Molecular beam study of the Cu+F2 chemiluminescent reactions

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Abstract
Chemiluminescence of CuF formed in the reaction of ground state Cu and F2 has been studied using a molecular beam–scattering gas arrangement. Relative rates for forming the A, B, and C states of CuF were determined, and an inversion of population is observed for the C relative to the B state. Computer simulations of the observed spectra have provided information on the vibrational and rotational distributions in the excited CuF states. Simulation of the B and C spectra is straightforward, but the A state must include 1Σ and 1Π parts of a p complex, as well as corrections for diffusion from the observation region. Average fractions of energy available disposed in vibration are 0.30, 0.34, and 0.29–0.38 for the C, B, and A states, respectively. Average fractions disposed in rotation for the same three states are 0.21, 0.20, and 0.21–0.22. These fractions correspond closely to prior expectations based on product densities for vibration, but are much less than prior expectations for rotation. Weak emission is also observed from the a(3Σ) state with average vibrational energy close to prior expectations.