Density Functional Theory Study of Transition-Metal Compounds Containing Metal−Metal Bonds. 1. Molecular Structures of Dinuclear Compounds by Complete Geometry Optimization

AbstractThe nature of the actinide-actinide bonds is of fundamental importance to understand the electronic structure of the 5f elements. It has attracted considerable theoretical attention, but little is known experimentally as the synthesis of these chemical bonds remains extremely challenging. Herein, we report a strong covalent Th-Th bond formed between two rarely accessible Th3+ ions, stabilized inside a fullerene cage nanocontainer as Th2@Ih(7)-C80. This compound is synthesized using the arc-discharge method and fully characterized using several techniques. The single-crystal X-Ray diffraction analysis determines that the two Th atoms are separated by 3.816 Å. Both experimental and quantum-chemical results show that the two Th atoms have formal charges of +3 and confirm the presence of a strong covalent Th-Th bond inside Ih(7)-C80. Moreover, density functional theory and ab initio multireference calculations suggest that the overlap between the 7s/6d hybrid thorium orbitals is so large that the bond still exists at Th-Th separations larger than 6 Å. This work demonstrates the authenticity of covalent actinide metal-metal bonds in a stable compound and deepens our fundamental understanding of f element metal bonds.

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Density Functional Theory Study of Ultrashort Metal--Metal Distance in Diberyllium Complexes Bearing Carbene Ligands

10.22541/au.160253878.81571157/v1 ◽

2020 ◽

Author(s):

Lili Sun

Keyword(s):

Density Functional Theory ◽

Density Functional ◽

Density Functional Theory Study ◽

Carbene Ligands ◽

Functional Theory ◽

Metal Metal

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A density functional theory study on the rearrangements of the 6-tricyclo[3.2.1.02,4]octyl cation and its isomers: a walk on the C8H11+ potential energy surface and a peek at molecular structures with AIM

ARKIVOC ◽

10.3998/ark.5550190.0002.c18 ◽

2002 ◽

Vol 2001 (12) ◽

pp. 187-197

Author(s):

Nick Henry Werstiuk ◽

Yi-Gui Wang

Keyword(s):

Density Functional Theory ◽

Potential Energy ◽

Potential Energy Surface ◽

Density Functional ◽

Energy Surface ◽

Molecular Structures ◽

Density Functional Theory Study ◽

Functional Theory

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Predicting bond dissociation energy and bond length for bimetallic diatomic molecules: a challenge for electronic structure theory

Physical Chemistry Chemical Physics ◽

10.1039/c6cp08896a ◽

2017 ◽

Vol 19 (8) ◽

pp. 5839-5854 ◽

Cited By ~ 15

Author(s):

Junwei Lucas Bao ◽

Xin Zhang ◽

Xuefei Xu ◽

Donald G. Truhlar

Keyword(s):

Density Functional Theory ◽

Active Sites ◽

Density Functional ◽

Electronic Structure Theory ◽

Structure Theory ◽

Strongly Correlated ◽

Functional Theory ◽

Metal Metal ◽

Catalytically Active ◽

Metal Bonds

We test the accuracy of Kohn–Sham density functional theory for strongly correlated metal–metal bonds that occur in catalytically active sites and intermediates and examine the orbitals and configurations involved to analyze the results.

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