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Title: Tip Functionalization of Finite Single-Walled Carbon Nanotubes and Its Impact on the Ground and Excited State Electronic Structure

Abstract

We explore the effect of capping of finite (10,5) carbon nanotube (SWCNT) with various functional groups, including methylene, ether, ester, and carboxylic derivatives, having different electron withdrawing/donating properties. Using density functional theory (DFT) and time-dependent DFT (TDDFT), we found that the sp2-hybridization of the bonding atom of the capping groups and the number of such groups plays the predominant role in eliminating optically inactive edge-localized midgap states, while withdrawing/donating properties of the functional groups are less significant. Our calculations show that two sp 2-groups, like methylene derivatives, combined with hydrogens are an optimal capping scheme for (10,5) SWCNT to provide the well-opened energy gap, since sp 2-groups can be placed relatively far from each other to minimize the dipole moment at the edges, while preserving conjugation of the edge according to the tube chirality. Absorption spectra demonstrate negligible effects of electron donating/withdrawing groups on the lowest optical E11 band. In contrast, the change in the bond order of the capping groups significantly changes optical spectra, resulting in red-shifted and less intensive E 11 band when sp 3-capping substitutes two sp 2-groups. Our findings can be helpful in choosing the functional groups for tuning the optoelectronic properties of SWCNTs. In addition,more » a complete understanding of the role of tube’s capping allows for using smaller computational models making computations of a wide range of phenomena in SWNTs practical.« less

Authors:
ORCiD logo [1];  [2]; ORCiD logo [2]
  1. North Dakota State Univ., Fargo, ND (United States). Dept. of Civil and Environmental Engineering
  2. North Dakota State Univ., Fargo, ND (United States). Dept. of Chemistry and Biochemistry
Publication Date:
Research Org.:
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). National Energy Research Scientific Computing Center (NERSC)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1480461
Grant/Contract Number:  
AC02-05CH11231
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Physical Chemistry. C
Additional Journal Information:
Journal Volume: 121; Journal Issue: 15; Journal ID: ISSN 1932-7447
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English

Citation Formats

Sharma, Anurag, Gifford, Brendan J., and Kilina, Svetlana. Tip Functionalization of Finite Single-Walled Carbon Nanotubes and Its Impact on the Ground and Excited State Electronic Structure. United States: N. p., 2017. Web. doi:10.1021/acs.jpcc.7b00147.
Sharma, Anurag, Gifford, Brendan J., & Kilina, Svetlana. Tip Functionalization of Finite Single-Walled Carbon Nanotubes and Its Impact on the Ground and Excited State Electronic Structure. United States. doi:10.1021/acs.jpcc.7b00147.
Sharma, Anurag, Gifford, Brendan J., and Kilina, Svetlana. Tue . "Tip Functionalization of Finite Single-Walled Carbon Nanotubes and Its Impact on the Ground and Excited State Electronic Structure". United States. doi:10.1021/acs.jpcc.7b00147. https://www.osti.gov/servlets/purl/1480461.
@article{osti_1480461,
title = {Tip Functionalization of Finite Single-Walled Carbon Nanotubes and Its Impact on the Ground and Excited State Electronic Structure},
author = {Sharma, Anurag and Gifford, Brendan J. and Kilina, Svetlana},
abstractNote = {We explore the effect of capping of finite (10,5) carbon nanotube (SWCNT) with various functional groups, including methylene, ether, ester, and carboxylic derivatives, having different electron withdrawing/donating properties. Using density functional theory (DFT) and time-dependent DFT (TDDFT), we found that the sp2-hybridization of the bonding atom of the capping groups and the number of such groups plays the predominant role in eliminating optically inactive edge-localized midgap states, while withdrawing/donating properties of the functional groups are less significant. Our calculations show that two sp2-groups, like methylene derivatives, combined with hydrogens are an optimal capping scheme for (10,5) SWCNT to provide the well-opened energy gap, since sp2-groups can be placed relatively far from each other to minimize the dipole moment at the edges, while preserving conjugation of the edge according to the tube chirality. Absorption spectra demonstrate negligible effects of electron donating/withdrawing groups on the lowest optical E11 band. In contrast, the change in the bond order of the capping groups significantly changes optical spectra, resulting in red-shifted and less intensive E11 band when sp3-capping substitutes two sp2-groups. Our findings can be helpful in choosing the functional groups for tuning the optoelectronic properties of SWCNTs. In addition, a complete understanding of the role of tube’s capping allows for using smaller computational models making computations of a wide range of phenomena in SWNTs practical.},
doi = {10.1021/acs.jpcc.7b00147},
journal = {Journal of Physical Chemistry. C},
number = 15,
volume = 121,
place = {United States},
year = {2017},
month = {3}
}

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