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The rotational temperature of CO in the supersonic expansion is presumably far below its temperature in the pulsed valve 300 K, although the vibrational temperature of CO in the expansion is likely to remain close to 300 K. The theoretical calculations, to which the experimental results are compared, sample initial CO rotations and vibrations from a 300 K distribution. However, the difference between the initial rotational distributions of CO in the experiment and theory is not expected to be significant for hyperthermal collision energies relevant to the current study
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The rotational temperature of CO in the supersonic expansion is presumably far below its temperature in the pulsed valve (300 K), although the vibrational temperature of CO in the expansion is likely to remain close to 300 K. The theoretical calculations, to which the experimental results are compared, sample initial CO rotations and vibrations from a 300 K distribution. However, the difference between the initial rotational distributions of CO in the experiment and theory is not expected to be significant for hyperthermal collision energies relevant to the current study.
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A key feature of the analysis, as described in ref 8, is the assumption that over the range of center-of-mass (c.m, collision energies resulting from the velocity spread in the oxygen atom beam, the shape of the c.m. translational energy distribution, Etrans, of the products remains constant. Thus, in the forward-convolution procedure, a translational energy function corresponding to the nominal collision energy is averaged over the collision-energy distribution in the experiment. At each point in the averaging process, the nominal translational energy function is shifted by the energy difference between the actual collision energy and the nominal collision energy. The c.m. translational energy distributions displayed in this paper are the distributions that correspond to the nominal collision energy i.e, 83 kcal mol-1 in the experiment, This approximation breaks down if the shape of the translational energy distribution is strongly dependent on collision ener
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-1 in the experiment). This approximation breaks down if the shape of the translational energy distribution is strongly dependent on collision energy. Nevertheless, in the experiments reported here it is believed that the temporal width of the incident oxygen atom beam in the lab frame results in more uncertainty in the determination of the c.m. translational energy distributions than does the range of c.m. collision energies.
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