Jet-Cooled Emission Spectra of the Xylenes

Selco, Jodye I.; Carrick, P. G.

doi:10.1006/jmsp.1995.1232

Cited by 21 publications

(30 citation statements)

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“…The latter value agrees well with the origin value reported by Selco and Carrick 53 It is of note that much of the vibrational activity is the same across the three molecules (evident because of the same vibrational labelling scheme used), but that there is significantly more structure in the 0-300 cm -1 region for pXyl and pFT than there is in the case of pDFB:…”

Section: A Rempi Spectrum -Overviewsupporting

confidence: 81%

“…Other workers have previously studied the S1  S0 spectrum of pXyl; 19,20,21,22,23,24,25,26,27 additionally, resonant absorption studies have been performed on the cation, combining REMPI spectroscopy with photoelectron spectroscopy (REMPI-PES) 22 as well as the higherresolution techniques of ZEKE spectroscopy 28 and mass-analyzed threshold ionization (MATI) spectroscopy. 25,26,29 In addition to a HeI photoelectron spectrum that exhibited some partially-resolved but unassigned vibrational bands.…”

Section: And M19m20mentioning

confidence: 99%

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

Tuttle

Gardner

O'Regan

et al. 2017

The Journal of Chemical Physics

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We assign the 0–600 cm−1 region of the S1 ← S0 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 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.

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Section: A Rempi Spectrum -Overviewsupporting

confidence: 81%

Section: And M19m20mentioning

confidence: 99%

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

Tuttle

Gardner

O'Regan

et al. 2017

The Journal of Chemical Physics

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“…Wavenumber values for the vapor phase were reported first by Draeger and Scott (1981). Recently, Selco and Carrick (1995) reported results of jet-cooled emission spectroscopic studies for the xylenes. Selco and Carrick reported wavenumbers for six fundamental vibrational modes (381.8 cm -1 , 646.8 cm -1 , 454.3 cm -1 , 824.3 cm -1 , 1208.2 cm -1 , and 1656.7 cm -1 ) and anharmonicity parameters, ω e and ω e χ e , for three of these (646.8 cm -1 , 824.3 cm -1 , and 1208.2 cm -1 ).…”

Section: Standard Entropies and Heat Capacities From Spectroscopic St...mentioning

confidence: 91%

Thermodynamic Equilibria in Xylene Isomerization. 1. The Thermodynamic Properties ofp-Xylene

Chirico¹,

Knipmeyer²,

Nguyen³

et al. 1997

J. Chem. Eng. Data

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Measurements and calculations leading to the determination of thermodynamic properties for the gaseous and condensed phases of p-xylene (Chemical Abstracts registry number (supplied by the authors) [106-42-3]) are reported. All measurement results reported were obtained with a differential-scanning calorimeter (DSC). The critical temperature was measured by DSC. Saturation heat capacities for the liquid phase between 370 K and 550 K, the critical density and the critical pressure were derived with fitting procedures involving the new DSC results and literature vapor pressures and densities. Results were combined with heat capacities reported in the literature obtained with adiabatic calorimetry and the enthalpy of combustion to derive standard molar entropies, enthalpies, and Gibbs free energies of formation at selected temperatures between 250 K and 550 K. The standard state is defined as the ideal gas at the pressure p ) p°) 101.325 kPa. Standard entropies are compared with those calculated statistically on the basis of assigned vibrational spectra. Results are compared with literature values. Literature vapor pressures, enthalpies of vaporization, virial coefficients, densities, and heat capacities for the condensed and gaseous phases are checked for consistency with the values used in this research.

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“…21 We note that other workers have studied the electronic spectrum of pXyl . 22,23,24,25,26,27,28,29,30 There have also been studies on the cation that have involved intermediate vibronic excitation steps: REMPI combined with photoelectron spectroscopy (REMPI-PES) 25 ; ZEKE spectroscopy; 31 and mass-analyzed threshold ionization (MATI) spectroscopic studies. 28,29,32 The latter studies have a much higher resolution than both an earlier photoionization study, 33 and HeI photoelectron work that at best only showed partially-resolved and unassigned vibrational bands.…”

Section: Introductionmentioning

confidence: 99%

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

Tuttle

Groner

et al. 2017

The Journal of Chemical Physics

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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 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 Paper II [W. D. Tuttle et al., J. Chem. Phys. 146, 124309 (2017)], 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.

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Jet-Cooled Emission Spectra of the Xylenes

Cited by 21 publications

References 0 publications

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

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

Thermodynamic Equilibria in Xylene Isomerization. 1. The Thermodynamic Properties ofp-Xylene

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

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