Covalency in Americium(III) Hexachloride

被引：89

作者：

Cross, Justin N. ^{[1
]}

Su, Jing ^{[1
]}

Batista, Enrique R. ^{[1
]}

Cary, Samantha K. ^{[1
]}

Evans, William J. ^{[2
]}

Kozimor, Stosh A. ^{[1
]}

Mocko, Veronika ^{[1
]}

Scott, Brian L. ^{[1
]}

Stein, Benjamin W. ^{[1
]}

Windorff, Cory J. ^{[1
,2
]}

Yang, Ping ^{[1
]}

机构：

[1] Los Alamos Natl Lab, Los Alamos, NM 87545 USA

[2] Univ Calif Irvine, Irvine, CA 92697 USA

来源：

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY | 2017年 / 139卷 / 25期

基金：

美国国家卫生研究院;

关键词：

X-RAY-ABSORPTION; DENSITY-FUNCTIONAL THEORY; CHLORINE K-EDGE; METAL-LIGAND COVALENCY; ELECTRONIC-STRUCTURE; METALLOCENE DICHLORIDES; COORDINATION CHEMISTRY; TRIVALENT LANTHANIDE; CRYSTAL-STRUCTURES; ACTINIDE;

D O I：

10.1021/jacs.7b03755

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

Developing a better understanding of covalency (or orbital mixing) is of fundamental importance. Covalency occupies a central role in directing chemical and physical properties for almost any given compound or material. Hence, the concept of covalency has potential to generate broad and substantial scientific advances, ranging from biological applications to condensed matter physics. Given the importance of orbital mixing combined with the difficultly in measuring covalency, estimating or inferring covalency often leads to fiery debate. Consider the 60-year controversy sparked by Seaborg and co-workers (Diamond, R. M.; Street, K., Jr.; Seaborg, G. T. J. Am. Chem. Soc. 1954, 76, 1461) when it was proposed that covalency from 5f-orbitals contributed to the unique behavior of americium in chloride matrixes. Herein, we describe the use of ligand K-edge X-ray absorption spectroscopy (XAS) and electronic structure calculations to quantify the extent of covalent bonding in arguably one of the most difficult systems to study, the Am-Cl interaction within AmCl63-. We observed both 5f- and 6d-orbital mixing with the Cl-3p orbitals; however, contributions from the 6d-orbitals were more substantial. Comparisons with the isoelectronic EuCl63- indicated that the amount of Cl 3p-mixing with Eu-III Sd-orbitals was similar to that observed with the Am-III 6d-orbitals. Meanwhile, the results confirmed Seaborg's 1954 hypothesis that Am-III 5f-orbital covalency was more substantial than 4f-orbital mixing for Eu-III.

引用

页码：8667 / 8677

页数：11

共 127 条

[1] Evidence for covalence in a N-donor complex of americium(III) [J].