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Magnetic-bottle and velocity-map imaging photoelectron spectroscopy of APS? (A = C14H10 or anthracene): electron structure, spin-orbit coupling of APS?, and dipole-bound state of APS?
Xue-BinWang
Author NameAffiliationE-mail
Xue-BinWang Environmental Molecular Sciences Laboratory, Pacific Northwest National Laboratory, P. O. Box 999, MS K8-91, Richland, WA 99352, USA xuebin.wang@pnnl.gov 
Abstract:
Gaseous dibenzo-7-phosphanorbornadiene P-sulfide anions APS? (A = C14H10 or anthracene) were generated via electrospray ionization, and characterized by magnetic-bottle photoelectron spectroscopy, velocity-map imaging (VMI) photoelectron spectroscopy, and quantum chemical calculations. The electron affinity (EA) and spin-orbit splitting (SO) of the APS? radical are determined from the photoelectron spectra and Franck?Condon factor simulations to be EA = 2.62 ± 0.05 eV and SO splitting = 43 ± 7 meV. VMI photoelectron images show strong and sharp peaks near detachment threshold with an identical electron kinetic energy (eKE) of 17.9 meV at three different detachment wavelengths, which are therefore assigned due to autodetachment from dipole-bound anion states. The B3LYP/6-31++g(d,p) calculations indicate APS? has a dipole moment of 3.31 Debye, large enough to support a dipole-bound electron.
Key words:  Dibenzo-7-phosphanorbornadiene P-sulfide, electron structure, spin-orbit coupling, dipole-bound state, VMI photoelectron spectroscopy
FundProject:
Magnetic-bottle and velocity-map imaging photoelectron spectroscopy of APS? (A = C14H10 or anthracene): electron structure, spin-orbit coupling of APS?, and dipole-bound state of APS?
Xue-BinWang
摘要:
Dibenzo-7-phosphanorbornadiene P-sulfide anions APS? (A = C14H10, 蒽) 是一种非常重要有机磷分子前驱体。该类化合物通过释放有机成分蒽,进而得到纯净的各种无机磷小分子。我们实验室通过电喷雾离子技术将其从溶液相转移到气相中, 然后通过磁瓶式光电子飞行时间能谱和速度成像光电子能谱,并结合计算对其几何和电子结构进行研究。通过不同波长的光谱对比以及Franck?Condon模拟,得到其电子亲和势 (2.62 ± 0.05 eV) 和自旋轨道劈裂 (43 ± 7 meV)。实验光谱不仅给出丰富的电子结构信息,而且呈现一个非常独特的现象: 不同波长 (440, 450,460 nm) 的速度成像光电子能谱在同一位置均出现一个尖锐的峰。理论计算显示APS有足够大偶极矩 (3.31 D), 能够产生自旋偶极电子。进一步的计算将具有相同动能 (17.9 meV) 的强峰归属来自振动-电子态耦合引起的电子自动脱附的态-态跃迁过程。通过对其几何结构和电子结构的研究,有助于理解磷转移反应中化学键的断裂和形成。
关键词:  Dibenzo-7-phosphanorbornadiene P-sulfide anions,电子结构,自旋轨道耦合,偶极束缚态(DBS),速度成像光电子能谱
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