Postler Johannes, Renzler Michael, Kaiser Alexander, Huber Stefan E, Probst Michael, Scheier Paul, Ellis Andrew M
Institut für Ionenphysik und Angewandte Physik, Universität Innsbruck , Technikerstr. 25, A-6020 Innsbruck, Austria.
Department of Chemistry, University of Leicester , University Road, Leicester, LE1 7RH, U. K.
J Phys Chem C Nanomater Interfaces. 2015 Sep 10;119(36):20917-20922. doi: 10.1021/acs.jpcc.5b05260. Epub 2015 Aug 11.
Electron addition to cobalt tricarbonyl nitrosyl (Co(CONO) and its clusters has been explored in helium nanodroplets. Anions were formed by adding electrons with controlled energies, and reaction products were identified by mass spectrometry. Dissociative electron attachment (DEA) to the Co(CO)NO monomer gave reaction products similar to those reported in earlier gas phase experiments. However, loss of NO was more prevalent than loss of CO, in marked contrast to the gas phase. Since the Co-N bond is significantly stronger than the Co-C bond, this preference for NO loss must be driven by selective reaction dynamics at low temperature. For [Co(CO)NO] clusters, the DEA chemistry is similar to that of the monomer, but the anion yields as a function of electron energy show large differences, with the relatively sharp resonances of the monomer being replaced by broad profiles peaking at much higher electron energies. A third experiment involved DEA of Co(CO)NO on a C molecule in an attempt to simulate the effect of a surface. Once again, broad ion yield curves are seen, but CO loss now becomes the most probable reaction channel. The implication of these findings for understanding focused electron beam induced deposition of cobalt is described.
在氦纳米液滴中研究了向三羰基亚硝酰钴（Co(CO)NO）及其团簇添加电子的过程。通过添加具有可控能量的电子形成阴离子，并通过质谱法鉴定反应产物。对Co(CO)NO单体的解离电子附着（DEA）产生的反应产物与早期气相实验中报道的产物相似。然而，与气相情况形成鲜明对比的是，NO的损失比CO的损失更为普遍。由于Co-N键明显强于Co-C键，这种对NO损失的偏好必定是由低温下的选择性反应动力学驱动的。对于[Co(CO)NO]团簇，DEA化学性质与单体相似，但作为电子能量函数的阴离子产率显示出很大差异，单体相对尖锐的共振被在高得多的电子能量处达到峰值的宽峰所取代。第三个实验涉及在C分子上对Co(CO)NO进行DEA，以试图模拟表面的影响。再次观察到宽离子产率曲线，但现在CO损失成为最可能的反应通道。描述了这些发现对于理解聚焦电子束诱导钴沉积的意义。
