Nagaoka Shin-Ichi, Kakiuchi Takuhiro, Ohshita Joji, Takahashi Osamu, Hikosaka Yasumasa
Department of Chemistry, Faculty of Science and Graduate School of Science and Engineering, Ehime University , Matsuyama 790-8577, Japan.
Graduate School of Medicine and Pharmaceutical Sciences, University of Toyama , Toyama 930-0194, Japan.
J Phys Chem A. 2016 Dec 22;120(50):9907-9915. doi: 10.1021/acs.jpca.6b09399. Epub 2016 Dec 12.
Site-specific electron relaxations caused by Si:2p core-level photoionizations in FSiCHCHSi(CH) and ClSiCHCHSi(CH) vapors have been studied by means of the photoelectron Auger electron coincidence spectroscopy. FSiCHCHSi(CH) shows almost 100% site-specificity in fragmentation caused by the Si:2p ionization. However, substitution of Cl for F of FSiCHCHSi(CH) considerably reduces the site-specificity at the Si atom bonded to three halogen atoms, with the site-specificity at the Si site bonded to three methyl groups remaining largely unchanged. The site-specificity reduction in ClSiCHCHSi(CH) is considered to take place during the transient period between Si:LVV Auger electron emission and the subsequent fragmentation. The reason for the reduction can be explained in terms of some differences between these two molecules in the LVV Auger decay at the Si site bonded to the three halogen atoms.
通过光电子俄歇电子符合光谱法研究了在FSiCHCHSi(CH)和ClSiCHCHSi(CH)蒸气中由Si:2p芯能级光电离引起的位点特异性电子弛豫。FSiCHCHSi(CH)在由Si:2p电离引起的碎片化过程中显示出几乎100%的位点特异性。然而,用Cl取代FSiCHCHSi(CH)中的F会显著降低与三个卤素原子键合的Si原子处的位点特异性,而与三个甲基键合的Si位点处的位点特异性基本保持不变。ClSiCHCHSi(CH)中位点特异性的降低被认为发生在Si:LVV俄歇电子发射和随后的碎片化之间的瞬态期间。这种降低的原因可以用这两个分子在与三个卤素原子键合的Si位点处的LVV俄歇衰变中的一些差异来解释。