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Title: The Superatom States of Fullerenes and Their Hybridization into the Nearly Free Electron Bands of Fullerites

Abstract

Motivated by the discovery of the superatom states of C₆₀ molecules, we investigate the factors that influence their energy and wave function hybridization into nearly free electron bands in molecular solids. As the n = 3 solutions of the radial Schro¨dinger equation of the central attractive potential consisting of the shortrange C atom core and the long-range collective screening potentials, respectively, located on the icosahedral C60 molecule shell and within its hollow core, superatom states are distinguished by their atom-like orbitals corresponding to different orbital angular momentum states (l = 0, 1, 2,...). Because they are less tightly bound than the π orbitals, that is, the n = 2 states, which are often exploited in the intermolecular electron transport in aromatic organic molecule semiconductors, superatom orbitals hybridize more extensively among aggregated molecules to form bands with nearly free electron dispersion. The prospect of exploiting the strong intermolecular coupling to achieve metal-like conduction in applications such as molecular electronics may be attained by lowering the energy of superatom states from 3.5 eV for single chemisorbed C₆₀ molecules to below the Fermi level; therefore, we study how the superatom state energies depend on factors such as their aggregation into 1D - 3Dmore » solids, cage size, and exo- and endohedral doping by metal atoms. We find, indeed, that if the ionization potential of endohedral atom, such as copper, is sufficiently large, superatom states can form the conduction band in the middle of the gap between the HOMO and LUMO of the parent C₆₀ molecule. Through a plane-wave density functional theory study, we provide insights for a new paradigm for intermolecular electronic interaction beyond the conventional one among the sp n hybridized orbitals of the organic molecular solids that could lead to design of novel molecular materials and quantum structures with extraordinary optical and electronic properties.« less

Authors:
 [1];  [1];  [2];  [3]
  1. Univ. of Pittsburgh, PA (United States)
  2. Univ. of Science and Technology of China, Hefei (China)
  3. Univ. of Pittsburgh, PA (United States); Donostia International Physics Center, San Sebastian (Spain)
Publication Date:
Research Org.:
Pacific Northwest National Lab. (PNNL), Richland, WA (United States). Environmental Molecular Sciences Lab. (EMSL)
Sponsoring Org.:
USDOE
OSTI Identifier:
966648
DOE Contract Number:  
AC05-76RL01830
Resource Type:
Journal Article
Journal Name:
ACS Nano, 3(4):853-864
Additional Journal Information:
Journal Volume: 3; Journal Issue: 4; Journal ID: ISSN 1936-086X
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; FULLERENES; HYBRIDIZATION; IONIZATION POTENTIAL; ORBITAL ANGULAR MOMENTUM; SCHROEDINGER EQUATION; WAVE FUNCTIONS; DENSITY FUNCTIONAL METHOD; ELECTRONIC STRUCTURE; Environmental Molecular Sciences Laboratory

Citation Formats

Zhao, Jin, Feng, Min, Yang, Jinlong, and Petek, Hrvoje. The Superatom States of Fullerenes and Their Hybridization into the Nearly Free Electron Bands of Fullerites. United States: N. p., 2009. Web. doi:10.1021/nn800834k.
Zhao, Jin, Feng, Min, Yang, Jinlong, & Petek, Hrvoje. The Superatom States of Fullerenes and Their Hybridization into the Nearly Free Electron Bands of Fullerites. United States. doi:10.1021/nn800834k.
Zhao, Jin, Feng, Min, Yang, Jinlong, and Petek, Hrvoje. Tue . "The Superatom States of Fullerenes and Their Hybridization into the Nearly Free Electron Bands of Fullerites". United States. doi:10.1021/nn800834k.
@article{osti_966648,
title = {The Superatom States of Fullerenes and Their Hybridization into the Nearly Free Electron Bands of Fullerites},
author = {Zhao, Jin and Feng, Min and Yang, Jinlong and Petek, Hrvoje},
abstractNote = {Motivated by the discovery of the superatom states of C₆₀ molecules, we investigate the factors that influence their energy and wave function hybridization into nearly free electron bands in molecular solids. As the n = 3 solutions of the radial Schro¨dinger equation of the central attractive potential consisting of the shortrange C atom core and the long-range collective screening potentials, respectively, located on the icosahedral C60 molecule shell and within its hollow core, superatom states are distinguished by their atom-like orbitals corresponding to different orbital angular momentum states (l = 0, 1, 2,...). Because they are less tightly bound than the π orbitals, that is, the n = 2 states, which are often exploited in the intermolecular electron transport in aromatic organic molecule semiconductors, superatom orbitals hybridize more extensively among aggregated molecules to form bands with nearly free electron dispersion. The prospect of exploiting the strong intermolecular coupling to achieve metal-like conduction in applications such as molecular electronics may be attained by lowering the energy of superatom states from 3.5 eV for single chemisorbed C₆₀ molecules to below the Fermi level; therefore, we study how the superatom state energies depend on factors such as their aggregation into 1D - 3D solids, cage size, and exo- and endohedral doping by metal atoms. We find, indeed, that if the ionization potential of endohedral atom, such as copper, is sufficiently large, superatom states can form the conduction band in the middle of the gap between the HOMO and LUMO of the parent C₆₀ molecule. Through a plane-wave density functional theory study, we provide insights for a new paradigm for intermolecular electronic interaction beyond the conventional one among the spn hybridized orbitals of the organic molecular solids that could lead to design of novel molecular materials and quantum structures with extraordinary optical and electronic properties.},
doi = {10.1021/nn800834k},
journal = {ACS Nano, 3(4):853-864},
issn = {1936-086X},
number = 4,
volume = 3,
place = {United States},
year = {2009},
month = {4}
}