Interactions in the B⁺–RG Complexes and Comparison with Be⁺–RG (RG = He–Rn): Evidence for Chemical Bonding

Potential energy curves for the interaction of B+ (1S) with RG (1S), RG = He–Rn, have been calculated at the CCSD­(T) level of theory employing quadruple-ζ and quintuple-ζ quality basis sets. The interaction energies from these curves were subsequently point-by-point extrapolated to the basis set limit. Rovibrational energy levels have been calculated for each extrapolated curve, from which spectroscopic parameters are determined. These are compared to previously determined experimental and theoretical values. The potentials have also been employed to calculate the transport coefficients for B+ traveling through a bath of RG atoms. We also investigate the interactions between B+ and the rare gases via contour plots, natural population analysis (NPA), and molecular orbital diagrams. In addition, we consider the atoms-in-molecules (AIM) parameters. The interactions here are compared and contrasted with those for Li+–He and Be+–RG; it is concluded that there is significant and increasing dative covalent bonding for the Be+–RG and B+–RG complexes for RG = Ar–Rn, while the other species are predominantly physically bound.本研究针对B⁺(¹S)与RG(¹S)（其中RG取值为He至Rn）之间的相互作用，采用CCSD(T)理论级别，结合四重ζ与五重ζ质量级别的基组，计算得到了其相互作用势能曲线。随后，基于该系列势能曲线，通过逐点外推法将相互作用能外推至基组极限。针对每条外推所得的势能曲线，计算其振转能级，并由此确定光谱学参数。将所得光谱参数与已报道的实验值及理论计算值进行对比分析。上述势能曲线还被用于计算B⁺在稀有气体原子气浴中运动时的输运系数。本研究还通过等高线图、自然布居分析（Natural Population Analysis）以及分子轨道图，对B⁺与稀有气体的相互作用展开了研究，并分析了分子中原子（Atoms-in-Molecules）参数。本研究将上述相互作用与Li⁺-He及Be⁺-RG体系的相互作用进行对比与辨析，结果表明：当RG为Ar至Rn时，Be⁺-RG与B⁺-RG配合物中存在显著且随原子序数递增而增强的配位共价键作用，其余体系则主要以物理结合为主。