【摘要】 基于ab initio/DFT理论,对磷基PH2分子X~2B1态和PH-2阴离子X~1A1态进行了几何结构优化和谐振频率计算.在B3LYP/6-311+G(2d,p)理论水平下,通过Franck-Condon因子计算模拟了PH-2实验的光电子能谱,计算得到的理论谱与实验谱完全一致,确认属于PH2(X~2B1)-PH-2(X~1A1)光脱附过程.另外,通过迭代Franck-Condon分析,得到优于ab initio/DFT理论计算的PH-2离子的几何结构参数R(PH)=0.1438±0.0002 nm和∠(HPH)=92.2±0.2°.更多还原

【Abstract】 Geometry optimization and harmonic vibrational frequency calculations have been performed on the X~2B1state of phosphino radical PH2 and X~1A1state of PH-2anion based on ab initio / DFT theory. The theoretical spectra obtained by employing B3 LYP /6- 311 + G( 2d,p) values are in excellent agreement with the observed photodetachment spectrum of phosphino radical. Additionally,the more reliable geometric parameters,R( PH)= 0. 1438 ± 0. 0002 nm and ∠( HPH) = 92. 2 ± 0. 2°,of X~1A1state of PH-2anion are derived by employing an iterative Franck-Condon analysis procedure in the spectral simulation.更多还原