Photoelectron spectroscopy and electronic structure of clusters of the group V elements. II. Tetramers: Strong Jahn–Teller coupling in the tetrahedral 2E ground states of P+4, As+4, and Sb+4
Photoelectron spectroscopy and electronic structure of clusters of the group V elements. II. Tetramers: Strong Jahn–Teller coupling in the tetrahedral 2E ground states of P+4, As+4, and Sb+4
复制标题
V 族元素簇的光电子能谱和电子结构：P+4、As+4 和 Sb+4 四面体 2E 基态中的强 Jahn-Teller 耦合。
DOI：
10.1063/1.459698
复制
发表时间：
1990
影响因子：
4.4
通讯作者：
E. Grant
中科院分区：
文献类型：
--
作者：
Lai‐Sheng Wang;B. Niu;Yuan‐Pern Lee;D. A. Shirley;E. Ghelichkhani;E. Grant
对V族元素P4、As4和Sb4的四聚体簇进行了高分辨率的HeI （584 A）光电子能谱分析。光谱证实了四面体P+4、As+4和Sb+4的基态在ν2(e)振动坐标上的畸变是不稳定的。本文对E⊗E Jahn-Teller问题进行了详细的处理，得到了模拟光谱，并与实验光谱进行了比较。P+4的振动计算扩展到二阶（二次耦合），解释了其光电子能谱中部分解析的振动结构。得到了P+4的Jahn-Teller稳定能为0.65 eV，其基态具有高度畸变和高通量的特征。对As+4和Sb+4进行了纯线性Jahn-Teller耦合计算，得到的稳定能分别为0.84 eV和1.4 eV，与实验光谱具有很好的定性一致性。
High resolution HeI (584 A) photoelectron spectra have been obtained for the tetrameric clusters of the group V elements: P4, As4, and Sb4. The spectra establish that the ground 2E states of tetrahedral P+4, As+4, and Sb+4 are unstable with respect to distortion in the ν2(e) vibrational coordinate. The E⊗e Jahn–Teller problem has been treated in detail, yielding simulated spectra to compare with experimental ones. Vibronic calculations, extended to second order (quadratic coupling) for P+4, account for vibrational structure which is partially resolved in its photoelectron spectrum. A Jahn–Teller stabilization energy of 0.65 eV is derived for P+4, which can be characterized in its ground vibronic state as being highly distorted, and highly fluxional. Linear‐only Jahn–Teller coupling calculations performed for As+4 and Sb+4, show good qualitative agreement with experimental spectra, yielding stabilization energies of 0.84 and 1.4 eV, respectively.