title: Vibrational and vibrational-torsional interactions in the 0-600 cm-1region of the S1← S0spectrum of p-xylene investigated with resonance-enhanced multiphoton ionization (REMPI) and zero-kinetic-energy (ZEKE) spectroscopy.
abstract: We assign the 0-600 cm-1region of the S1← S0transition in p-xylene (p-dimethylbenzene) using resonance-enhanced multiphoton ionization (REMPI) and zero-kinetic-energy (ZEKE) spectroscopy. In the 0-350 cm-1range as well as the intense origin band, there are a number of torsional and vibration-torsion (vibtor) features. The latter are discussed in more detail in Paper I [A. M. Gardner et al., J. Chem. Phys. 146, 124308 (2017)]. Here we focus on the origin and the 300-600 cm-1region, where vibrational bands and some vibtor activity are observed. From the origin ZEKE spectrum, we derive the ionization energy of p-xylene as 68200 ± 5 cm-1. The assignment of the REMPI spectrum is based on the activity observed in the ZEKE spectra coupled with knowledge of the vibrational wavenumbers obtained from quantum chemical calculations. We assign several isolated vibrations and a complex Fermi resonance that is found to comprise contributions from both vibrations and vibtor levels, and we examine this via a two-dimensional ZEKE spectrum. A number of the vibrational features in the REMPI and ZEKE spectra of p-xylene that have been reported previously are reassigned and now largely consist of totally symmetric contributions. We briefly discuss the appearance of non-Franck-Condon allowed transitions. Finally, we find remarkably similar spectral activity to that in the related disubstituted benzenes, para-difluorobenzene, and para-fluorotoluene.
authors.affiliation: School of Chemistry, University of Nottingham, University Park, Nottingham NG7 2RD, United Kingdom.
authors.forename: William D
authors.initials: WD
authors.lastname: Tuttle
authors.affiliation: School of Chemistry, University of Nottingham, University Park, Nottingham NG7 2RD, United Kingdom.
authors.forename: Adrian M
authors.initials: AM
authors.lastname: Gardner
authors.affiliation: School of Chemistry, University of Nottingham, University Park, Nottingham NG7 2RD, United Kingdom.
authors.forename: Kieran B
authors.initials: KB
authors.lastname: O'Regan
authors.affiliation: School of Chemistry, University of Nottingham, University Park, Nottingham NG7 2RD, United Kingdom.
authors.forename: William
authors.initials: W
authors.lastname: Malewicz
authors.affiliation: School of Chemistry, University of Nottingham, University Park, Nottingham NG7 2RD, United Kingdom.
authors.forename: Timothy G
authors.identifier: 0000000178366705
authors.initials: TG
authors.lastname: Wright