冷叔丁基过氧化物的慢光电子速度成像。

Slow photoelectron velocity-map imaging of cold tert-butyl peroxide.

机构信息

Department of Chemistry, University of California, Berkeley, California 94720, USA.

出版信息

J Chem Phys. 2017 Jul 7;147(1):013915. doi: 10.1063/1.4979951.

Abstract

Photoelectron spectra of cryogenically cooled X∼A' tert-butyl peroxide anions are obtained using slow electron velocity-map imaging. The spectra show highly structured bands corresponding to detachment to the X∼A″ and A∼A electronic states of the neutral radical and represent a notable improvement in resolution over previous photoelectron spectra. We report an electron affinity of 1.1962(20) eV and a term energy T(A∼A) of 0.9602(24) eV for the tert-butyl peroxy radical. New vibrational structure is resolved, providing several frequencies for both neutral states. Additionally, the threshold behavior of the photodetachment cross section is investigated within the context of Dyson orbital calculations.

摘要

使用慢电子速度映射成像技术获得低温冷却的 X∼A'叔丁基过氧阴离子的光电子能谱。这些光谱显示出高度结构化的谱带，对应于中性自由基的 X∼A″和 A∼A 电子态的脱附，分辨率明显高于以前的光电子能谱。我们报告叔丁基过氧自由基的电子亲和能为 1.1962(20) eV，A∼A 态的能级 T(A∼A)为 0.9602(24) eV。解析出了新的振动结构，为两个中性态提供了几个频率。此外，还在 Dyson 轨道计算的框架内研究了光电子分离截面的阈值行为。