基态BBrx(x=0,-1,+1)分子离子的势能函数与稳定性

用原子分子反应静力学原理推导出了BBrx(x=0,-1,+1)分子离子的基态电子状态及其离解极限.在CC-PVDZ水平基础上,用B3LYP方法计算了BBrx(x=0,- 1,+1)分子离子的基态电子状态的平衡几何Re和离解能De分别为BBr+:0.176 6 nm、3.530 7 eV; BBr-:0.221 7 nm、1.500 0 eV,并在计算出来的一系列单点势能基础上,用正规方程组拟合Murrell-Sorbie(M-S)势能函数,得到相应态的解析势能函数,由此计算对应的光谱参数(Be、αe、ωe、ωeχe),计算结果分别为:BBr+:0.577cm -1、0.004 8 cm-1、932.513 0 cm-1和6.506 5 cm-1;BBr-:0. 360 2 cm-1、0.005 5 cm-1、348.428 3 cm-1和3.541 7 cm-1, 计算值与实验和文献值基本一致,计算表明BBrx(x=0,-1,+1)分子离子是可稳定存在的,其稳定性次序为BBr>BBr+>BBr-.

Potentional energy function and stability of the ground BBr x(x=0,-1,+1)

Based on the Atomic and Molecular Reaction Statics, the ground electronic states for BBr( X 1Σ + ), BBr +( X 2Σ + ) and BBr -( X 2Π ) and the corresponding reasonable dissociative limits have been derived.Using density functional method (B3LYP) and CC PVDZ basis sets, the molecular equilibrium geometry and dissociation energy for BBr x(x =0,-1,+1) have been calculated, then, with Murrell Sorbie function form, spectroscopic date for BBr x(x =0,-1,+1) have been derived.The calculated results for R e, D e, B e, α e, ω e and ω eχ e are 0.1776 nm, 3.530 7 cm -1 , 0.567 7 cm -1 , 0.004 8 cm -1 , 932.513 0 cm -1 and 3.451 7 cm -1 respectively for BBr +;0.221 7 nm, 1.500 0 cm -1 , 0.360 2 cm -1 , 0.005 5 cm -1 , 348.428 3 cm -1 and 3.451 7 cm -1 respectively for BBr -, which are in good agreement with experimental or calculated values in references.It shows that BBr, BBr + and BBr - can be stable, the order of stableness is BBr>BBr+>BBr-.