Show simple item record

dc.creatorPerry, David S.en_US
dc.creatorGo, J.en_US
dc.date.accessioned2006-06-15T19:21:12Z
dc.date.available2006-06-15T19:21:12Z
dc.date.issued1999en_US
dc.identifier1999-TF-06en_US
dc.identifier.urihttp://hdl.handle.net/1811/19471
dc.descriptionAuthor Institution: Department of Chemistry, University of Akronen_US
dc.description.abstractMethanol is important in combustion both as a fuel and as an intermediate. Vibrational mode coupling results in energy flow within vibrationally excited methanol and thereby affects its subsequent reactivity. The large amplitude torsional mode of methanol is at the center of the present study and may serve as a model for the behavior of other combustion intermediates with large amplitude vibrations. Coupling between the methyl C-H stretches and the torsion in methanol results in a $42 cm^{-1}$ splitting between the $\nu_{2}$ and $\nu_{9}$ modes and results in an inversion of the torsional tunnelling splitting in these modes. Ab initio calculations (up to $MP2/6-311G+(3df,2p)$ and $MP4/6-311G+(2d,p))$ appear to converge to a $\nu_{2}-\nu_{9}$ splitting of $60 cm^{-1}$, still substantially larger than the experimental value. This difference is attributed to 1:2 stretch-bend resonances involving the methyl C-H bonds. The torsional tunnelling splitting in methanol decreases monotonically from $9.1 cm^{-1}$ in the ground state to $1.6 cm^{-1}$ at the fifth overtone of the O-H stretch. This trend indicates an increase in the torsional barrier height with vibrational excitation of the O-H bond. Optimized ab initio calculations indicate that the torsional barrier increases as the O-H band length is either lengthened or shortened from the equilibrium distance.en_US
dc.format.extent112190 bytes
dc.format.mimetypeimage/jpeg
dc.language.isoEnglishen_US
dc.publisherOhio State Universityen_US
dc.titleAB INITIO CALCULATIONS OF VIBRATIONAL MODE COUPLING IN METHANOLen_US
dc.typearticleen_US


Files in this item

Thumbnail

Items in Knowledge Bank are protected by copyright, with all rights reserved, unless otherwise indicated.

This item appears in the following Collection(s)

Show simple item record