Molecular symmetry group analysis of the low-wavenumber torsions and vibration-torsions in the S1 state and ground state cation of p-xylene: an investigation using resonance-enhanced multiphoton ionization (REMPI) and zero-kinetic-energy (ZEKE) spectroscopy

Gardner, Adrian M.; Tuttle, William D.; Groner, Peter; Wright, Timothy G.

Abstract

For the first time, a molecular symmetry group (MSG) analysis has been undertaken in the investigation of the electronic spectroscopy of p-xylene (p-dimethylbenzene). Torsional and vibration-torsional (vibtor) levels in the S1 state and ground state of the cation of p-xylene (p-dimethylbenzene) are investigated using resonance-enhanced multiphoton ionization (REMPI) and zero-kinetic-energy (ZEKE) spectroscopy. In the present work, we concentrate on the 0–350 cm 1 region, where there are a number of torsional and vibtor bands and we discuss the assignment of this region. In an accompanying paper [Tuttle et al. J. Chem. Phys. XXX, xxxxxx (2016)], we examine the 350–600 cm 1 region where vibtor levels are observed as part of a Fermi resonance. The similarity of much of the observed spectral activity to that in the related substituted benzenes, toluene and para-fluorotoluene, is striking, despite the different symmetries. The discussion necessitates a consideration of the MSG of p-xylene, which has been designated G72, but we shall also designate [3,3]D2h and we include the symmetry operations, character table and direct product table for this. We also discuss the symmetries of the internal rotor (torsional) levels and the selection rules for the particular electronic transition of p-xylene investigated here.

Citation

Gardner, A. M., Tuttle, W. D., Groner, P., & Wright, T. G. (in press). Molecular symmetry group analysis of the low-wavenumber torsions and vibration-torsions in the S1 state and ground state cation of p-xylene: an investigation using resonance-enhanced multiphoton ionization (REMPI) and zero-kinetic-energy (ZEKE) spectroscopy. Journal of Chemical Physics, 146(12), https://doi.org/10.1063/1.4977896

• Journal Article Type: Article
• Acceptance Date: Feb 20, 2017
• Online Publication Date: Mar 23, 2017
• Deposit Date: Feb 21, 2017
• Publicly Available Date: Mar 23, 2017
• Journal: Journal of Chemical Physics
• Print ISSN: 0021-9606
• Electronic ISSN: 1089-7690
• Publisher: American Institute of Physics
• Peer Reviewed: Peer Reviewed
• Volume: 146
• Issue: 12
• DOI: https://doi.org/10.1063/1.4977896
• Public URL: https://nottingham-repository.worktribe.com/output/851671
• Publisher URL: http://aip.scitation.org/doi/10.1063/1.4977896
• Additional Information: The following article appeared in The Journal of Chemical Physics 146, 124308 (2017); doi: http://dx.doi.org/10.1063/1.4977896 and may be found at http://aip.scitation.org/doi/10.1063/1.4977896
• Contract Date: Feb 21, 2017