Vibrational and vibrational-torsional interactions in the 0-600 cm-1 region of the S1 ← S0 spectrum of p-xylene investigated with resonance-enhanced multiphoton ionization (REMPI) and zero-kinetic-energy (ZEKE) spectroscopy

We assign the 0-600 cm(-1) region of the S-1 <- S-0 transition in p-xylene (p-dimethylbenzene) using resonance-enhanced multiphoton ionization (REMPI) and zero-kinetic-energy (ZEKE) spectroscopy. In the 0-350 cm(-1) range 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(-1) region, where vibrational bands and some vibtor activity are observed. From the origin ZEKE spectrum, we derive the ionization energy of p-xylene as 68 200 +/- 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. Anumber 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 nonFranck- Condon allowed transitions. Finally, we find remarkably similar spectral activity to that in the related disubstituted benzenes, para-difluorobenzene, and para-fluorotoluene. Published by AIP Publishing.