JILA, NIST, and Department of Chemistry and Biochemistry, University of Colorado, Boulder, Colorado 80309, USA.
J Phys Chem A. 2010 Apr 1;114(12):4017-30. doi: 10.1021/jp910675n.
If a negative ion has vibrational energy in excess of the binding energy of its most weakly bound electron, the anion can undergo vibrational autodetachment, similar to thermionic emission. When this effect occurs after targeted infrared excitation of a specific vibrational mode in the anion, it encodes information on the intramolecular vibrational relaxation processes that take place between excitation and electron emission. We present examples on how vibrational autodetachment can be used to obtain infrared spectra of molecular anions, and we discuss how a vibrational autodetachment photoelectron spectrum can be modeled, using vibrational autodetachment after excitation of CH stretching modes of nitromethane anions as a case study.
如果负离子的振动能超过其最弱束缚电子的结合能，则阴离子可以经历振动自脱附，类似于热电子发射。当这种效应在阴离子中特定振动模式的靶向红外激发后发生时，它编码了关于激发和电子发射之间发生的分子内振动弛豫过程的信息。我们展示了如何使用振动自脱附来获得分子阴离子的红外光谱的示例，并讨论了如何使用振动自脱附模型来模拟振动自脱附光电电子光谱，以硝基甲烷阴离子的 CH 伸缩模式激发后的振动自脱附为例。
