Vibronic structure of the 3s Rydberg state of the 2-methylallyl radical
Vibronic structure of the 3s Rydberg state of the 2-methylallyl radical
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2-甲基烯丙基基团 3s Rydberg 态的电子振动结构
DOI：
10.1016/j.jms.2010.07.008
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发表时间：
2010
影响因子：
1.4
通讯作者：
A. Bach
中科院分区：
文献类型：
--
作者：
M. Gasser;J. Frey;J. M. Hostettler;A. Bach
共振增强多光子电离与喷射冷却 2-甲基烯丙基 (C4H7) 自由基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。对电子冷 2-甲基烯丙基自由基及其同位素异体 C4H4D3 和 C4D7 进行一光子和两光子激发后的电子振动结构分析揭示了 3s 里德堡态中超过 30 个振动能级的跃迁，这些振动能级是根据从头计算的预测和获得的脉冲场电离零动能光电子能谱的结果进行识别和重新分配的通过选定的中间态进行共振多光子激发。耗尽光谱揭示了向具有较大振荡强度的短寿命 3p 里德堡态的转变。
Resonance-enhanced multiphoton ionization combined with electronic ground state depletion spectroscopy of jet-cooled 2-methylallyl (C4H7) radicals provides vibronic spectra of the 3s and 3p Rydberg states. Analysis of the vibronic structure following one-photon and two-photon excitation of rovibronically cold 2-methylallyl radicals and its isotopologues C4H4D3and C4D7reveals transitions to more than 30 vibrational levels in the 3s Rydberg state that are identified and reassigned on the basis of predictions from ab initio calculations and results from pulsed-field-ionization zero-kinetic-energy photoelectron spectra obtained with resonant multiphoton excitation via selected intermediate states. Depletion spectroscopy reveals transitions to short-lived 3p Rydberg states that have a large oscillator strength.