密度泛函理论
分子轨道
价(化学)
电子结构
双原子分子
原子轨道
硅
过渡金属
化学
价电子
电子组态
原子物理学
材料科学
计算化学
离子
电子
物理
分子
有机化学
催化作用
量子力学
生物化学
作者
K. Don Dasitha Gunaratne,Cüneyt Berkdemir,Christopher L. Harmon,A. W. Castleman
摘要
Evolution of electronic properties and the nature of bonding of the 4d-transition metal silicides (ZrSi, NbSi, MoSi and PdSi) are discussed, revealing interesting trends in the transition metal-silicon interactions across the period. The electronic properties of select transition metal silicide diatomics have been determined by anion photoelectron imaging spectroscopy and theoretical methods. The electron binding energy spectra and photoelectron angular distributions obtained by 2.33 eV (532 nm) photons have revealed the distinct features of these diatomics. The theoretical calculations were performed at the density functional theory (DFT) level using the unrestricted B3LYP hybrid functional and at the ab initio unrestricted coupled cluster singles and doubles (triplets) (UCCSD(T)) methods to assign the ground electronic states of the neutral and anionic diatomics. The excited electronic states were calculated by the DFT (TD-DFT)/UB3LYP method. We have observed that the valence molecular orbital configuration of the ZrSi and NbSi anions are significantly different from that of the MoSi and PdSi anions. By combining our experimental and theoretical results, we report that the composition of the highest occupied molecular orbitals shift from a majority of transition metal s- and d-orbital contribution in ZrSi and NbSi, to mainly silicon p-orbital contribution for MoSi and PdSi. We expect these observed atomic scale transition metal-silicon interactions to be of increasing importance with the miniaturization of devices approaching the sub-nanometer size regime.
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