Cage-like B40+: a perfect borospherene monocation

The recent discovery of perfect cage-like D-2d B-40(-) and D-2d B-40 (all-boron fullerenes) has led to the emergence of a borospherene family. However, the geometrical and electronic structures of their cationic counterpart B-40(+), previously detected in gas phase, remain unknown to date. Based on extensive first-principles theory calculations, we present herein the possibility of a perfect cage-like D-2d B-40(+) (1) ((2)A(1)) for the monocation, which turns out to be the global minimum of the system similar to B-40(-) and B-40, adding a new member to the borospherene family. Molecular dynamics simulations indicate that D-2d B-40(+) (1) is dynamically stable at 300 K, whereas it starts to fluctuate at 500 K between the two lowest-lying isomers D-2d B-40(+) (1) (W) and C-s B-40(+) (3) (M) in concerted W-X-M mechanisms via the transition state of C-1 B-40(+) (X), with forward (W -> X -> M) and backward (M -> X -> W) activation energies (E-a) of 14.6 and 6.9 kcal mol(-1), respectively. The spectra from IR, Raman, and UV-vis analyses were simulated to facilitate future characterization of this important borospherene monocation.