Through a fit to methanol CH overtone data, a previously developed 4-dimensional torsion-vibration Hamiltonian is extended to high CH stretch excitation as well as to high torsional excitation. The strength of the torsion-vibration coupling is found to increase with CH stretch excitation. Systematic patterns of near degeneracy (3-, 4-, and 6-fold) are found in different regions of quantum number space. In the region of the CH fundamentals, an approximate a diabatic separation of the torsion (slow degree of freedom) from the CH stretches (fast degrees of freedom) accounts for the pattern of the energy levels and for the signs of the torsional tunneling splittings. For the higher CH overtones (v(CH) > or = 4), a diabatic representation accounts for the torsional structure obtained from the fully coupled calculation and for certain trends found in the pattern of the energy levels.
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http://dx.doi.org/10.1021/jp077269q | DOI Listing |
J Chem Theory Comput
August 2024
ELTE, Eötvös Loránd University, Institute of Chemistry, Budapest 1117, Hungary.
Full-dimensional (12D) vibrational states of the methanol molecule (CHOH) have been computed using the GENIUSH-Smolyak approach and the potential energy surface from Qu and Bowman (2013). All vibrational energies are converged better than 0.5 cm with respect to the basis and grid size up to the first overtone of the CO stretch, ca.
View Article and Find Full Text PDFJ Phys Chem A
April 2022
College of Science and Engineering, Flinders University, GPO Box 2100, Adelaide, SA 5001, Australia.
An interaction between methyl torsion and the low-lying out-of-plane methyl wag vibration has been observed in toluene, -fluorotoluene, and -fluorotoluene, contravening the traditional assumption used when analyzing spectra that methyl torsion can be treated independently of the small-amplitude vibrations. When a methyl group is attached to a planar frame, out-of-plane methyl wag vibrations always occur, and hence this type of interaction between methyl torsion and vibration is potentially extensive. To probe whether this coupling occurs beyond toluene and its derivatives, we have studied the far-infrared absorption band for the out-of-plane methyl wagging mode in -methylpyrrole.
View Article and Find Full Text PDFJ Chem Phys
September 2021
College of Science and Engineering, Flinders University, GPO Box 2100, Adelaide, SA 5001, Australia.
Observations of the torsional and low-lying vibrational-torsional states of toluene, p-fluorotoluene, and m-fluorotoluene using the technique of two dimensional laser induced fluorescence (2D-LIF) have revealed interactions between the methyl torsion and low frequency out-of-plane methyl wagging vibration. These interactions can change the values of constants extracted from the analysis of rotational spectra, which usually assume that the large amplitude torsional motion can be treated independent of the small amplitude vibrations. Since out-of-plane methyl wagging modes will be present whenever a methyl group is attached to a planar frame, this type of torsion-vibration interaction is potentially widespread; it is thus important to establish the extent and strength of this type of interaction.
View Article and Find Full Text PDFJ Chem Phys
May 2019
College of Science and Engineering, Flinders University, G.P.O. Box 2100, Adelaide SA 5001, Australia.
We report results of a two dimensional laser induced fluorescence study of torsional states, low frequency vibrations, and combinations of torsion with low frequency vibration in m-fluorotoluene up to 560 cm in S and 350 cm in S. Evidence is presented for interactions between torsion and low frequency vibrations in both S and S, demonstrating that the coupling of torsion and vibration observed previously in toluene and p-fluorotoluene extends to a molecule with a threefold torsional barrier. This barrier is low in S (20 cm) and modest in S (116 cm).
View Article and Find Full Text PDFJ Chem Phys
August 2018
College of Science and Engineering, Flinders University, G.P.O. Box 2100, Adelaide, SA 5001, Australia.
We report two dimensional laser induced fluorescence spectral images exploring the lower torsion-vibration manifolds in S ( < 560 cm) and S ( < 420 cm) -fluorotoluene. Analysis of the images reveals strong torsion-vibration interactions and provides an extensive set of torsion-vibration state energies in both electronic states (estimated uncertainty ±0.2 cm), which are fit to determine key constants including barrier heights, torsional constants, and torsion-vibration interaction constants.
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