Investigation on the correlation of stability, reactivity, and structural properties of C/C2-doped neutral and charged Aln (n = 2–7) clusters

Abstract

The equilibrium geometries, electronic structures, reactivity, and stability of C/C2-doped Aln0,± (n = 2–7) clusters were investigated computationally at B3LYP-D4/def2-TZVPP and CCSD(T)/def2-TZVPP levels of theory. The lowest energy structures of AlnC1,20,± clusters were the carbon atoms inserted inside the aluminium clusters. The stability of the neutral and charged clusters were investigated under various reaction conditions, such as dissociation of the clusters via Al0,+,C0,-,C20,--elimination and electron elimination from neutral (ionization) and anionic species (electron detachment). The dominant dissociation reaction channels are the Al-elimination from the neutral and anionic clusters, Al+-elimination from cationic clusters, rather than the C/C2-elimintion reaction. On the other hand, C-elimination are were more favorable compared to C2-elimination due to the stronger CC and Al-C bonds. In addition, binding energy, second-order difference of energy, chemical hardness, and electron affinity parameters were used to determine the stability and reactivity. The results show the singlet cluster (Al2,4,6C1,2 and Al3,5,7C0-20,±) have the greater stability than the doublet clusters (Al3,5,7C0-2 and Al2,4,6C1,20,±) and triplet clusters (Al2,4,6). It has been demonstrated that anionic clusters are more stable than the neutral species, and cationic species are less stable than that of neutral species. The current study could be useful in understanding the stability and reactivity of metal clusters after carbon doping, which is important in combustion, material science, and the astrochemical community.