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Title: Exciton Localization and Optical Emission in Aryl-Functionalized Carbon Nanotubes

Abstract

Recent spectroscopic studies have revealed the appearance of multiple low-energy peaks in the fluorescence of single-walled carbon nanotubes (SWCNTs) upon their covalent functionalization by aryl groups. The photophysical nature of these low energy optical bands is of significant interest in the quest to understand their appearance and to achieve their precise control via chemical modification of SWCNTs. This theoretical study explains the specific energy dependence of emission features introduced in chemically functionalized (6,5) SWCNTs with aryl bromides at different conformations and in various dielectric media. Calculations using density functional theory (DFT) and time dependent DFT (TD-DFT) show that the specific isomer geometry—the relative position of functional groups on the carbon-ring of the nanotube—is critical for controlling the energies and intensities of optical transitions introduced by functionalization, while the dielectric environment and the chemical composition of functional groups play less significant roles. The predominant effects on optical properties as a result of functionalization conformation are rationalized by exciton localization on the surface of the SWCNT near the dopant sp3-defect but not onto the functional group itself.

Authors:
 [1]; ORCiD logo [1]; ORCiD logo; ORCiD logo; ORCiD logo
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  1. Department of Chemistry and Biochemistry, North Dakota State University, Fargo, North Dakota 58108, United States
Publication Date:
Research Org.:
Los Alamos National Laboratory (LANL), Los Alamos, NM (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1409122
Alternate Identifier(s):
OSTI ID: 1417173; OSTI ID: 1508080
Report Number(s):
LA-UR-17-28653
Journal ID: ISSN 1932-7447
Grant/Contract Number:  
AC02-05CH11231; AC52-06NA25396
Resource Type:
Published Article
Journal Name:
Journal of Physical Chemistry. C
Additional Journal Information:
Journal Name: Journal of Physical Chemistry. C Journal Volume: 122 Journal Issue: 3; Journal ID: ISSN 1932-7447
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Inorganic and Physical Chemistry; Material Science

Citation Formats

Gifford, Brendan J., Kilina, Svetlana, Htoon, Han, Doorn, Stephen K., and Tretiak, Sergei. Exciton Localization and Optical Emission in Aryl-Functionalized Carbon Nanotubes. United States: N. p., 2017. Web. doi:10.1021/acs.jpcc.7b09558.
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Gifford, Brendan J., Kilina, Svetlana, Htoon, Han, Doorn, Stephen K., & Tretiak, Sergei. Exciton Localization and Optical Emission in Aryl-Functionalized Carbon Nanotubes. United States. https://doi.org/10.1021/acs.jpcc.7b09558
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Gifford, Brendan J., Kilina, Svetlana, Htoon, Han, Doorn, Stephen K., and Tretiak, Sergei. Thu . "Exciton Localization and Optical Emission in Aryl-Functionalized Carbon Nanotubes". United States. https://doi.org/10.1021/acs.jpcc.7b09558.
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@article{osti_1409122,
title = {Exciton Localization and Optical Emission in Aryl-Functionalized Carbon Nanotubes},
author = {Gifford, Brendan J. and Kilina, Svetlana and Htoon, Han and Doorn, Stephen K. and Tretiak, Sergei},
abstractNote = {Recent spectroscopic studies have revealed the appearance of multiple low-energy peaks in the fluorescence of single-walled carbon nanotubes (SWCNTs) upon their covalent functionalization by aryl groups. The photophysical nature of these low energy optical bands is of significant interest in the quest to understand their appearance and to achieve their precise control via chemical modification of SWCNTs. This theoretical study explains the specific energy dependence of emission features introduced in chemically functionalized (6,5) SWCNTs with aryl bromides at different conformations and in various dielectric media. Calculations using density functional theory (DFT) and time dependent DFT (TD-DFT) show that the specific isomer geometry—the relative position of functional groups on the carbon-ring of the nanotube—is critical for controlling the energies and intensities of optical transitions introduced by functionalization, while the dielectric environment and the chemical composition of functional groups play less significant roles. The predominant effects on optical properties as a result of functionalization conformation are rationalized by exciton localization on the surface of the SWCNT near the dopant sp3-defect but not onto the functional group itself.},
doi = {10.1021/acs.jpcc.7b09558},
journal = {Journal of Physical Chemistry. C},
number = 3,
volume = 122,
place = {United States},
year = {Thu Nov 16 00:00:00 EST 2017},
month = {Thu Nov 16 00:00:00 EST 2017}
}
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https://doi.org/10.1021/acs.jpcc.7b09558
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