CH Stretch Vibrational Spectroscopy and Tunneling Dynamics in通道拉伸振动光谱和隧穿动力学.ppt

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2016-12-30 发布于上海
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CH Stretch Vibrational Spectroscopy and Tunneling Dynamics in通道拉伸振动光谱和隧穿动力学.ppt

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CH Stretch Vibrational Spectroscopy and Tunneling Dynamics in Vinyl Radical F. Dong1, M. A. Roberts, R. S. Walters and D. J. Nesbitt JILA, Department of Chemistry and Biochemistry, University of Colorado 1Los Gatos Research, Inc. Mountain View, CA. Prototype for unsaturated radical combustion chemistry Large amplitude in-plane tunneling pathway Mid-IR: H. Kanamori, Y. Endo, E. Hirota. J.Chem. Phys. 92, 197 (1990). FTIR: L. Letendre, D.-K. Liu, C. D. Pibel, J. B. Halpern, H.-L. Dai. J. Chem. Phys. 112, 9209 (2000). mm: K. Tanaka, M. Toshimitsu, K. Harada, T. Tanaka. J. Chem. Phys. 120, 3604 (2004). Vinyl Expectations CH Stretches Jet Cooled Hydrocarbon Radicals Clean synthesis of radicals by dissociative attachment (RX + e- → R + X-) High radical densities at slit orifice (1013-15 #/cm3) Localized discharge (~ 105 cm/s, ~ 1 ms transit time) – can avoid radical-radical chemistry! “Simple” high resolution spectroscopy at 5-10 K Bending/Tunneling Potentials(CCSD(T) AVnZ, CBS) High level CCSD(T) AVnZ (n=2,3,4) surface calculations Extrapolated to complete basis set CBS limit (Dunning, Peterson et al) Corrected for ZPE in 3N-7 orthogonal coordinates Adiabatic PES for ground state as well as vibrationally excited states Reduced Mass (m) Tunneling path (q) as psuedo 1D coordinate embedded in full 3N-6 D space Reduced mass as rigorous function of full 1D tunneling and 3N-7 D orthogonal coordinates… …calculated at each point q (Rush-Wiberg) Large Amplitude Tunneling Methods(Rush-Wiberg/HBJ) Wave Functions/Tunneling Splittings Summary First high resolution CH stretch spectra of vinyl radical. Three A-type bands observed: two tunneling (a,s) bands out of ground state and one hot band. Tunneling splittings consistent with previous studies. Agreement with ab initio anharmonic predictions for symmetric CH2 stretch. Vibrationally adiabatic tunneling PES and barrier heights. Thanks * * JILA Time-Resolved FTIR (Dai and coworkers) Medium resolution IR emission from the ph