State-specific unimolecular dissociation dynamics of HFCO. II. CO rotational distribution and Doppler widths

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Abstract

Rovibrational state distributions and Doppler widths of CO fragments formed from unimolecular dissociation of HFCO in its ground electronic state are measured by vacuum ultraviolet laser-induced fluorescence, following state-selective preparation of the molecule in a single quantum state in the energy region of 2000 to 3000 cm-1 above the dissociation threshold by stimulated emission pumping. CO fragments are rotationally hot and distributed over J≤15 to J=63 with distributions peaking at J=45 to 50 depending upon the initial HFCO dissociative state. Although CO rotational distributions are significantly different for different initial states, about 20% of the total available energy is released on average as rotational energy of CO for all three initial states studied. The yield of CO(υ=1) fragments is determined to be about 10% and CO(υ≥2) fragments are not observed. The average Doppler width of CO fragments is 0.85 cm-1, which indicates that ∼50% of the total available energy is released as translation. The CO product state distributions and Doppler widths may be rationalized using a modified impulsive model with the ab initio transition state geometry. The dependence of product state distributions on the initial HFCO quantum state may reflect incomplete intramolecular vibrational energy redistribution. © 1995 American Institute of Physics.

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Choi, Y. S., & Moore, C. B. (1995). State-specific unimolecular dissociation dynamics of HFCO. II. CO rotational distribution and Doppler widths. The Journal of Chemical Physics, 103(23), 9981–9988. https://doi.org/10.1063/1.469887

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