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:
-
- North Dakota State Univ., Fargo, ND (United States); Los Alamos National Lab. (LANL), Los Alamos, NM (United States)
- Univ. of Southern California, Los Angeles, CA (United States); Los Alamos National Lab. (LANL), Los Alamos, NM (United States)
- Los Alamos National Lab. (LANL), Los Alamos, NM (United States)
- 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:
- Journal Article: 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. 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. 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},
url = {https://www.osti.gov/biblio/1481994},
journal = {Journal of Physical Chemistry Letters},
issn = {1948-7185},
number = 10,
volume = 9,
place = {United States},
year = {2018},
month = {4}
}
Web of Science
Works referencing / citing this record:
Narrow-band single-photon emission through selective aryl functionalization of zigzag carbon nanotubes
journal, September 2018
- Saha, Avishek; Gifford, Brendan J.; He, Xiaowei
- Nature Chemistry, Vol. 10, Issue 11
Controlling the optical properties of carbon nanotubes with organic colour-centre quantum defects
journal, June 2019
- Brozena, Alexandra H.; Kim, Mijin; Powell, Lyndsey R.
- Nature Reviews Chemistry, Vol. 3, Issue 6
Thermodynamic control of quantum defects on single-walled carbon nanotubes
journal, January 2019
- Maeda, Yutaka; Murakoshi, Hiyori; Tambo, Haruto
- Chemical Communications, Vol. 55, Issue 91
Optical properties of semiconducting zigzag carbon nanotubes with and without defects
journal, January 2019
- Mu, Jinglin; Ma, Yuchen; Liu, Huichun
- The Journal of Chemical Physics, Vol. 150, Issue 2