Photodissociation dynamics of methyl iodide across the A-band probed by femtosecond extreme ultraviolet photoelectron spectroscopy

Photodissociation dynamics of methyl iodide across the A-band probed by femtosecond extreme ultraviolet photoelectron spectroscopy
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飞秒极紫外光电子能谱探测甲基碘在 A 波段的光解离动力学

DOI:
10.1088/1361-6455/ac08f3
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发表时间:
2021
期刊:
Atomic, Molecular and Optical Physics
影响因子:
--
通讯作者:
Downes-Ward B
Downes-Ward B
中科院分区:
--
文献类型:
--
作者:
Downes-Ward B

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在时间分辨光电子能谱实验中,用极紫外光探针测量了CH3I在三个紫外泵浦光波长(279 nm、254 nm、243 nm)下的解离动力学。将结果与之前发表的269 nm泵浦波长下的数据进行了比较,[2020,Phys.化学。化学。Phys,22,25695],使用多光子电离(MPI)探针进行互补光电子能谱实验[2019年,Phys.化学。化学。Phys,21,11142]和最近Murillo-Sánchez等人的动作光谱测量[2020年,J.物理,152,014304]。在279 nm和243 nm处的测量显示了与C-I键在时间尺度上发生的快速解离一致的信号,这与之前的测量结果一致。在254 nm处的测量表明,激发态寿命明显较长,在100fs之后出现第二个特征,这表明激发态的动力学更加复杂。这些变化的时间依赖性与之前测量的Warne等人的MPI光电子能谱测量结果一致[2019,Phys.化学。化学。物理,21,11142]。电离过程中信号出现的一致性表明,在254 nm处延长的观察时间不是先前使用的MPI过程的产物,而是由更复杂的激发态势的动力学引起的。这是由占主导地位的3Q0态的复杂振动动力学引起的,还是由于1Q1态上的布居和动力学增强引起的,仍然是一个悬而未决的问题。
The dissociation dynamics of CH 3 I at three UV pump wavelengths (279 nm, 254 nm, 243 nm) are measured using an extreme ultraviolet probe in a time-resolved photoelectron spectroscopy experiment. The results are compared with previously published data at a pump wavelength of 269 nm,[2020, Phys. Chem. Chem. Phys., 22, 25695], with complementary photoelectron spectroscopy experiments performed using a multiphoton ionization (MPI) probe [2019, Phys. Chem. Chem. Phys., 21, 11142] and with the recent action spectroscopy measurements of Murillo-Sánchez et al [2020, J. Chem. Phys., 152, 014304]. The measurements at 279 nm and 243 nm show signals that are consistent with rapid dissociation along the C–I bond occurring on timescales that are consistent with previous measurements. The measurements at 254 nm show a significantly longer excited state lifetime with a secondary feature appearing after 100 fs which is indicative of more complex dynamics in the excited state. The time-dependence of the changes are consistent with the previously measured MPI photoelectron spectroscopy measurements of Warne et al,[2019, Phys. Chem. Chem. Phys., 21, 11142]. The consistency of the signal appearance across ionization processes suggests that the extended observation time at 254 nm is not an artefact of the previously used MPI process but is caused by more complex dynamics on the excited state potential. Whether this is caused by complex vibrational dynamics on the dominant 3 Q 0 state or is due to enhanced population and dynamics on the 1 Q 1 state remains an open question.
对齐的CH(3)I和C(6)H(3)F(3)F(2)I分子的光解离,该分子用位点选择性的极端紫外线离子化探测了时间分辨的库仑爆炸成像。
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