Slit discharge IR spectroscopy of a jet-cooled cyclopropyl radical: structure and intramolecular tunneling dynamics

The Journal of Physical Chemistry. a
Feng DongDavid J Nesbitt

Abstract

High-resolution infrared spectra of a jet-cooled cyclopropyl radical are reported for the first time, specifically sampling the in-phase antisymmetric CH2 stretch (nu7) vibration. In addition to yielding the first precise gas-phase structural information, the spectra reveal quantum level doubling into lower (+) and upper (-) states due to tunneling of the lone alpha-CH with respect to the CCC plane. The bands clearly reveal intensity alternation due to H atom nuclear spin statistics (6:10 and 10:6 for even:odd Ka+Kc in lower (+) and upper (-) tunneling levels, respectively) consistent with C2v symmetry of the cyclopropyl-tunneling transition state. The two ground-state-tunneling levels fit extremely well to a rigid asymmetric rotor Hamiltonian, but there is clear evidence for both local and global state mixing in the vibrationally excited nu7 tunneling levels. In particular, the upper (-) tunneling component of the nu7 state is split by anharmonic coupling with a nearly isoenergetic dark state, which thereby acquires oscillator strength via intensity sharing with this bright state. From thermal Boltzmann analysis of fractional populations, tunneling splittings for a cyclopropyl radical are estimated to be 3.2 +/- 0.3 cm(-1) and...Continue Reading

References

Nov 30, 1999·Journal of Molecular Spectroscopy·J D DeSain, R F Curl
Mar 28, 2002·Journal of the American Chemical Society·David J Mann, William L Hase
Apr 8, 2004·Chemphyschem : a European Journal of Chemical Physics and Physical Chemistry·Alex J HuneycuttRichard J Saykally

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Citations

Oct 18, 2006·The Journal of Chemical Physics·Feng Dong, David J Nesbitt
Feb 17, 2011·The Journal of Chemical Physics·Erin N Sharp-WilliamsDavid J Nesbitt
Dec 24, 2013·The Journal of Chemical Physics·Christopher M LeavittGary E Douberly
Aug 1, 2016·The Journal of Chemical Physics·Chih-Hsuan Chang, David J Nesbitt
Jan 28, 2012·The Journal of Chemical Physics·Amit R SharmaDavid J Nesbitt
Aug 9, 2008·Physical Chemistry Chemical Physics : PCCP·David J Nesbitt, Feng Dong
Nov 8, 2008·Physical Chemistry Chemical Physics : PCCP·Erin N SharpDavid J Nesbitt
Oct 15, 2018·The Journal of Chemical Physics·Chih-Hsuan ChangDavid J Nesbitt
Sep 8, 2011·Physical Chemistry Chemical Physics : PCCP·Erin N Sharp-WilliamsDavid J Nesbitt
Jul 15, 2009·The Journal of Physical Chemistry. a·Matthew NikowHai-Lung Dai
Jan 7, 2009·Journal of the American Chemical Society·Fabien GoulayStephen R Leone
Mar 30, 2013·The Journal of Physical Chemistry. a·Grant T BuckinghamDavid J Nesbitt
Mar 9, 2013·The Journal of Physical Chemistry. a·Melanie A RobertsDavid J Nesbitt

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