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

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. Furthermore, 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 [2] ; ORCiD logo [3] ; ORCiD logo [3] ; ORCiD logo [3]
  1. North Dakota State Univ., Fargo, ND (United States); Los Alamos National Lab. (LANL), Los Alamos, NM (United States)
  2. North Dakota State Univ., Fargo, ND (United States)
  3. Los Alamos National Lab. (LANL), Los Alamos, NM (United States)
Publication Date:
Report Number(s):
LA-UR-17-28653
Journal ID: ISSN 1932-7447; TRN: US1801003
Grant/Contract Number:
AC52-06NA25396; AC02-05CH11231
Type:
Published Article
Journal Name:
Journal of Physical Chemistry. C
Additional Journal Information:
Journal Volume: 122; Journal Issue: 3; Journal ID: ISSN 1932-7447
Publisher:
American Chemical Society
Research Org:
Los Alamos National Lab. (LANL), Los Alamos, NM (United States)
Sponsoring Org:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Inorganic and Physical Chemistry; Material Science
OSTI Identifier:
1409122
Alternate Identifier(s):
OSTI ID: 1417173

Gifford, Brendan Joel, Kilina, Svetlana, Htoon, Han, Doorn, Stephen K., and Tretiak, Sergei. Exciton Localization and Optical Emission in Aryl-Functionalized Carbon Nanotubes. United States: N. p., Web. doi:10.1021/acs.jpcc.7b09558.
Gifford, Brendan Joel, Kilina, Svetlana, Htoon, Han, Doorn, Stephen K., & Tretiak, Sergei. Exciton Localization and Optical Emission in Aryl-Functionalized Carbon Nanotubes. United States. doi:10.1021/acs.jpcc.7b09558.
Gifford, Brendan Joel, Kilina, Svetlana, Htoon, Han, Doorn, Stephen K., and Tretiak, Sergei. 2017. "Exciton Localization and Optical Emission in Aryl-Functionalized Carbon Nanotubes". United States. doi:10.1021/acs.jpcc.7b09558.
@article{osti_1409122,
title = {Exciton Localization and Optical Emission in Aryl-Functionalized Carbon Nanotubes},
author = {Gifford, Brendan Joel 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. Furthermore, 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 = {2017},
month = {10}
}