Vibrations of the low energy states of toluene (X1A1 and A1B2) and the toluene cation (X2B1)
Vibrations of the low energy states of toluene (X1A1 and A1B2) and the toluene cation (X2B1)
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DOI：
10.1063/1.4796204
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发表时间：
2013-04-07
影响因子：
4.4
通讯作者：
Wright, Timothy G.
中科院分区：
文献类型：
--
作者：
Gardner, Adrian M.;Green, Alistair M.;Wright, Timothy G.
我们首先概述甲苯分子在基态 (S-0) 的振动频率分配。给出的分配是根据最近提出的命名法，它允许直接比较不同单取代苯的环局部振动。频率和分配不仅基于一系列先前的工作，还基于从密度泛函理论 (DFT) 获得的完全氢化 (甲苯-h(8)) 和氘化甲基同位素体 α(3)-甲苯-d(3)) 的计算波数，包括人工同位素位移。对于S-1态，采用单色共振增强多光子电离（REMPI）光谱，振动分配也基于先前的工作和时间相关密度泛函理论（TDDFT）计算值；还利用了双色零动能 (ZEKE) 光谱中观察到的活性。 ZEKE 实验采用 (1 + 1') 电离方案进行，使用能量为 S-1 态的各种振动能级
We commence by presenting an overview of the assignment of the vibrational frequencies of the toluene molecule in its ground (S-0) state. The assignment given is in terms of a recently proposed nomenclature, which allows the ring-localized vibrations to be compared straightforwardly across different monosubstituted benzenes. The frequencies and assignments are based not only on a range of previous work, but also on calculated wavenumbers for both the fully hydrogenated (toluene-h(8)) and the deuterated-methyl group isotopologue alpha(3)-toluene-d(3)), obtained from density functional theory (DFT), including artificial-isotope shifts. For the S-1 state, one-colour resonance-enhanced multiphoton ionization (REMPI) spectroscopy was employed, with the vibrational assignments also being based on previous work and time-dependent density functional theory (TDDFT) calculated values; but also making use of the activity observed in two-colour zero kinetic energy (ZEKE) spectroscopy. The ZEKE experiments were carried out employing a (1 + 1') ionization scheme, using various vibrational levels of the S-1 state with an energy