Quantum modeling of the optical spectra of carbon cluster structural families and relation to the interstellar extinction UV bump

Context. The UV bump observed in the interstellar medium extinction curve of galaxies has been assigned to π → π ⋆ transitions within the sp 2 conjugated network of carbon grains. These grains are commonly thought to be graphitic particles or polycyclic aromatic hydrocarbons. However, questions are still open regarding the shape and degree of amorphization of these particles, which could account for the variations in the 2175 Å astronomical bump. Optical spectra of graphitic and onion-like carbon structures were previously obtained from dielectric constant calculations based on oscillating dipole models. In the present study, we compute the optical spectra of entire populations of carbon clusters using an explicit quantum description of their electronic structure for each individual isomer. Aims. Our aim is to determine the optical spectra of pure carbon clusters C n =24,42,60 sorted into structural populations according to specific order parameters, namely asphericity and sp 2 fraction, and to correlate these order parameters to the spectral features of the band in the region of the UV bump. Our comparison involves data measured for the astronomical UV bump as well as experimental spectra of carbon species formed in laboratory flames. Methods. The individual spectrum of each isomer is determined using the time-dependent density functional tight-binding method. The final spectrum for a given population is obtained by averaging the individual spectra for all isomers of a given family. Our method allows for an explicit description of particle shape, as well as structural and electronic disorder with respect to purely graphitic structures. Results. The spectra of the four main populations of cages, flakes, pretzels, and branched structures (Dubosq et al. 2019, A&A, 625, L11) all display strong absorption in the 2–8 eV domain, mainly due to π → π ⋆ transitions. The absorption features, however, differ from one family to another and our quantum modeling indicates that the best candidates for the interstellar UV bump at 217.5 nm are cages and then flakes, while the opposite trend is found for the carbonaceous species formed in flame experiments; the other two families of pretzels and branched structures play a lesser role in both cases. Conclusions. Our quantum modeling shows the potential contribution of carbon clusters with a high fraction of conjugated sp 2 atoms to the astronomical UV bump and to the spectrum of carbonaceous species formed in flames. While a