Density functional theory has been applied to investigate the structures and properties of asymmetric clusters (HFBN3)n (n=1-6). When n≥2, B–Nα bonds form easily, and B–B and Nα–Nα bonds are not found in the clusters. The geometric parameters of clusters along with cluster size n are discussed. The relative stabilities of asymmetric clusters (HFBN3)n (n=1-6) are analyzed based on the averaged binding energy and second-order difference of energy. It is found that (HFBN3)3 clusters are more stable than other clusters. The calculated IR spectra have four main characteristic regions. Trends in thermodynamic properties with temperature T and cluster size n are discussed, respectively. Monomer 1 forms clusters (2, 3, 4, 5 and 6) thermodynamically favorable by the enthalpies at 298.2 K.
