A theoretical survey on the structures, energetics, and isomerization pathways of the B5O radical

Abstract

Boron-centered radicals have received growing interest. Recently, two groups reported density functional theory investigations (GGA-PW91 and B3LYP) on a hexa-atomic boron-oxide radical, B(5)O, which has led to great discrepancies on the type of low-lying structures. In this article, we not only explore the energetics of doublet and quartet B(5)O isomers at high electron-correlated levels (CCSD(T)/6-311+G(2df), CCSD(T)/aug-cc-pVTZ, and G3B3) but also investigate the isomerization and fragmentation stability of the low-lying B(5)O isomers. All the high-level studies consistently show that the B(5)O radical possesses a belt-like ground structure (2)01 in doublet electronic state followed by isomer (2)02 with an exocyclic - BO moiety at around 3.0 kcal/mol. Kinetically, (2)01 and (2)02 are separated by a considerable barrier of about 20 kcal/mol. Thus, the two isomeric forms of B(5)O radical should be very promising for isolation in laboratory. However, the other four isomers reported recently are all kinetically unstable toward conversion to (2)01 and (2)02. The high thermodynamic and kinetic stability of (2)01 and (2)02 might make them as important building cores in the growth of boron-oxide clusters. This results would also help deeply understand the oxidation and doping mechanism of pure boron clusters.