Endohedral metal–metal-bonding fullerenes, in which encapsulated metals form covalent metal–metal bonds inside, are an emerging class of endohedral metallofullerenes. Herein, we reported quantum-chemical studies on the electronic structures, chemical bonding, and dynamic fluxionality behavior of endohedral metal–metal-bonding fullerenes Lu2@C2n (2n = 76–88). Multiple bonding analysis approaches, including molecular orbital analysis, the natural bond orbital analysis, electron localization function, adaptive natural density partitioning analysis, and quantum theory of atoms in molecules, have unambiguously revealed one two-center two-electron σ covalent bond between two Lu ions in fullerenes. Energy decomposition analysis with the natural orbitals for chemical valence method on the bonding nature between the encapsulated metal dimer and the fullerene cage suggested the existence of two covalent bonds between the metal dimer and fullerenes, giving rise to a covalent bonding nature between the metal dimer and fullerene cage and a formal charge model of [Lu2]2+@[C2n]2−. For Lu2@C76, the dynamic fluxionality behavior of the metal dimer Lu2 inside fullerene C76 has been revealed via locating the transition state with an energy barrier of 5 kcal/mol. Further energy decomposition analysis calculations indicate that the energy barrier is controlled by a series of terms, including the geometric deformation energy, electrostatic interaction, and orbital interactions.
Skip Nav Destination
,
,
,
,
,
,
Article navigation
14 November 2022
Research Article|
November 10 2022
Understanding electronic structures, chemical bonding, and fluxional behavior of Lu2@C2n (2n = 76–88) by a theoretical study
Special Collection:
Nature of the Chemical Bond
Yuan Shui
;
Yuan Shui
(Data curation, Investigation, Visualization, Writing – original draft)
1
MOE Key Laboratory for Non-Equilibrium Synthesis and Modulation of Condensed Matter, School of Physics, Xi’an Jiaotong University
, Xi’an 710049, Shaanxi, China
Search for other works by this author on:
Gerui Pei;
Gerui Pei
(Data curation, Investigation, Visualization)
1
MOE Key Laboratory for Non-Equilibrium Synthesis and Modulation of Condensed Matter, School of Physics, Xi’an Jiaotong University
, Xi’an 710049, Shaanxi, China
Search for other works by this author on:
Pei Zhao
;
Pei Zhao
a)
(Investigation, Validation, Visualization, Writing – review & editing)
2
Research Center for Computational Science, Institute for Molecular Science
, Nishigonaka 38, Myodaiji, Okazaki 444-8585, Japan
Search for other works by this author on:
Mo Xiong;
Mo Xiong
(Data curation)
1
MOE Key Laboratory for Non-Equilibrium Synthesis and Modulation of Condensed Matter, School of Physics, Xi’an Jiaotong University
, Xi’an 710049, Shaanxi, China
Search for other works by this author on:
Sidian Li;
Sidian Li
(Writing – review & editing)
3
Nanocluster Laboratory, Institute of Molecular Science, Shanxi University
, Taiyuan 030006, China
Search for other works by this author on:
Masahiro Ehara
;
Masahiro Ehara
(Software, Writing – review & editing)
2
Research Center for Computational Science, Institute for Molecular Science
, Nishigonaka 38, Myodaiji, Okazaki 444-8585, Japan
Search for other works by this author on:
Tao Yang
Tao Yang
b)
(Conceptualization, Funding acquisition, Project administration, Software, Supervision, Writing – review & editing)
1
MOE Key Laboratory for Non-Equilibrium Synthesis and Modulation of Condensed Matter, School of Physics, Xi’an Jiaotong University
, Xi’an 710049, Shaanxi, China
b)Author to whom correspondence should be addressed: [email protected]
Search for other works by this author on:
Yuan Shui
1
Gerui Pei
1
Pei Zhao
2,a)
Mo Xiong
1
Sidian Li
3
Masahiro Ehara
2
Tao Yang
1,b)
1
MOE Key Laboratory for Non-Equilibrium Synthesis and Modulation of Condensed Matter, School of Physics, Xi’an Jiaotong University
, Xi’an 710049, Shaanxi, China
2
Research Center for Computational Science, Institute for Molecular Science
, Nishigonaka 38, Myodaiji, Okazaki 444-8585, Japan
3
Nanocluster Laboratory, Institute of Molecular Science, Shanxi University
, Taiyuan 030006, China
a)
E-mail: [email protected]
b)Author to whom correspondence should be addressed: [email protected]
Note: This paper is part of the JCP Special Topic on Nature of the Chemical Bond.
J. Chem. Phys. 157, 184306 (2022)
Article history
Received:
May 26 2022
Accepted:
October 03 2022
Citation
Yuan Shui, Gerui Pei, Pei Zhao, Mo Xiong, Sidian Li, Masahiro Ehara, Tao Yang; Understanding electronic structures, chemical bonding, and fluxional behavior of Lu2@C2n (2n = 76–88) by a theoretical study. J. Chem. Phys. 14 November 2022; 157 (18): 184306. https://doi.org/10.1063/5.0100652
Download citation file:
Pay-Per-View Access
$40.00
Sign In
You could not be signed in. Please check your credentials and make sure you have an active account and try again.
Citing articles via
DeePMD-kit v2: A software package for deep potential models
Jinzhe Zeng, Duo Zhang, et al.
CREST—A program for the exploration of low-energy molecular chemical space
Philipp Pracht, Stefan Grimme, et al.
Related Content
Dual structural fluxionality in the copper borozene complex Cu3B8−: A two-layered molecular rotor
J. Chem. Phys. (November 2024)
Fluxional behaviour of Sc3N in endohedral Sc3N@C80
AIP Conf. Proc. (October 2002)
Fluxional and aromatic behavior in small magic silicon clusters: A full ab initio study of Si n , Si n 1 − , Si n 2 − , and Si n 1 + , n = 6 , 10 clusters
J. Chem. Phys. (July 2007)