Ban Loren, Yoder Bruce L, Signorell Ruth
Department of Chemistry and Applied Biosciences, ETH Zurich, Vladimir-Prelog-Weg 2, CH-8093 Zurich, Switzerland.
J Phys Chem A. 2021 Jun 24;125(24):5326-5334. doi: 10.1021/acs.jpca.1c03631. Epub 2021 Jun 11.
Cluster-size-resolved ultrafast dynamics of the solvated electron in neutral water clusters with = 3 to ∼200 molecules are studied with pump-probe time-of-flight mass spectrometry after below band gap excitation. For the smallest clusters, no longer-lived (>100-200 fs) hydrated electrons were detected, indicating a minimum size of ∼ 14 for being able to sustain hydrated electrons. Larger clusters show a systematic increase of the number of hydrated electrons per molecule on the femtosecond to picosecond time scale. We propose that with increasing cluster size the underlying dynamics is governed by more effective electron formation processes combined with less effective electron loss processes, such as ultrafast hydrogen ejection and recombination. It appears unlikely that any size dependence of the solvent relaxation dynamics would be reflected in the observed time-resolved ion yields.
在带隙以下激发后,利用泵浦 - 探测飞行时间质谱法研究了含有3至约200个分子的中性水团簇中溶剂化电子的团簇尺寸分辨超快动力学。对于最小的团簇,未检测到寿命更长(>100 - 200飞秒)的水合电子,这表明能够维持水合电子的最小尺寸约为14。较大的团簇在飞秒到皮秒的时间尺度上显示出每个分子水合电子数量的系统性增加。我们提出,随着团簇尺寸的增加,其潜在动力学由更有效的电子形成过程和效率较低的电子损失过程(如超快氢喷射和复合)共同控制。溶剂弛豫动力学的任何尺寸依赖性似乎不太可能反映在观察到的时间分辨离子产率中。