Understanding the Electronic Structure and Chemical Bonding in the 2D Fullerene Monolayer

Zhao, Xiao-Kun1,2,3; Zhang, Yang-Yang3,4; Zhao, Jing1,2; Hu, Han-Shi1,2; Li, Jun1,2,3,4

2024-06-12

10.1021/acs.inorgchem.4c00811

INORGANIC CHEMISTRY   影响因子和分区

0020-1669

1520-510X

Recently synthesized two-dimensional (2D) monolayer quasi-hexagonal-phase fullerene (qHPC(60)) demonstrates excellent thermodynamic stability. Within this monolayer, each fullerene cluster is surrounded by six adjacent C-60 cages along an equatorial plane and is connected by both C-C single bonds and [2 + 2] cycloaddition bonds that serve as bridges. In this study, we investigate the stability mechanism of the 2D qHPC(60) monolayer by examining the electronic structure and chemical bonding through state-of-the-art theoretical methodologies. Density functional theory (DFT) studies reveal that 2D qHPC(60) possesses a moderate direct electronic band gap of 1.46 eV, close to the experimental value (1.6 eV). It is found that the intermolecular bridge bonds play a crucial role in enhancing the charge flow and redistribution among C-60 cages, leading to the formation of dual pi-aromaticity within the C-60 sphere and stabilizing the 2D framework structure. Furthermore, we identify a series of delocalized superatom molecular orbitals (SAMOs) within the 2D qHPC(60) monolayer, exhibiting atomic orbital-like behavior and hybridization to form nearly free-electron (NFE) bands with sigma/pi bonding and sigma*/pi* antibonding properties. Our findings provide insights into the design and potential applications of NFE bands derived from SAMOs in 2D qHPC(60) monolayers.

SCI ; EI

英语

通讯

Chemistry

Chemistry, Inorganic & Nuclear

WOS:001247434900001

AMER CHEMICAL SOC

CHEMISTRY

Web of Science

1.Tsinghua Univ, Dept Chem, Beijing 100084, Peoples R China
2.Tsinghua Univ, Engn Res Ctr Adv Rare Earth Mat, Minist Educ, Beijing 100084, Peoples R China
3.Southern Univ Sci & Technol, Dept Chem, Shenzhen 518055, Peoples R China
4.Chinese Acad Sci, Ganjiang Innovat Acad, Fundamental Sci Ctr Rare Earths, Ganzhou 341000, Peoples R China

Zhao, Xiao-Kun,Zhang, Yang-Yang,Zhao, Jing,et al. Understanding the Electronic Structure and Chemical Bonding in the 2D Fullerene Monolayer[J]. INORGANIC CHEMISTRY,2024,63(25).

Zhao, Xiao-Kun,Zhang, Yang-Yang,Zhao, Jing,Hu, Han-Shi,&Li, Jun.(2024).Understanding the Electronic Structure and Chemical Bonding in the 2D Fullerene Monolayer.INORGANIC CHEMISTRY,63(25).

Zhao, Xiao-Kun,et al."Understanding the Electronic Structure and Chemical Bonding in the 2D Fullerene Monolayer".INORGANIC CHEMISTRY 63.25(2024).