Vibronic structure of the 3s and 3p Rydberg states of the allyl radical.
Vibronic structure of the 3s and 3p Rydberg states of the allyl radical.
复制标题
烯丙基的 3s 和 3p Rydberg 态的电子振动结构。
DOI：
10.1021/jp907524s
复制
发表时间：
2010
期刊：
影响因子：
--
通讯作者：
Peter Chen
中科院分区：
文献类型：
--
作者：
M. Gasser;J. Frey;J. M. Hostettler;A. Bach;Peter Chen
共振增强多光子电离与喷射冷却烯丙基自由基 (C(3)H(5)) 的电子基态耗尽光谱相结合，提供了 3s 和 3p 里德伯态的振动光谱。对振动冷烯丙基自由基双光子激发后的电子振动结构的分析揭示了向 3p(z) ((2)A(1)) Rydberg 态的跃迁，其电子起源位于 42230 cm(-1)。根据从头计算的预测以及最近使用共振多光子激发通过这两种材料的选定振动能级获得的脉冲场电离零动能光电子能谱的结果和模拟，识别并重新分配了 3p(y) ((2)B(2)) 里德堡态和 3s ((2)A(1)) 里德堡态部分重叠光谱中的 40 多个振动能级跃迁Rydberg 指出（J. Chem. Phys. 2009, 131, 014304）。耗尽光谱表明，理论上预测的三态相同对称圆锥形交叉点附近向短命 3p(x) ((2)B(1)) 里德堡态的转变承载了这些耦合的 3s 和 3p 里德堡态的大部分振荡强度。该结果首次通过实验推导了烯丙基自由基 3p 里德伯态的能量排序。
Resonance-enhanced multiphoton ionization combined with electronic ground state depletion spectroscopy of jet-cooled allyl radicals (C(3)H(5)) provides vibronic spectra of the 3s and 3p Rydberg states. Analysis of the vibronic structure following two-photon excitation of rovibrationally cold allyl radicals reveals transitions to the 3p(z) ((2)A(1)) Rydberg state with an electronic origin at 42230 cm(-1). More than 40 transitions to vibrational levels in the partially overlapping spectra of the 3p(y) ((2)B(2)) Rydberg state and the 3s ((2)A(1)) Rydberg state are identified and reassigned on the basis of predictions from ab initio calculations and results and simulations of pulsed-field-ionization zero-kinetic-energy photoelectron spectra obtained recently using resonant multiphoton excitation via selected vibrational levels of these two Rydberg states (J. Chem. Phys. 2009, 131, 014304). Depletion spectroscopy reveals that the transition to the short-lived 3p(x) ((2)B(1)) Rydberg state in vicinity of three-state same symmetry conical intersections predicted theoretically carries most of the oscillator strength of these coupled 3s and 3p Rydberg states. The results allow for the first time to experimentally derive the energetic ordering of the 3p Rydberg states of the allyl radical.