-440e-86e0-9da8dc6afda0
relation.isOrgUnitOfPublication 42864f6e-7a3d-4be3-8b5a-0ae3c3830a11
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