Infrared Spectra and Ab Initio Calculations for the F-−(CH4)n (n = 1−8) Anion Clusters Loh, Zoë Wilson, R. L. Gordon, Mark Wild, D. A. Bieske, Evan Lisy, J. M. Njegic, Bosiljka Gordon, Mark
dc.contributor.department Chemistry 2018-02-17T08:22:30.000 2020-06-30T01:20:28Z 2020-06-30T01:20:28Z Sun Jan 01 00:00:00 UTC 2006 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="" target="_blank">10.1021/jp0654112</a>. Copyright 2006 American Chemical Society.</p>
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dc.identifier.articleid 1489
dc.identifier.contextkey 7935849
dc.identifier.s3bucket isulib-bepress-aws-west
dc.identifier.submissionpath chem_pubs/475
dc.language.iso en
dc.source.bitstream archive/|||Sat Jan 15 00:25:55 UTC 2022
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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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