Hoerner Paul, Schlegel H Bernhard
Department of Chemistry, Wayne State University , Detroit, Michigan 48202, United States.
J Phys Chem A. 2017 Feb 16;121(6):1336-1343. doi: 10.1021/acs.jpca.6b11415. Epub 2017 Feb 3.
The angular dependence of ionization by linear and circularly polarized light has been examined for N, NH, HO, CO, CHO, pyrazine, methyloxirane, and vinyloxirane. Time-dependent configuration interaction with single excitations and a complex absorbing potential was used to simulate ionization by a seven cycle 800 nm cosine squared pulse with intensities ranging from 0.56 × 10 to 5.05 × 10 W cm. The shapes of the ionization yield for linearly polarized light can be understood primarily in terms of the nodal structure of the highest occupied orbitals. Depending on the orbital energies, ionization from lower-lying orbitals may also make significant contributions to the shapes. The shapes of the ionization yield for circularly polarized light can be readily explained in terms of the shapes for linearly polarized light. Averaging the results for linear polarization over orientations perpendicular to the direction of propagation yields shapes that are in very good agreement with direct calculations of the ionization yield by circularly polarized light.
已对N、NH、HO、CO、CHO、吡嗪、甲基环氧乙烷和乙烯基环氧乙烷研究了线性偏振光和圆偏振光电离的角度依赖性。采用含单激发的含时组态相互作用和复吸收势，来模拟强度范围为0.56×10至5.05×10 W/cm的七周期800 nm余弦平方脉冲的电离。线性偏振光电离产率的形状主要可以根据最高占据轨道的节点结构来理解。根据轨道能量，来自较低轨道的电离对形状也可能有显著贡献。圆偏振光电离产率的形状可以根据线性偏振光的形状很容易地解释。对垂直于传播方向的取向的线性偏振结果进行平均，得到的形状与圆偏振光电离产率的直接计算结果非常吻合。
