Reaction Probability and Infrared Detection of the Primary Ozonide in Collisions of O₃ with Surface-Bound C₆₀

Abstract

The kinetics and mechanism of reactions between gas-phase ozone and surface-bound C60 have been investigated by monitoring changes to reflection-absorption infrared spectra within a well-characterized film of C60 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 C60. The spectral assignments of this highly unstable intermediate have been verified using electronic structure calculations. Theory and experiment revealed that C60 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 ± 0.2 × 10(-4). Once formed, the ozonide quickly thermally decomposed to a variety of carbonyl-containing products.

Heterogeneous chemistry and reaction dynamics of the atmospheric oxidants, O3, NO3, and OH, on organic surfaces

“…In the gas phase, O 3 initiates reactions with vinyl-containing organics and polycyclic aromatics via addition across double bonds to form an unstable primary ozonide, which triggers a series of subsequent reactions. [42][43][44] Analogous chemistry may occur on surfaces; [45][46][47] however, scientists are only beginning to decipher how surface structure and functionality affect ozone accommodation, diffusion, and reaction pathways. A quintessential result for these processes is the reactive uptake coefficient: the probability that a gas-phase molecule that collides with the surface will react with the surface.…”

A theoretical study of the ozonolysis of C60: primary ozonide formation, dissociation, and multiple ozone additions

“…The experiments of Davis et al 27 provided a variety of information about the reaction of O 3 with C 60 that motivates the work we present in this paper. First, while the measured IR spectrum at low ozone exposures agrees well with the calculated spectrum for a single POZ on a 6,6 bond, the possibility exists that more than one POZ can be formed on the same cage.…”

“…3b) is significantly different from that of the single POZ. Therefore, it seems unlikely that the di-POZ isomer A forms in the low-exposure regime of the study of Davis et al 27 For other isomers, the differences between the IR spectra of the di-POZ species and the primary ozonide are small enough that we cannot determine unequivocally whether the experimental IR spectrum corresponds to a single POZ, to a species that contains two POZs, or to a combination in which some of the C 60 molecules in the film contain a single POZ and some others possess two. For instance, even though the IR spectra of di-POZ isomers B and C exhibit more bands in the 977 cm À1 region than the single POZ, these bands have a smaller intensity and are sufficiently close to other, more intense peaks to be enveloped by the broader experimental bands.…”

Theoretical study of the corannulene ozonolysis and evaluation of the various reaction paths

“…In defective graphene, the arrangement of defects determines the local deviation from planarity. The 1,3-dipolar cycloaddition reactions are among the most straightforward procedures for fullerene and nanotube functionalization [14][15][16][17][18][19][20][21][22][23]. The ozonization of C 60 and the dissociation of the formed ozonide C 60 O 3 have been investigated theoretically at the AM1 level of theory [24] and experimentally [25,26].…”