The kinetics and mechanism of reactions between gas-phase ozone and surface-bound C
60 have been investigated by monitoring changes to reflection鈥揳bsorption infrared spectra within a well-characterized film of C
60 during exposure to a controlled flux of pure ozone. These ultrahigh vacuum studies provide direct infrared spectroscopic evidence for the formation and decomposition of a primary ozonide of C
60. The spectral assignments of this highly unstable intermediate have been verified using electronic structure calculations. Theory and experiment revealed that C
60 oxidized nearly exclusively via addition of ozone across the double bond that links two six-carbon-containing rings of the molecule. Following spectral characterization, the initial probability for ozone to react with the surface was found to be 5.8 卤 0.2 脳 10
鈥?. Once formed, the ozonide quickly thermally decomposed to a variety of carbonyl-containing products.
Keywords:
ozonide; ozone; fullerene; oxidation; infrared; mechanism