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

Abstract

Context. The UV bump observed in the interstellar medium extinction curve of galaxies has been assigned to π → π⋆ transitions within the sp2 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 Cn=24,42,60 sorted into structural populations according to specific order parameters, namely asphericity and sp2 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 sp2 atoms to the astronomical UV bump and to the spectrum of carbonaceous species formed in flames. While astronomical spectra are better accounted for using rather spherical isomers such as cages, planar flake structures are involved as a much greater component in flame experiments. Interestingly, these flake isomers have been proposed as likely intermediates in the formation mechanisms leading to buckminsterfullerene, which was recently detected in space. This study, although restricted here to the case of pure carbon clusters, will be extended towards several directions of astronomical relevance. In particular, the ability of the present approach to deal with large-scale molecular systems at an explicit quantum level of electronic structure and its transferable character towards different charge states and the possible presence of heteroatoms makes it the method of choice to address the important case of neutral and ionic hydrogenated compounds.

Void-Defect Induced Magnetism and Structure Change of Carbon Material-Ⅱ: Graphene Molecules

“…These infrared features appear to be coincident with planar C24 having seven carbon hexagon rings. However, full observed bands still cannot be explained by C24 or hexagon network molecules 38) . Some hints come from carbon SP3 defect among SP2 network caused by single void-defect in carbon hexagon network by Ota 39) .…”

Hydrogenation of C$_{24}$ carbon clusters : structural diversity and energetic properties

“…Before generating sets of carbonaceous clusters for different H/C ratios, we performed preliminary simulations to check the efficiency of the GA in terms of PES exploration and thus diversity of structures. We chose C 24 as its PES exploration followed by structural and spectral analysis was achieved in our previous works 18,27 . In those studies, the PES exploration was performed using parallel tempering molecular dynamics (PTMD) 41 with the REBO force field 42 , followed by local SCC-DFTB optimization.…”

Adsorption of helium on a charged propeller molecule: hexaphenylbenzene

“…PAHs or other carbonaceous materials [8]. Fullerenes and PAHs are also likely to play a role in astrochemistry [9].…”