Stabilizing heteroatom-centered 16-vertex group 11 tetrahedral architectures

Bonding and structural considerations toward versatile endohedral species

Franck Gam, Ramiro Arratia-Pérez, Samia Kahlal, Jean Yves Saillard, Alvaro Muñoz-Castro

Research output: Contribution to journalArticle

Abstract

Density functional theory (DFT) calculations were carried out on a series of clusters made of a centered tetrahedral 16-atom superatomic cage having 20 or 18 jellium electrons (je) and structurally related to [Au20], namely [X@M16] (M = group 11; X = group 2, 4, 12, 14 element). Such species provide further information of how two different electron counts offer a more preferred endohedral situation for specific group elements. Calculations show that the encapsulated atom provides supplementary orbitals to stabilize the bonding M16 MO's. Different favored electron counts are found depending on the nature of the encapsulated atom, as observed by the formation of 20-je species when encapsulating a group 14 element and 18-je species when encapsulating a group 2 element. In addition, the capabilities to enable reactive sites along the cage structure are found via the formation of σ holes at the coinage-metal edges, as shown by their electrostatic potential surface. Such naked species, which constitute an interesting addition to libraries of examples as small models for doped M(111) surfaces of fcc metals, reveal that different superatomic electronic configurations can favor the encapsulation of certain group elements. These results can guide further design of endohedral species.

Original languageEnglish
Article numbere26038
JournalInternational Journal of Quantum Chemistry
DOIs
Publication statusPublished - 12 Aug 2019

Fingerprint

apexes
Electrons
encapsulating
Atoms
electrons
Coinage
Metals
Alkaline Earth Metals
atoms
Encapsulation
Density functional theory
Electrostatics
metals
electrostatics
density functional theory
orbitals
configurations
electronics

Keywords

  • DFT
  • heteroatom doping
  • superatoms
  • tetrahedral structure

ASJC Scopus subject areas

  • Atomic and Molecular Physics, and Optics
  • Condensed Matter Physics
  • Physical and Theoretical Chemistry

Cite this

@article{3176023b86b1447e8bc7fb63268a120e,
title = "Stabilizing heteroatom-centered 16-vertex group 11 tetrahedral architectures: Bonding and structural considerations toward versatile endohedral species",
abstract = "Density functional theory (DFT) calculations were carried out on a series of clusters made of a centered tetrahedral 16-atom superatomic cage having 20 or 18 jellium electrons (je) and structurally related to [Au20], namely [X@M16] (M = group 11; X = group 2, 4, 12, 14 element). Such species provide further information of how two different electron counts offer a more preferred endohedral situation for specific group elements. Calculations show that the encapsulated atom provides supplementary orbitals to stabilize the bonding M16 MO's. Different favored electron counts are found depending on the nature of the encapsulated atom, as observed by the formation of 20-je species when encapsulating a group 14 element and 18-je species when encapsulating a group 2 element. In addition, the capabilities to enable reactive sites along the cage structure are found via the formation of σ holes at the coinage-metal edges, as shown by their electrostatic potential surface. Such naked species, which constitute an interesting addition to libraries of examples as small models for doped M(111) surfaces of fcc metals, reveal that different superatomic electronic configurations can favor the encapsulation of certain group elements. These results can guide further design of endohedral species.",
keywords = "DFT, heteroatom doping, superatoms, tetrahedral structure",
author = "Franck Gam and Ramiro Arratia-P{\'e}rez and Samia Kahlal and Saillard, {Jean Yves} and Alvaro Mu{\~n}oz-Castro",
year = "2019",
month = "8",
day = "12",
doi = "10.1002/qua.26038",
language = "English",
journal = "International Journal of Quantum Chemistry",
issn = "0020-7608",
publisher = "John Wiley and Sons Inc.",

}

TY - JOUR

T1 - Stabilizing heteroatom-centered 16-vertex group 11 tetrahedral architectures

T2 - Bonding and structural considerations toward versatile endohedral species

AU - Gam, Franck

AU - Arratia-Pérez, Ramiro

AU - Kahlal, Samia

AU - Saillard, Jean Yves

AU - Muñoz-Castro, Alvaro

PY - 2019/8/12

Y1 - 2019/8/12

N2 - Density functional theory (DFT) calculations were carried out on a series of clusters made of a centered tetrahedral 16-atom superatomic cage having 20 or 18 jellium electrons (je) and structurally related to [Au20], namely [X@M16] (M = group 11; X = group 2, 4, 12, 14 element). Such species provide further information of how two different electron counts offer a more preferred endohedral situation for specific group elements. Calculations show that the encapsulated atom provides supplementary orbitals to stabilize the bonding M16 MO's. Different favored electron counts are found depending on the nature of the encapsulated atom, as observed by the formation of 20-je species when encapsulating a group 14 element and 18-je species when encapsulating a group 2 element. In addition, the capabilities to enable reactive sites along the cage structure are found via the formation of σ holes at the coinage-metal edges, as shown by their electrostatic potential surface. Such naked species, which constitute an interesting addition to libraries of examples as small models for doped M(111) surfaces of fcc metals, reveal that different superatomic electronic configurations can favor the encapsulation of certain group elements. These results can guide further design of endohedral species.

AB - Density functional theory (DFT) calculations were carried out on a series of clusters made of a centered tetrahedral 16-atom superatomic cage having 20 or 18 jellium electrons (je) and structurally related to [Au20], namely [X@M16] (M = group 11; X = group 2, 4, 12, 14 element). Such species provide further information of how two different electron counts offer a more preferred endohedral situation for specific group elements. Calculations show that the encapsulated atom provides supplementary orbitals to stabilize the bonding M16 MO's. Different favored electron counts are found depending on the nature of the encapsulated atom, as observed by the formation of 20-je species when encapsulating a group 14 element and 18-je species when encapsulating a group 2 element. In addition, the capabilities to enable reactive sites along the cage structure are found via the formation of σ holes at the coinage-metal edges, as shown by their electrostatic potential surface. Such naked species, which constitute an interesting addition to libraries of examples as small models for doped M(111) surfaces of fcc metals, reveal that different superatomic electronic configurations can favor the encapsulation of certain group elements. These results can guide further design of endohedral species.

KW - DFT

KW - heteroatom doping

KW - superatoms

KW - tetrahedral structure

UR - http://www.scopus.com/inward/record.url?scp=85070719242&partnerID=8YFLogxK

U2 - 10.1002/qua.26038

DO - 10.1002/qua.26038

M3 - Article

JO - International Journal of Quantum Chemistry

JF - International Journal of Quantum Chemistry

SN - 0020-7608

M1 - e26038

ER -