Functionalization of Benzene Ices by Atomic Oxygen

TL;DR

This study demonstrates that singlet oxygen atoms can efficiently react with benzene in icy environments, forming phenol and other oxygenated aromatics, which could explain their presence in comets and star-forming regions.

Contribution

It provides experimental evidence for O($^1$D) reacting with benzene in ices, revealing a potential pathway for forming oxygenated aromatics in space.

Findings

O($^1$D) reacts with benzene to produce phenol, benzene oxide, and oxepine.

Phenol formation is temperature-independent, indicating a barrierless process.

Estimated benzene-to-phenol conversion fraction is 27-44% in interstellar conditions.

Abstract

Small aromatic molecules, including functionalized derivatives of benzene, are known to be present throughout the different stages of star and planet formation. In particular, oxygen-bearing monosubstituted aromatics, likely including phenol, have been identified in the coma of comet 67P. This suggests that, earlier in the star and planet formation evolution, icy grains may act as both reservoirs and sites of functionalization for these small aromatics. We investigate the ice-phase reactivity of singlet oxygen atoms (O($^1$D)) with benzene, using ozone as a precursor that is readily photodissociated by relatively low-energy. Our experiments show that O($^1$D) efficiently reacts with benzene, forming phenol, benzene oxide, and oxepine as the main products. Phenol formation is temperature-independent, consistent with a barrierless insertion mechanism. In contrast, the formation of benzene oxide/oxepine shows a slight temperature dependence, suggesting that additional reaction pathways involving either ground-state or excited-state oxygen atoms may contribute. In H$_2$O and \COO ice matrices we find that dilution does not suppress formation of phenol. We extrapolate an experimental upper limit for the benzene-to-phenol conversion fraction of 27-44$\%$ during the lifetime of an interstellar cloud, assuming O($^1$D) production rates based on CO$_2$ ice abundances and a cosmic-ray induced UV field. We compare these estimates with a new analysis of data from the comet 67P, where the C$_6$H$_6$O/C$_6$H$_6$ ratio is 20$\pm$6$\%$. This value lies within our estimated range, suggesting that O($^1$D)-mediated chemistry is a viable pathway for producing oxygenated aromatics in cold astrophysical ices, potentially enriching icy planetesimals with phenol and other biorelevant compounds.