Theoretical prediction on low-lying states of HBP and HPB radicals

• Published in: Chemical physics letters Vol. 532; pp. 36 - 39
• Main Authors: Li, Wen-Zuo, Pei, Yu-Wei, Sun, Cai-Xia, Li, Qing-Zhong, Cheng, Jian-Bo
• Format: Journal Article
• Language: English
• Published: Elsevier B.V 12.04.2012
• ISSN: 0009-2614; 1873-4448
• DOI: 10.1016/j.cplett.2012.02.069

The low-lying states of the HBP and HPB radicals have been studied using CASSCF, CASPT2, and B3LYP methods. [Display omitted] ► The structures of the low-lying states of HBP and HPB radicals were studied. ► The ground states of HBP and HPB radicals were predicted. ► The state-correlations between the HBP and HPB radicals were clearly described. Some low-lying states of the nine-valence-electron systems HBP and HPB radicals have been studied using three methods CASSCF, CASPT2, and B3LYP with the contracted atomic natural orbital (ANO) and cc-pVTZ basis sets. The geometries of all stationary points along the potential energy surfaces were optimized at the CASSCF/ANO, CASPT2/ANO, and B3LYP/cc-pVTZ levels. The potential energy curves of isomerization reactions between HBP and HPB were calculated as a function of HBP bond angle. The calculated results indicated that the ground-state HBP is linear, while the ground-state HPB is bent, which is in contradiction to Walsh’s rules predicting linear structures for the HXY systems containing 10 or less valency electrons.