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Methyl group internal rotation in 2,6-difluorotoluene (S{sub 1}) and 2,6-difluorotoluene{sup +} (D{sub 0})

Journal Article · · Journal of Physical Chemistry
; ; ;  [1]
  1. Univ. of Wisconsin, Madison, WI (United States)
In this paper we investigate 2,6-difluorotoluene which provides an example of a sterically hindered 6-fold symmetric methyl rotor. We present the S{sub 1}-S{sub 0} resonant two-photon ionization spectrum and analyze the barrier problem in S{sub 1}, including isolated spectral perturbations involving coupling of torsion with an out-of-plane bending mode. Pulsed field ionization spectra through a variety of S{sub 1}-S{sub 0} bands yield the barrier in D{sub 0} and important double-resonance crosschecks on the S{sub 1}-S{sub 0} assignments. The potential parameter V{sub 6} is -10.6 cm{sup -1} in S{sub 1} (staggered minimum) and +15 cm{sup -1} in D{sub 0} (eclipsed minimum) similar to the other 6-fold examples. We also present the results of ab initio calculations in both S{sub 0} and D{sub 0}. 35 refs., 9 figs., 5 tabs.
Sponsoring Organization:
USDOE
DOE Contract Number:
FG02-92ER14306
OSTI ID:
102872
Journal Information:
Journal of Physical Chemistry, Journal Name: Journal of Physical Chemistry Journal Issue: 33 Vol. 99; ISSN JPCHAX; ISSN 0022-3654
Country of Publication:
United States
Language:
English