Photon Factory, Institute of Materials Structure Science, KEK, Oho 1-1, Tsukuba 305-0801, Japan.
J Chem Phys. 2012 Feb 21;136(7):074305. doi: 10.1063/1.3687006.
Recoil frame photoelectron angular distributions (RFPADs) of BF(3) molecules are presented over the energy region of the shape resonance in the F 1s continuum. Time-dependent density functional theory calculations are also given to understand the shape resonance dynamics. The RFPADs have been compared with the theoretical calculations. It is found that the RFPADs calculated by the localized core-hole model are in better agreement with the experimental, compared with those by the delocalized core hole. Dipole matrix elements and dipole prepared continuum wavefunctions show that the shape resonance in the F 1s ionization continuum of BF(3) is induced by p-partial waves as previously reported by Swanson et al. [J. Chem. Phys. 75, 619 (1981)]. However, due to the couplings with the other partial waves the feature characteristic of the p-partial waves has not been observed in the RFPADs.
BF(3)分子的反冲框架光电子角分布（RFPAD）在 F 1s 连续谱中的形状共振能区呈现出来。还给出了基于时间相关密度泛函理论的计算，以理解形状共振动力学。将 RFPAD 与理论计算进行了比较。结果发现，与离域芯孔相比，局域芯孔模型计算的 RFPAD 与实验结果更为吻合。偶极矩矩阵元以及偶极准备连续波函数表明，BF(3)的 F 1s 离化连续谱中的形状共振是由 p 部分波诱导的，这与 Swanson 等人之前的报道一致[J. Chem. Phys. 75, 619 (1981)]。然而，由于与其他部分波的耦合，RFPAD 中并未观察到 p 部分波的特征。
