Geometries, Electronic Structures, Bonding Properties, and Stability Strategy of Endohedral Metallofullerenes TM@C28 (TM = Sc−, Y−, La−, Ti, Zr, Hf, V+, Nb+, Ta+)

We performed quantum chemical calculations on the geometries, electronic structures, bonding properties, and stability strategy of endohedral metallofullerenes TM@C28 (TM = Sc−, Y−, La−, Ti, Zr, Hf, V<sup&...

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Main Authors:	Dong Liu, Yuan Shui, Tao Yang
Format:	Article
Language:	English
Published:	MDPI AG 2024-01-01
Series:	Inorganics
Subjects:	fullerenes quantum-chemical calculations chemical bonding stability
Online Access:	https://www.mdpi.com/2304-6740/12/2/40

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author	Dong Liu Yuan Shui Tao Yang
author_facet	Dong Liu Yuan Shui Tao Yang
author_sort	Dong Liu
collection	DOAJ
description	We performed quantum chemical calculations on the geometries, electronic structures, bonding properties, and stability strategy of endohedral metallofullerenes TM@C<sub>28</sub> (TM = Sc<sup>−</sup>, Y<sup>−</sup>, La<sup>−</sup>, Ti, Zr, Hf, V<sup>+</sup>, Nb<sup>+</sup>, Ta<sup>+</sup>). Our calculations revealed that there are three different lowest-energy structures with C<sub>2v</sub>, C<sub>3v</sub>, and T<sub>d</sub> symmetries for TM@C<sub>28</sub>. The HOMO–LUMO gap of all these structures ranges from 1.35 eV to 2.31 eV, in which [V@C<sub>28</sub>]<sup>+</sup> has the lowest HOMO–LUMO gap of 1.35 eV. The molecular orbitals are mainly composed of fullerene cage orbitals and slightly encapsulated metal orbitals. The bonding analysis on the metal–cage interactions reveals they are dominated by the Coulomb term ΔE<sub>elstat</sub> and the orbital interaction term ΔE<sub>orb</sub>, in which the orbital interaction term ΔE<sub>orb</sub> contributes more than the Coulomb term ΔE<sub>elstat</sub>. The addition of one or two CF<sub>3</sub> groups to [V@C<sub>28</sub>]<sup>+</sup> could increase the HOMO–LUMO gap and further increase the stability of [V@C<sub>28</sub>]<sup>+</sup>.
first_indexed	2024-03-07T22:27:57Z
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institution	Directory Open Access Journal
issn	2304-6740
language	English
last_indexed	2024-03-07T22:27:57Z
publishDate	2024-01-01
publisher	MDPI AG
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series	Inorganics
spelling	doaj.art-c341cff5ffc14df8b24b12c579ad60ec2024-02-23T15:21:18ZengMDPI AGInorganics2304-67402024-01-011224010.3390/inorganics12020040Geometries, Electronic Structures, Bonding Properties, and Stability Strategy of Endohedral Metallofullerenes TM@C<sub>28</sub> (TM = Sc<sup>−</sup>, Y<sup>−</sup>, La<sup>−</sup>, Ti, Zr, Hf, V<sup>+</sup>, Nb<sup>+</sup>, Ta<sup>+</sup>)Dong Liu0Yuan Shui1Tao Yang2MOE Key Laboratory for Non-Equilibrium Synthesis and Modulation of Condensed Matter, School of Physics, Xi’an Jiaotong University, Xi’an 710049, ChinaMOE Key Laboratory for Non-Equilibrium Synthesis and Modulation of Condensed Matter, School of Physics, Xi’an Jiaotong University, Xi’an 710049, ChinaMOE Key Laboratory for Non-Equilibrium Synthesis and Modulation of Condensed Matter, School of Physics, Xi’an Jiaotong University, Xi’an 710049, ChinaWe performed quantum chemical calculations on the geometries, electronic structures, bonding properties, and stability strategy of endohedral metallofullerenes TM@C<sub>28</sub> (TM = Sc<sup>−</sup>, Y<sup>−</sup>, La<sup>−</sup>, Ti, Zr, Hf, V<sup>+</sup>, Nb<sup>+</sup>, Ta<sup>+</sup>). Our calculations revealed that there are three different lowest-energy structures with C<sub>2v</sub>, C<sub>3v</sub>, and T<sub>d</sub> symmetries for TM@C<sub>28</sub>. The HOMO–LUMO gap of all these structures ranges from 1.35 eV to 2.31 eV, in which [V@C<sub>28</sub>]<sup>+</sup> has the lowest HOMO–LUMO gap of 1.35 eV. The molecular orbitals are mainly composed of fullerene cage orbitals and slightly encapsulated metal orbitals. The bonding analysis on the metal–cage interactions reveals they are dominated by the Coulomb term ΔE<sub>elstat</sub> and the orbital interaction term ΔE<sub>orb</sub>, in which the orbital interaction term ΔE<sub>orb</sub> contributes more than the Coulomb term ΔE<sub>elstat</sub>. The addition of one or two CF<sub>3</sub> groups to [V@C<sub>28</sub>]<sup>+</sup> could increase the HOMO–LUMO gap and further increase the stability of [V@C<sub>28</sub>]<sup>+</sup>.https://www.mdpi.com/2304-6740/12/2/40fullerenesquantum-chemical calculationschemical bondingstability
spellingShingle	Dong Liu Yuan Shui Tao Yang Geometries, Electronic Structures, Bonding Properties, and Stability Strategy of Endohedral Metallofullerenes TM@C<sub>28</sub> (TM = Sc<sup>−</sup>, Y<sup>−</sup>, La<sup>−</sup>, Ti, Zr, Hf, V<sup>+</sup>, Nb<sup>+</sup>, Ta<sup>+</sup>) Inorganics fullerenes quantum-chemical calculations chemical bonding stability
title	Geometries, Electronic Structures, Bonding Properties, and Stability Strategy of Endohedral Metallofullerenes TM@C<sub>28</sub> (TM = Sc<sup>−</sup>, Y<sup>−</sup>, La<sup>−</sup>, Ti, Zr, Hf, V<sup>+</sup>, Nb<sup>+</sup>, Ta<sup>+</sup>)
title_full	Geometries, Electronic Structures, Bonding Properties, and Stability Strategy of Endohedral Metallofullerenes TM@C<sub>28</sub> (TM = Sc<sup>−</sup>, Y<sup>−</sup>, La<sup>−</sup>, Ti, Zr, Hf, V<sup>+</sup>, Nb<sup>+</sup>, Ta<sup>+</sup>)
title_fullStr	Geometries, Electronic Structures, Bonding Properties, and Stability Strategy of Endohedral Metallofullerenes TM@C<sub>28</sub> (TM = Sc<sup>−</sup>, Y<sup>−</sup>, La<sup>−</sup>, Ti, Zr, Hf, V<sup>+</sup>, Nb<sup>+</sup>, Ta<sup>+</sup>)
title_full_unstemmed	Geometries, Electronic Structures, Bonding Properties, and Stability Strategy of Endohedral Metallofullerenes TM@C<sub>28</sub> (TM = Sc<sup>−</sup>, Y<sup>−</sup>, La<sup>−</sup>, Ti, Zr, Hf, V<sup>+</sup>, Nb<sup>+</sup>, Ta<sup>+</sup>)
title_short	Geometries, Electronic Structures, Bonding Properties, and Stability Strategy of Endohedral Metallofullerenes TM@C<sub>28</sub> (TM = Sc<sup>−</sup>, Y<sup>−</sup>, La<sup>−</sup>, Ti, Zr, Hf, V<sup>+</sup>, Nb<sup>+</sup>, Ta<sup>+</sup>)
title_sort	geometries electronic structures bonding properties and stability strategy of endohedral metallofullerenes tm c sub 28 sub tm sc sup sup y sup sup la sup sup ti zr hf v sup sup nb sup sup ta sup sup
topic	fullerenes quantum-chemical calculations chemical bonding stability
url	https://www.mdpi.com/2304-6740/12/2/40
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Geometries, Electronic Structures, Bonding Properties, and Stability Strategy of Endohedral Metallofullerenes TM@C<sub>28</sub> (TM = Sc<sup>−</sup>, Y<sup>−</sup>, La<sup>−</sup>, Ti, Zr, Hf, V<sup>+</sup>, Nb<sup>+</sup>, Ta<sup>+</sup>)

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