dc.creator Xu, Li-Hong en_US dc.creator Lees, Ronald M. en_US dc.creator Hougen, Jon T. en_US dc.date.accessioned 2012-07-09T19:35:29Z dc.date.available 2012-07-09T19:35:29Z dc.date.issued 2012 en_US dc.identifier 2012-WF-10 en_US dc.identifier.uri http://hdl.handle.net/1811/52490 dc.description Author Institution: Centre for Laser, Atomic and Molecular Sciences (CLAMS) Physics Department University of New Brunswick, 100 Tucker Park Road, Saint John, NB, Canada E2L 4L5; Sensor Sciences Division, National Institute of Standards and Technology, Gaithersburg, MD 20899-8441 en_US dc.description.abstract Stemming from the observation of inverted $A/E$ splittings for the $\nu_{2}$ and $\nu_{9}$ asymmetric CH-stretching modes in methanol, there has been much theoretical interest in attempting to explain the nature of the inversion. We have recently examined the ab initio normal-mode vibrational displacement vectors along the internal rotation path for the three C-H stretching vibrations in methanol, both in the symmetrized and non-symmetrized PAM coordinates. Graphical representations of the Cartesian atomic normal mode displacement vectors $d_{i}(\gamma)$ determined by the Gaussian suite of programs for the three CH stretching motions, $\nu_{2}(A_{1}), \nu_{3}(A_{1})$ and $\nu_{9}(A_{2})$, along the steepest-descent internal rotation path $\gamma$ in methanol (CH$_3$OH) will be presented and discussed, where $A_{1}$ and $A_{2}$ are notations in permutation-inversion group $G_{6}$. These modes are interesting because the symmetry environment of each C-H bond changes significantly during the internal rotation, i.e., each of the methyl bonds takes turns passing (twice for a complete torsional revolution) through the plane of symmetry of the COH frame of the molecule. We present some simple theoretical models which can be used to help understand these displacement vectors. Although this is work in progress, some explanation is already possible for the rather irregular (avoided-crossing-like) behavior of these displacement vectors. en_US dc.language.iso en en_US dc.publisher Ohio State University en_US dc.title ANALYSIS OF AB INITIO NORMAL-MODE DISPLACEMENT VECTORS ALONG THE INTERNAL ROTATION PATH FOR THE THREE C-H STRETCHING VIBRATIONS IN METHANOL en_US dc.type Article en_US
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