Role of Atomic Electronics in f-Element Bond Formation: Bond Energies of Lanthanide and Actinide Oxide Molecules
Role of Atomic Electronics in f-Element Bond Formation: Bond Energies of Lanthanide and Actinide Oxide Molecules
复制标题
DOI：
10.1021/jp035003n
复制
发表时间：
2003-08
影响因子：
2.9
通讯作者：
J. Gibson
中科院分区：
文献类型：
--
作者：
J. Gibson
从科学和技术的角度来看，金属氧化物分子由于其基本性质和在高温蒸发等过程中的作用而特别令人感兴趣。一个基本和重要的性质是中性和离子一氧化物分子BDE[MO]和BDE[MO+]中金属中心和氧之间的键能。对于4f区镧系元素（Ln）和5 f区锕系元素（An）内过渡金属，已经证明许多化学性质可以从孤立金属原子或离子的电子结构和能量学合理化。在目前的工作中，开发的关系，可靠地预测已知的BDE[LnO]，BDE[LnO+]，BDE[AnO]，和BDE[AnO+]的能量从光谱确定的电子特性;这种关系是用来估计未知的键能。一个值得注意的结果是，有效的金属中心和氧原子之间的键合需要两个不成对的价d电子在这些物种。
Metal oxide molecules are of particular interest from both a scientific and technological perspective in view of their elementary nature and role in such processes as high-temperature vaporization. A fundamental and important property is the bond energy between the metal center and the oxygen in neutral and ionic monoxide molecules, BDE[MO] and BDE[MO+]. For the 4f-block lanthanide (Ln) and 5f-block actinide (An) inner transition metals, it has been demonstrated that many chemical properties can be rationalized from the electronic structures and energetics of the isolated metal atom or ion. In the present work, a relationship is developed to reliably predict known BDE[LnO], BDE[LnO+], BDE[AnO], and BDE[AnO+] energies from spectroscopically determined electronic properties; this relationship is employed to estimate unknown bond energies. A notable implication of the results is that effective bonding between the metal center and the oxygen atom in these species requires two unpaired valence d electrons.