A semiclassical adiabatic calculation of state densities for molecules exhibiting torsion: application to hydrogen peroxide and its isotopomers

A practical computational method is discussed for obtaining the rotational–vibrational molecular state densities of molecules with large amplitude torsional degrees of freedom (DoFs). This method goes beyond the traditional harmonic oscillator/rigid rotor or separable hindered rotor approximations in that it includes coupling between the torsion, the remaining vibrational modes, and the overall rotation. The method is based on the vibrationally adiabatic approximation whereby the torsional motion is assumed to be slow compared to the remaining vibrational DoFs although the nonseparability may be large. The torsional coordinate therefore parameterizes the rotational constants and the effective vibrational potential. A semiclassical method is then introduced to calculate the total state density in which the torsion is treated classically while the remaining coordinates are treated quantum mechanically. The method is also formulated for reactive problems in which the density of states is parameterized by a second large amplitude degree of freedom, the reaction coordinate. The performance of the method is assessed using the dissociation reaction of the hydrogen peroxide molecule and its isotopomers. It is found that the method performs well based on numerical tests. The torsional nonseparability is found to yield errors of factors of 2–3 in the statistical rate coefficient when compared with results of traditional separable models.     

Signatures of reactive resonance: three case studies

 Recent advances in the study of short-lived reactive resonances are reviewed. Special emphasis is given to addressing the question of how reactive resonances might be observed in molecular beam scattering experiments. Three case studies are presented for simple triatomic systems that are believed to exhibit resonance phenomena: F + HD → D + HF, F + H₂ → H + HF, and H + HD → D + H₂. It is seen that reactive resonances do strongly influence collision observables, but in a different way for each case. At this stage, there does not appear to be a unique resonance signature that can be applied to all reactions. Received: 2 March 2002 / Accepted: 2 June 2002 / Published online: 17 October 2002 Acknowledgements. For their valuable input into the research discussed here, we are grateful to our collaborators, K. Liu, S.H. nk;Lee, F. Dong, D.E. Manolopoulos, D, Skouteris, X. Yang, S. Harich, D. Dai, and C.C. Wang. This work was supported by the National Science Foundation. Correspondence to: R. T. Skodje e-mail: skokje@spot.colorado.edu     

Experimental and theoretical study of the OH vibrational spectra and overtone chemistry of gas-phase vinylacetic acid

In this study we present the gas-phase vibrational spectrum of vinylacetic acid with a focus on the nu = 1-5 vibrational states of the OH stretching transitions. Cross sections for nu = 1, 2, 4 and 5 of the OH stretching vibrational transitions are derived on the basis of the vapor pressure data obtained for vinylacetic acid. Ab initio calculations are used to assist in the band assignments of the experimental spectra, and to determine the threshold for the decarboxylation of vinylacetic acid. When compared to the theoretical energy barrier to decarboxylation, it is found that the nu OH = 4 transition with thermal excitation of low frequency modes or rotational motion and nu OH = 5 transitions have sufficient energy for the reaction to proceed following overtone excitation.