Nishitani Junichi, Yamamoto Yo-Ichi, West Christopher W, Karashima Shutaro, Suzuki Toshinori
Department of Chemistry, Graduate School of Science, Kyoto University, Kitashirakawa-Oiwakecho, Sakyo-Ku, Kyoto, 606-8502, Japan.
Sci Adv. 2019 Aug 30;5(8):eaaw6896. doi: 10.1126/sciadv.aaw6896. eCollection 2019 Aug.
The electronic energy and dynamics of solvated electrons, the simplest yet elusive chemical species, is of interest in chemistry, physics, and biology. Here, we present the electron binding energy distributions of solvated electrons in liquid water, methanol, and ethanol accurately measured using extreme ultraviolet (EUV) photoelectron spectroscopy of liquids with a single-order high harmonic. The distributions are Gaussian in all cases. Using the EUV and UV photoelectron spectra of solvated electrons, we succeeded in retrieving sharp electron kinetic energy distributions from the spectra broadened and energy shifted by inelastic scattering in liquids, overcoming an obstacle in ultrafast UV photoelectron spectroscopy of liquids. The method is demonstrated for the benchmark systems of charge transfer to solvent reaction and ultrafast internal conversion of hydrated electron from the first excited state.
溶剂化电子是最简单却又难以捉摸的化学物种，其电子能量和动力学在化学、物理和生物学领域备受关注。在此，我们展示了利用单级高谐波液体极紫外（EUV）光电子能谱精确测量的液态水、甲醇和乙醇中溶剂化电子的电子结合能分布。在所有情况下，这些分布均为高斯分布。利用溶剂化电子的EUV和紫外光电子能谱，我们成功地从因液体中的非弹性散射而展宽和能量位移的谱图中获取了尖锐的电子动能分布，克服了液体超快紫外光电子能谱中的一个障碍。该方法在电荷转移到溶剂反应以及水合电子从第一激发态的超快内转换等基准体系中得到了验证。
