Shape Symmetrization and IR-Spectral Enhancement of Aluminum Clusters via Doping with a Carbon Core

Composite nanosystems are a class of objects with interesting and potentially useful properties. Here we study mixed-composition species representing interfaces at the molecular level between such technologically relevant materials as carbon and aluminum. Specifically, core-shell C₈@Al (n = 16, 18) species and their isomers with the core and relaxed-shell attached outside are investigated at a DFT level in terms of structures and stabilities, charge distributions and polarities, and IR spectra and electron affinities. Among the interesting findings is the possibility of bringing the aluminum cluster into a more symmetric shape (thus making a convenient building block) via insertion of a suitable molecular-carbon skeleton. Another notable feature is the system-selective dependence of polarity on spin multiplicity, suggesting possible molecular-electronic applications. The IR spectra of the composite species are much brighter compared to those of the separated components and are highly focused for the core-shell isomers. A related aspect of interest is the apparent reflections of the system structural details in the IR spectra features (line intensities and separations) via related vibrations, facilitating an experimental analysis of the structure and detection of the species formation and transformation as well as potentially enabling the means of achieving desirable optical characteristics via a geometric design.