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团簇内光电离相互作用对 I(-)*CH(3)I 光电子脱附角分布的影响。

The effect of intracluster photoelectron interactions on the angular distribution in I(-)*CH(3)I photodetachment.

机构信息

Department of Chemistry, Washington University, One Brookings Dr., Campus Box 1134, Saint Louis, Missouri 63130, USA.

出版信息

J Chem Phys. 2009 Nov 28;131(20):204306. doi: 10.1063/1.3266936.

Abstract

I(-) and I(-)*CH(3)I velocity mapped photodetachment images are recorded over wavelengths between 270 and 370 nm. Spectral similarities, in conjunction with ab initio calculations show that the cluster anion comprises an atomic iodide anion moiety solvated by a relatively unperturbed CH(3)I molecule. Between 340-370 nm and at 280 nm, free I(-) is produced via a process analogous to dissociative electron attachment within the cluster anion. More strikingly, the photoelectron angular distribution for each species at a given electron kinetic energy is very different, despite detachment occurring from the iodide 5p orbital in each case. These observations reveal the effect of interaction of the photoelectron with the neutral cluster residue and are discussed in terms of resonances associated primarily with the CH(3)I molecule.

摘要

I(-)和 I(-)*CH(3)I 速度映射光电子离解图像记录在 270nm 至 370nm 之间的波长范围内。光谱相似性,再加上从头算计算表明,团簇阴离子由一个原子碘阴离子部分组成,被一个相对未受干扰的 CH(3)I 分子溶剂化。在 340-370nm 之间,并且在 280nm 处,通过类似于簇阴离子内的离解电子附加的过程产生游离 I(-)。更引人注目的是,尽管在每种情况下都是从碘化物 5p 轨道中脱离,但在给定电子动能下每种物质的光电子角分布非常不同。这些观察结果揭示了光电子与中性团簇残基相互作用的影响,并根据主要与 CH(3)I 分子相关的共振进行了讨论。

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