Covalency in the f-element-chalcogen bond computational studies of [M(N(EPH2)2)3] (M = La, U, Pu; E = O, S, Se, Te)

被引：46

作者：

Ingram, Kieran I. M.

Kaltsoyannis, Nikolas

Gaunt, Andrew J.

Neu, Mary P.

机构：

[1] UCL, Dept Chem, London WC1H 0AJ, England

[2] Los Alamos Natl Lab, Div Chem, C IIAC, Los Alamos, NM 87545 USA

来源：

JOURNAL OF ALLOYS AND COMPOUNDS | 2007年 / 444卷

基金：

英国工程与自然科学研究理事会;

关键词：

actinide molecules; DFT; electronic structure; covalency; separation;

D O I：

10.1016/j.jallcom.2007.03.048

中图分类号：

O64 [物理化学（理论化学）、化学物理学];

学科分类号：

070304 ; 081704 ;

摘要：

The geometric and electronic structures of the title complexes have been studied using gradient corrected density functional theory. Excellent agreement is observed between computed r(M-E) and experimental values in analogous Pr-i complexes. Natural charge analysis indicates that the M-E bond becomes less ionic in the order O > S > S > Te, and that this decrease is largest for U and smallest for La. Natural and Mulliken overlap populations suggest increasing M-E covalency as group 16 is descended, and also in the order La < Pu < U for a given chalcogen. Increased covalency down group 16 arises from increased metal d (and s) participation in the bonding, while that from La to Pu and U stems from larger 5f orbital involvement compared with 4f. (c) 2007 Elsevier B.V. All rights reserved.

引用

页码：369 / 375

页数：7

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