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中国物理学会期刊

从头计算研究BP分子的势能曲线和光谱性质

CSTR: 32037.14.aps.63.073302

Ab initio calculation of the potential energy curves and spectroscopic properties of BP molecule

CSTR: 32037.14.aps.63.073302
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  • 利用高精度的量子化学从头计算MRCI+Q方法结合相关一致aug-cc-pVQZ基组计算了磷化硼分子X3,3-,5和5-态的势能曲线,计算所得的电子态在大键长位置处收敛于同一个离解极限B(2Pu)+P(4Su). 为了得到更精确的结果,计算中首次纳入了旋轨耦合(SOC)效应,使得BP分子的4个-S态分裂成为15个态,其中30+ 态被确定为基态. 此外,SOC效应还使两个三重态X3和3-分裂出的0+和1态的势能曲线产生了避免交叉,表明在当前的计算中考虑SOC效应是非常必要的. 利用LEVEL8.0程序对计算所得的-S态和态的势能曲线进行拟合,得到了相应的光谱常数,通过与其他理论和实验工作进行比较,可知我们的结果更加精确、完整,可以为实验和理论方面进一步研究BP分子的光谱性质提供可靠的参考.

     

    A high-precision quantum chemistry ab initio multi-reference configuration interaction method with aug-cc-pVQZ basis sets has been used to calculate the four states of BP molecule. The four -S states are X3, 3-, 5 and 5-, which are correlated to the lowest dissociation limit of B(2Pu)+P(4Su). Analysis of the electronic structures of -S states shows that the -S electronic states are essentially multi-configurational. We take the spin-orbit interaction into account for the first time so far as we know, which makes the four -S states split into fifteen states. 30+ state is confirmed to be the ground state. The SOC effect is essential for the BP molecule, which leads to the avoided crossings for 0+ and 1 states from X3 and 3-. Based on the PECs of -S and states, the accurate spectroscopic constants are obtained by solving the radial Schrdinger equation. The spectroscopic results may be conducive to further research on BP molecule in experiment and theory.

     

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