Stereodynamics and rovibrational effect for H+CH[sub 4](v,j,K,n)→H[sub 2]+CH[sub 3] reaction

Wang, Mingliang; Zhang, J. Z. H.
April 2002
Journal of Chemical Physics;4/15/2002, Vol. 116 Issue 15, p6497
Academic Journal
In this work, we employ the semirigid vibrating rotor target (SVRT) model to study the influence of rotational and vibrational excitation of the reagent on reactivity for the benchmark reaction H+CH[sub 4](v,j,K,n). The excitation of the pseudo H–CH[sub 3] stretching vibration of the SVRT model gives significant enhancement of reaction probability, consistent with the later position of the reaction barrier on the potential energy surface. The vibrationally thermal-averaged rate constant is much larger than the rate constant of the ground vibrational state. Detailed study of the influence of initial rotational states on reaction probability shows strong steric effect. The reaction probability is directly correlated with the angular distribution of the initial wave function determined by different angular momentum relationships among three vectors j, R, and r. The steric effect of polyatomic reactions, treated by the SVRT model, is more complex and richer than theoretical calculations involving linear molecular models. © 2002 American Institute of Physics.


Related Articles

  • Vibrational energy pooling in CO on NaCl(100): Methods. Corcelli, S. A.; Tully, J. C. // Journal of Chemical Physics;5/8/2002, Vol. 116 Issue 18, p8079 

    Vibrational states as high as n = 15 have been experimentally observed in CO molecules adsorbed in a monolayer on the NaCl(100) surface after pumping the n = 0 → 1 vibrational transition with a short (5 µs) infrared laser pulse. These high states become populated from successive single...

  • Coherent vibrational motion in metal particles: Determination of the vibrational amplitude and excitation mechanism. Hartland, Gregory V. // Journal of Chemical Physics;5/8/2002, Vol. 116 Issue 18, p8048 

    Ultrafast laser excitation of metal particles coherently excites the symmetric breathing mode. This changes the electron density in the particle, which produces a periodic redshift in the position of the plasmon band. In this paper transient absorption data recorded over a range of wavelengths...

  • Unexpected simplicity in the S[sub 1]–S[sub 0] dispersed fluorescence spectra of [sup 13]C[sub 2]H[sub 2]. Silva, Michelle L.; Jacobson, Matthew P.; Duan, Zicheng; Field, Robert W. // Journal of Chemical Physics;5/8/2002, Vol. 116 Issue 18, p7939 

    We have recorded dispersed fluorescence (DF) spectra (18 cm[sup -1] resolution) from the J[sub K[sub a]K[sub c]] = 110 rotational level of six vibrational levels in the S[sub 1] (Ã[sup 1]A[sub u]) state of [sup 13]C[sub 2]H[sub 2]. Improvements in our methods of recording and calibrating DF...

  • Vibrational spectroscopy of HOD in liquid D[sub 2]O. I. Vibrational energy relaxation. Lawrence, C. P.; Skinner, J. L. // Journal of Chemical Physics;9/22/2002, Vol. 117 Issue 12, p5827 

    We present calculations of the vibrational lifetimes for the three fundamentals of HOD in liquid D[sub 2]O. The calculations build on the work of Oxtoby and of Rey and Hynes, but also introduce some new ideas, the most important of which is a self-consistent renormalization scheme for...

  • Vibrational interactions of acetonitrile: Doubly vibrationally resonant IR–IR–visible four-wave-mixing spectroscopy. Kwak, Kyungwon; Cha, Sangyob; Cho, Minhaeng; Wright, John C. // Journal of Chemical Physics;9/22/2002, Vol. 117 Issue 12, p5675 

    The origin of the vibrational coupling that was observed between the CC and CN stretching modes of acetonitrile by doubly vibrationally enhanced (DOVE) IR-IR-Vis four-wave-mixing (IIV-FWM) spectroscopy is investigated by various ab initio calculations including DFT(B3LYP), HF, and MP2 methods...

  • In situ chemical information at the semiconductor/electrolyte interface from infrared vibrational spectroscopy. Tardella, A.; Chazalviel, J.-N. // Applied Physics Letters;8/1/1985, Vol. 47 Issue 3, p334 

    We have investigated the n-Si/acetonitrile electrolyte interface using attenuated total reflection spectroscopy in the 1.2-5-µm spectral region. Characteristic information from the surface has been extracted by using modulation of the electrode potential and lock-in detection of the optical....

  • On the Effect of Ordering on Vibrational Spectrum of Relaxor Ferroelectric PbSc[sub 1/2]Ta[sub 1/2]O[sub 3] in Paraphase. Lushnikov, S. G.; Gvasaliya, S. N.; Rogacheva, E. A.; Siny, I. G. // Crystallography Reports;May2000, Vol. 45 Issue 3, p466 

    The effect of the ordering of Sc[sup 3+] and Ta[sup 5+] ions on the behavior of the phonon subsystem in the relaxor ferroelectric PbSc[sub 1/2]Ta[sub 1/2]O[sub 3] from the numerous A B'[sub x]B'[sub x-1] O[sub 3] family has been studied. The nature of an additional contribution to the...

  • Vibrational Spectrum of Li[sub 2]B[sub 4]O[sub 7] Crystals. Vdovin, A. V.; Moiseenko, V. N.; Burak, Ya. V. // Optics & Spectroscopy;Apr2001, Vol. 90 Issue 4, p555 

    Polarized IR reflection spectra of Li[sub 2]B[sub 4]O[sub 7] crystals are studied in a spectral range of 80-1600 cm[sup -1] and compared with their Raman spectra. Based on the results of the dispersion analysis of the spectra, the frequencies, damping constants, and oscillator strengths of all...

  • Simulation of Time-Resolved Vibronic Spectra and the Possibility of Analyzing Molecules with Similar Spectral Properties. Astakhov, S. A.; Baranov, V. I. // Optics & Spectroscopy;Jan2002, Vol. 92 Issue 1, p20 

    The possibility of using time-resolved vibronic spectroscopy for spectral analysis of mixtures of chemical compounds with similar optical properties, when traditional methods (based on stedy-state spectra) are inefficient, is demonstrated by using the method of computer simulation. The analysis...


Read the Article


Sorry, but this item is not currently available from your library.

Try another library?
Sign out of this library

Other Topics