Ray Manisha, Felton Jeremy A, Kafader Jared O, Topolski Josey E, Jarrold Caroline Chick
Department of Chemistry, Indiana University, 800 East Kirkwood Avenue, Bloomington, Indiana 47405, USA.
J Chem Phys. 2015 Feb 14;142(6):064305. doi: 10.1063/1.4907714.
The photoelectron spectrum of CeO(-) exhibits what appears to be a single predominant electronic transition over an energy range in which numerous close-lying electronic states of CeO neutral are well known. The photoelectron spectrum of Ce(OH)2 (-), a molecule in which the Ce atom shares the same formal oxidation state as the Ce atom in CeO(-), also exhibits what appears to be a single transition. From the spectra, the adiabatic electron affinities of CeO and Ce(OH)2 are determined to be 0.936 ± 0.007 eV and 0.69 ± 0.03 eV, respectively. From the electron affinity of CeO, the CeO(-) bond dissociation energy was determined to be 7.7 eV, 0.5 eV lower than the neutral bond dissociation energy. The ground state orbital occupancies of both CeO(-) and Ce(OH)2 (-) are calculated to have 4f 6s(2) Ce(+) superconfigurations, with open-shell states having 4f5d6s superconfiguration predicted to be over 1 eV higher in energy. Low-intensity transitions observed at higher electron binding energies in the spectrum of CeO(-) are tentatively assigned to the (1)Σ(+) (Ω = 0) state of CeO with the Ce+26s2 superconfiguration.
CeO(-)的光电子能谱在一个能量范围内呈现出似乎是单一的主要电子跃迁,而在这个能量范围内,CeO中性分子的众多紧密相邻的电子态是广为人知的。Ce(OH)2 (-)分子中Ce原子的形式氧化态与CeO(-)中Ce原子相同,其光电子能谱也呈现出似乎是单一的跃迁。根据这些能谱,CeO和Ce(OH)2的绝热电子亲和能分别确定为0.936±0.007 eV和0.69±0.03 eV。根据CeO的电子亲和能,CeO(-)的键解离能确定为7.7 eV,比中性键解离能低0.5 eV。计算得出CeO(-)和Ce(OH)2 (-)的基态轨道占据情况均为4f 6s(2) Ce(+)超构型,预计开壳层态的4f5d6s超构型能量高出1 eV以上。在CeO(-)能谱中较高电子结合能处观察到的低强度跃迁初步归属于具有Ce+26s2超构型的CeO的(1)Σ(+) (Ω = 0)态。