Correction to “Photoinduced Thermionic Emission from [M25(SR)18]- (M = Au, Ag) Revealed by Anion Photoelectron Spectroscopy”
Correction to “Photoinduced Thermionic Emission from [M25(SR)18]- (M = Au, Ag) Revealed by Anion Photoelectron Spectroscopy”
复制标题
对“阴离子光电子能谱揭示的 [M25(SR)18]- (M = Au, Ag) 的光致热电子发射”的修正
DOI：
10.1021/acs.jpcc.2c02963
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发表时间：
2022
期刊：
影响因子：
--
通讯作者：
Tsukuda Tatsuya
中科院分区：
文献类型：
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作者：
Hirata Keisuke;Ito Shun;Kim Kuenhee;Nakamura Katsunosuke;Kitazawa Hirokazu;Hayashi Shun;Koyasu Kiichirou;Tsukuda Tatsuya
在355 nm和266 nm处记录了真空中分离的硫代保护硬币金属簇合物[Au25(SC2H4Ph)18]−和[Ag25(SPhMe2)18]−的光电子(PE)谱。在355 nm处测得它们的绝热电子亲和能分别为2.36±0.01 eV和2.02±0.02 eV。在266 nm光的照射下，观察到慢电子的发射是主要的过程，同时抑制了电子的直接脱离和解离成阴离子碎片。对266nmPE谱的曲线拟合分析表明，慢电子发射归属于[M25(SR)18]−(M=Au，Ag)中振动热的M13核的热电子发射(TE)。这里观察到的新的光致TE归因于选择性地跃迁到嵌入在电子脱离连续体中的电子激发态[M25(SR)18]−*，然后在电子基态快速内转换到振动激发态。
Photoelectron (PE) spectra of thiolate-protected coinage metal clusters [Au25(SC2H4Ph)18]−and [Ag25(SPhMe2)18]−isolated in vacuum were recorded at 355 and 266 nm. Their adiabatic electron affinities were determined to be 2.36 ± 0.01 and 2.02 ± 0.02 eV, respectively, from the onsets of the PE spectra recorded at 355 nm. Upon irradiation with a 266 nm light, the emission of slow electrons was observed as the major process, while suppressing the direct electron detachment and dissociation into anionic fragments. Curve fitting analysis of the PE spectra at 266 nm suggests that the slow electron emission is assigned to thermionic emission (TE) from the vibrationally hot M13core in [M25(SR)18]−(M = Au, Ag). The novel photoinduced TE observed here is ascribed to the selective transition to an electronically excited state [M25(SR)18]−* embedded in the electron detachment continuum followed by quick internal conversion to a vibrationally excited state in the electronically ground state.