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首页> 外文期刊>The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory >Formation of Metastable Triplet Acetylene from the #(↑(1)A↓(u)) State Near the Dissociation Threshold
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Formation of Metastable Triplet Acetylene from the #(↑(1)A↓(u)) State Near the Dissociation Threshold

机译：从离解阈值附近的＃（↑（1）A↓（u））状态形成亚稳三重乙炔

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摘要

The triplet metastable states of acetylene produced by intersystem crossing from the #(↑(1)A↓(u)) state have been detected by a sensitized phosphorescence (SP) method. The phosphorescence was observed from C↓(2)H↓(2) the energy region below the barrier to dissociation in the a state suggested by Hashimoto and Suzuki ［J. Chem. Phys. 1996, 104, 6070]. The lifetimes of the triplet states coupled with the V↑(3)K↑(1) and V↑(4)K↑(1) levels in the #(↑(1)A↓(u)) state were estimated to be 80 and 100 μs. The rotational structures of the laser-induced fluorescence and SP spectra were similar, except that the enhancement of many weak absorption lines makes the latter more congested. The feature of the SP spectrum exemplifies the complicated singlet-triplet mixing at the V↑(3)K↑(1) level. The SP signal was observed with different phosphors, where benzil was found to be the most sensitive. The SP spectrum of C↓(2)D↓(2) was observed only by using benzil. In addition to SP, the collision of metastable triplet acetylene with a phosphor surface yielded fluorescence. This is most likely to be fluorescence from the #(↑(1)A↓(u)) state of acetylene. The lifetime of the triplet states and the threshold energy to dissociation in C↓(2)H↓(2) and C↓(2)D↓(2) suggest that tunneling occurs on the # state and that the energy barrier to dissociation is higher than the previous estimation.
机译：已通过敏化磷光（SP）方法检测到系统间从＃（↑（1）A↓（u））交叉产生的乙炔的三重亚稳态。在桥本和铃木提出的状态下，从离解能垒以下的能量区域C↓（2）H↓（2）观察到磷光［J．化学物理1996，104，6070]。三态态的寿命与＃（↑（1）A↓（u））状态下的V↑（3）K↑（1）和V↑（4）K↑（1）耦合的寿命估计为80和100μs。激光诱导的荧光和SP光谱的旋转结构相似，不同之处在于许多弱吸收线的增强使后者更加拥挤。 SP光谱的特征体现了V↑（3）K↑（1）级别的复杂单重态-三重态混合。用不同的荧光粉观察到了SP信号，其中苯甲酰是最敏感的。仅使用苯甲醚可观察到C↓（2）D↓（2）的SP光谱。除SP外，亚稳态三重态乙炔与荧光粉表面的碰撞还产生荧光。这很可能是来自乙炔的＃（↑（1）A↓（u））状态的荧光。在C↓（2）H↓（2）和C↓（2）D↓（2）中三重态的寿命和解离的阈值能量表明，隧穿发生在＃状态，并且解离的能垒为高于先前的估计。

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