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Title: Correction Scheme for Comparison of Computed and Experimental Optical Transition Energies in Functionalized Single-Walled Carbon Nanotubes

Abstract

We present that covalent functionalization of single-walled carbon nanotubes (SWCNTs) introduces red-shifted emission features in the near-infrared spectral range due to exciton localization around the defect site. Such chemical modifications increase their potential use as near-infrared emitters and single-photon sources in telecommunications applications. Density functional theory (DFT) studies using finite-length tube models have been used to calculate their optical transition energies. Predicted energies are typically blue-shifted compared to experiment due to methodology errors including imprecise self-interaction corrections in the density functional and finite-size basis sets. Furthermore, artificial quantum confinement in finite models cannot be corrected by a constant-energy shift since they depend on the degree of exciton localization. Herein, we present a method that corrects the emission energies predicted by time-dependent DFT. Confinement and methodology errors are separately estimated using experimental data for unmodified tubes. Finally, corrected emission energies are in remarkable agreement with experiment, suggesting the value of this straightforward method toward predicting and interpreting the optical features of functionalized SWCNTs.

Authors:
ORCiD logo [1]; ORCiD logo [2]; ORCiD logo [3]; ORCiD logo [3]; ORCiD logo [4]; ORCiD logo [3]
  1. North Dakota State Univ., Fargo, ND (United States); Los Alamos National Lab. (LANL), Los Alamos, NM (United States)
  2. Univ. of Southern California, Los Angeles, CA (United States); Los Alamos National Lab. (LANL), Los Alamos, NM (United States)
  3. Los Alamos National Lab. (LANL), Los Alamos, NM (United States)
  4. North Dakota State Univ., Fargo, ND (United States)
Publication Date:
Research Org.:
Los Alamos National Lab. (LANL), Los Alamos, NM (United States)
Sponsoring Org.:
USDOE Office of Science (SC). Advanced Scientific Computing Research (ASCR) (SC-21)
OSTI Identifier:
1481994
Report Number(s):
LA-UR-18-21776
Journal ID: ISSN 1948-7185
Grant/Contract Number:  
AC52-06NA25396; AC02-05CH11231
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Physical Chemistry Letters
Additional Journal Information:
Journal Volume: 9; Journal Issue: 10; Journal ID: ISSN 1948-7185
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; 36 MATERIALS SCIENCE

Citation Formats

Gifford, Brendan Joel, Sifain, Andrew E., Htoon, Han, Doorn, Stephen K., Kilina, Svetlana, and Tretiak, Sergei. Correction Scheme for Comparison of Computed and Experimental Optical Transition Energies in Functionalized Single-Walled Carbon Nanotubes. United States: N. p., 2018. Web. doi:10.1021/acs.jpclett.8b00653.
Gifford, Brendan Joel, Sifain, Andrew E., Htoon, Han, Doorn, Stephen K., Kilina, Svetlana, & Tretiak, Sergei. Correction Scheme for Comparison of Computed and Experimental Optical Transition Energies in Functionalized Single-Walled Carbon Nanotubes. United States. doi:https://doi.org/10.1021/acs.jpclett.8b00653
Gifford, Brendan Joel, Sifain, Andrew E., Htoon, Han, Doorn, Stephen K., Kilina, Svetlana, and Tretiak, Sergei. Fri . "Correction Scheme for Comparison of Computed and Experimental Optical Transition Energies in Functionalized Single-Walled Carbon Nanotubes". United States. doi:https://doi.org/10.1021/acs.jpclett.8b00653. https://www.osti.gov/servlets/purl/1481994.
@article{osti_1481994,
title = {Correction Scheme for Comparison of Computed and Experimental Optical Transition Energies in Functionalized Single-Walled Carbon Nanotubes},
author = {Gifford, Brendan Joel and Sifain, Andrew E. and Htoon, Han and Doorn, Stephen K. and Kilina, Svetlana and Tretiak, Sergei},
abstractNote = {We present that covalent functionalization of single-walled carbon nanotubes (SWCNTs) introduces red-shifted emission features in the near-infrared spectral range due to exciton localization around the defect site. Such chemical modifications increase their potential use as near-infrared emitters and single-photon sources in telecommunications applications. Density functional theory (DFT) studies using finite-length tube models have been used to calculate their optical transition energies. Predicted energies are typically blue-shifted compared to experiment due to methodology errors including imprecise self-interaction corrections in the density functional and finite-size basis sets. Furthermore, artificial quantum confinement in finite models cannot be corrected by a constant-energy shift since they depend on the degree of exciton localization. Herein, we present a method that corrects the emission energies predicted by time-dependent DFT. Confinement and methodology errors are separately estimated using experimental data for unmodified tubes. Finally, corrected emission energies are in remarkable agreement with experiment, suggesting the value of this straightforward method toward predicting and interpreting the optical features of functionalized SWCNTs.},
doi = {10.1021/acs.jpclett.8b00653},
journal = {Journal of Physical Chemistry Letters},
number = 10,
volume = 9,
place = {United States},
year = {2018},
month = {4}
}

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