Search Menu
DOE PAGES title logo U.S. Department of Energy
Office of Scientific and Technical Information
Search Scholarly Publications

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 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 themore » 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]
+ Show Author Affiliations
  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)
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
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

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.
Copy to clipboard
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. https://doi.org/10.1021/acs.jpcc.7b00147
Copy to clipboard
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. https://doi.org/10.1021/acs.jpcc.7b00147. https://www.osti.gov/servlets/purl/1480461.
Copy to clipboard
@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 = {Tue Mar 28 00:00:00 EDT 2017},
month = {Tue Mar 28 00:00:00 EDT 2017}
}
Copy to clipboard
Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record
https://doi.org/10.1021/acs.jpcc.7b00147
Copyright Statement
Other availability
Search WorldCat Search WorldCat to find libraries that may hold this journal
Citation Metrics:
Cited by: 21 works
Citation information provided by
Web of Science
Save / Share:
Export Metadata
Save to My Library
You must Sign In or Create an Account in order to save documents to your library.

Works referenced in this record:

Improved Dispersion of Carbon Nanotubes in Polymers at High Concentrations
journal, October 2012

  • Liu, Chao-Xuan; Choi, Jin-Woo
  • Nanomaterials, Vol. 2, Issue 4, p. 329-347
  • DOI: 10.3390/nano2040329

Polymer Structure and Solvent Effects on the Selective Dispersion of Single-Walled Carbon Nanotubes
journal, March 2008

  • Hwang, Jeong-Yuan; Nish, Adrian; Doig, James
  • Journal of the American Chemical Society, Vol. 130, Issue 11
  • DOI: 10.1021/ja0777640

Structure-Based Carbon Nanotube Sorting by Sequence-Dependent DNA Assembly
journal, November 2003

Electronic band structure of isolated and bundled carbon nanotubes
journal, March 2002

Chemistry of Carbon Nanotubes
journal, March 2006

  • Tasis, Dimitrios; Tagmatarchis, Nikos; Bianco, Alberto
  • Chemical Reviews, Vol. 106, Issue 3
  • DOI: 10.1021/cr050569o

Morphology and dispersion of polycarbazole wrapped carbon nanotubes
journal, January 2013

  • Mayo, Michael L.; Hogle, David; Yilmaz, Baris
  • RSC Advances, Vol. 3, Issue 43
  • DOI: 10.1039/c3ra44136a

Molecular Perspective on Diazonium Adsorption for Controllable Functionalization of Single-Walled Carbon Nanotubes in Aqueous Surfactant Solutions
journal, April 2012

  • Lin, Shangchao; Hilmer, Andrew J.; Mendenhall, Jonathan D.
  • Journal of the American Chemical Society, Vol. 134, Issue 19
  • DOI: 10.1021/ja301635e

Advanced technology for functionalization of carbon nanotubes
journal, July 2009

  • Meng, Lingjie; Fu, Chuanlong; Lu, Qinghua
  • Progress in Natural Science, Vol. 19, Issue 7, p. 801-810
  • DOI: 10.1016/j.pnsc.2008.08.011

High-Purity Semiconducting Single-Walled Carbon Nanotubes via Selective Dispersion in Solution Using Fully Conjugated Polytriarylamines
journal, November 2016

Industrial-scale separation of high-purity single-chirality single-wall carbon nanotubes for biological imaging
journal, June 2016

  • Yomogida, Yohei; Tanaka, Takeshi; Zhang, Minfang
  • Nature Communications, Vol. 7, Issue 1
  • DOI: 10.1038/ncomms12056

The influence of carbon nanotubes in inkjet printing of conductive polymer suspensions
journal, August 2009

Electronic Properties of Semiconducting Polymer-Functionalized Single Wall Carbon Nanotubes
journal, March 2013

  • Kourkouli, Souzana N.; Siokou, Angeliki; Stefopoulos, Andreas A.
  • Macromolecules, Vol. 46, Issue 7
  • DOI: 10.1021/ma3025464

Thermal Conversion of Electronic and Electrical Properties of AuCl 3 -Doped Single-Walled Carbon Nanotubes
journal, January 2011

  • Yoon, Seon-Mi; Kim, Un Jeong; Benayad, Anass
  • ACS Nano, Vol. 5, Issue 2
  • DOI: 10.1021/nn103055u

The Studies of Equilibrium and Thermodynamic Adsorption of Pb(II), Cd(II) and Cu(II) Ions from Aqueous Solution onto SWCNTs and SWCNT–COOH Surfaces
journal, May 2010

  • Moradi, O.; Zare, K.; Monajjemi, M.
  • Fullerenes, Nanotubes and Carbon Nanostructures, Vol. 18, Issue 3
  • DOI: 10.1080/15363831003783005

Porphyrin-Functionalized Single-Walled Carbon Nanotube Chemiresistive Sensor Arrays for VOCs
journal, February 2012

  • Shirsat, Mahendra D.; Sarkar, Tapan; Kakoullis, James
  • The Journal of Physical Chemistry C, Vol. 116, Issue 5
  • DOI: 10.1021/jp210582t

Controlled Functionalization of Multiwalled Carbon Nanotubes by in Situ Atom Transfer Radical Polymerization
journal, January 2004

  • Kong, Hao; Gao, Chao; Yan, Deyue
  • Journal of the American Chemical Society, Vol. 126, Issue 2
  • DOI: 10.1021/ja0380493

Chemical Engineering of the Single-Walled Carbon Nanotube−Nylon 6 Interface
journal, June 2006

  • Gao, Junbo; Zhao, Bin; Itkis, Mikhail E.
  • Journal of the American Chemical Society, Vol. 128, Issue 23
  • DOI: 10.1021/ja057484p

Preparation and Toxicological Assessment of Functionalized Carbon Nanotube-Polymer Hybrids
journal, September 2014

Carbon Nanotubes as Intracellular Protein Transporters:  Generality and Biological Functionality
journal, March 2005

  • Kam, Nadine Wong Shi; Dai, Hongjie
  • Journal of the American Chemical Society, Vol. 127, Issue 16
  • DOI: 10.1021/ja050062v

Highly Efficient Binding of DNA on the Sidewalls and Tips of Carbon Nanotubes Using Photochemistry
journal, January 2004

  • Moghaddam, Minoo J.; Taylor, Sarah; Gao, Mei
  • Nano Letters, Vol. 4, Issue 1
  • DOI: 10.1021/nl034915y

DNA-functionalized single-walled carbon nanotubes
journal, September 2002

Carbon nanotube proximity influences rice DNA
journal, July 2015

Biomolecules-carbon nanotubes doped conducting polymer nanocomposites and their sensor application
journal, December 2007

Carbon Nanotubes: Applications in Pharmacy and Medicine
journal, January 2013

  • He, Hua; Pham-Huy, Lien Ai; Dramou, Pierre
  • BioMed Research International, Vol. 2013
  • DOI: 10.1155/2013/578290

Carbon nanotubes modified with porphyrin units for gaseous phase chemical sensing
journal, July 2012

Functionalization of carbon nanotubes
journal, March 2004

The Role of Carboxylated Carbonaceous Fragments in the Functionalization and Spectroscopy of a Single-Walled Carbon-Nanotube Material
journal, March 2007

  • Salzmann, C. G.; Llewellyn, S. A.; Tobias, G.
  • Advanced Materials, Vol. 19, Issue 6
  • DOI: 10.1002/adma.200601310

Investigation of optical properties of pristine and functionalized single-walled carbon nanotubes
journal, January 2015

  • Kumar, Dinesh; Singh, Karamjit; Verma, Veena
  • Journal of Materials Science: Materials in Electronics, Vol. 26, Issue 4
  • DOI: 10.1007/s10854-014-2656-x

Infrared Spectral Evidence for the Etching of Carbon Nanotubes:  Ozone Oxidation at 298 K
journal, March 2000

  • Mawhinney, Douglas B.; Naumenko, Viktor; Kuznetsova, Anya
  • Journal of the American Chemical Society, Vol. 122, Issue 10
  • DOI: 10.1021/ja994094s

Chemically Functionalized Carbon Nanotubes
journal, February 2005

Adsorption of anionic and cationic dyes from aqueous solution using gelatin-based magnetic nanocomposite beads comprising carboxylic acid functionalized carbon nanotube
journal, January 2017

  • Saber-Samandari, Samaneh; Saber-Samandari, Saeed; Joneidi-Yekta, Hamed
  • Chemical Engineering Journal, Vol. 308
  • DOI: 10.1016/j.cej.2016.10.017

Sidewall Carboxylic Acid Functionalization of Single-Walled Carbon Nanotubes
journal, December 2003

  • Peng, Haiqing; Alemany, Lawrence B.; Margrave, John L.
  • Journal of the American Chemical Society, Vol. 125, Issue 49
  • DOI: 10.1021/ja037746s

Unveiling Stability Criteria of DNA-Carbon Nanotubes Constructs by Scanning Tunneling Microscopy and Computational Modeling
journal, January 2011

  • Kilina, Svetlana; Yarotski, Dzmitry A.; Talin, A. Alec
  • Journal of Drug Delivery, Vol. 2011, p. 1-9
  • DOI: 10.1155/2011/415621

Scanning Tunneling Microscopy of DNA-Wrapped Carbon Nanotubes
journal, January 2009

  • Yarotski, Dzmitry A.; Kilina, Svetlana V.; Talin, A. Alec
  • Nano Letters, Vol. 9, Issue 1, p. 12-17
  • DOI: 10.1021/nl801455t

Covalently Functionalized SWCNTs as Tailored p-Type Dopants for Perovskite Solar Cells
journal, October 2016

  • Miletić, Tanja; Pavoni, Eleonora; Trifiletti, Vanira
  • ACS Applied Materials & Interfaces, Vol. 8, Issue 41
  • DOI: 10.1021/acsami.6b08398

Violation of the Condon Approximation in Semiconducting Carbon Nanotubes
journal, May 2011

  • Duque, Juan G.; Chen, Hang; Swan, Anna K.
  • ACS Nano, Vol. 5, Issue 6
  • DOI: 10.1021/nn201430z

Substituted Carborane-Appended Water-Soluble Single-Wall Carbon Nanotubes:  New Approach to Boron Neutron Capture Therapy Drug Delivery
journal, July 2005

  • Yinghuai, Zhu; Peng, Ang Thiam; Carpenter, Keith
  • Journal of the American Chemical Society, Vol. 127, Issue 27
  • DOI: 10.1021/ja0517116

Light-Driven and Phonon-Assisted Dynamics in Organic and Semiconductor Nanostructures
journal, May 2015

Functionalization of carbon nanotubes with –CH n , –NH n fragments, –COOH and –OH groups
journal, May 2013

  • Milowska, Karolina Z.; Majewski, Jacek A.
  • The Journal of Chemical Physics, Vol. 138, Issue 19
  • DOI: 10.1063/1.4804652

Electronic structure and optical spectra of semiconducting carbon nanotubes functionalized by diazonium salts
journal, February 2013

Brightening of the Lowest Exciton in Carbon Nanotubes via Chemical Functionalization
journal, April 2012

  • Kilina, Svetlana; Ramirez, Jessica; Tretiak, Sergei
  • Nano Letters, Vol. 12, Issue 5
  • DOI: 10.1021/nl300165w

Brightening of carbon nanotube photoluminescence through the incorporation of sp3 defects
journal, July 2013

  • Piao, Yanmei; Meany, Brendan; Powell, Lyndsey R.
  • Nature Chemistry, Vol. 5, Issue 10
  • DOI: 10.1038/nchem.1711

Electronic Structure and Chemical Nature of Oxygen Dopant States in Carbon Nanotubes
journal, October 2014

  • Ma, Xuedan; Adamska, Lyudmyla; Yamaguchi, Hisato
  • ACS Nano, Vol. 8, Issue 10
  • DOI: 10.1021/nn504553y

Oxygen Doping Modifies Near-Infrared Band Gaps in Fluorescent Single-Walled Carbon Nanotubes
journal, November 2010

Excitons and Peierls Distortion in Conjugated Carbon Nanotubes
journal, January 2007

  • Tretiak, Sergei; Kilina, Svetlana; Piryatinski, Andrei
  • Nano Letters, Vol. 7, Issue 1
  • DOI: 10.1021/nl0622000

Determination of Exciton-Phonon Coupling Elements in Single-Walled Carbon Nanotubes by Raman Overtone Analysis
journal, January 2007

Third and Fourth Optical Transitions in Semiconducting Carbon Nanotubes
journal, February 2007

Excitonic and Vibrational Properties of Single-Walled Semiconducting Carbon Nanotubes
journal, October 2007

Bright and dark excitons in semiconductor carbon nanotubes: insights from electronic structure calculations
journal, January 2009

  • Kilina, Svetlana; Badaeva, Ekaterina; Piryatinski, Andrei
  • Physical Chemistry Chemical Physics, Vol. 11, Issue 21
  • DOI: 10.1039/b818473a

Cross-polarized excitons in carbon nanotubes
journal, May 2008

  • Kilina, S.; Tretiak, S.; Doorn, S. K.
  • Proceedings of the National Academy of Sciences, Vol. 105, Issue 19
  • DOI: 10.1073/pnas.0711646105

Morphology and Optical Response of Carbon Nanotubes Functionalized by Conjugated Polymers
journal, March 2012

  • Furmanchuk, Al’ona; Leszczynski, Jerzy; Tretiak, Sergei
  • The Journal of Physical Chemistry C, Vol. 116, Issue 12
  • DOI: 10.1021/jp211541q

DFT studies of COOH tip-functionalized zigzag and armchair single wall carbon nanotubes
journal, October 2011

  • Chełmecka, Elżbieta; Pasterny, Karol; Kupka, Teobald
  • Journal of Molecular Modeling, Vol. 18, Issue 5
  • DOI: 10.1007/s00894-011-1242-x

The effect on acidity of size and shape of carboxylated single-wall carbon nanotubes. A DFT-SLDB study
journal, July 2008

Open-ended modified single-wall carbon nanotubes: A theoretical study of the effects of purification
journal, May 2006

OH-functionalized open-ended armchair single-wall carbon nanotubes (SWCNT) studied by density functional theory
journal, July 2011

  • Chełmecka, Elżbieta; Pasterny, Karol; Kupka, Teobald
  • Journal of Molecular Modeling, Vol. 18, Issue 4
  • DOI: 10.1007/s00894-011-1181-6

The geometrical and electronic structures of open-end fully functionalized single-walled carbon nanotubes
journal, March 2009

  • Wongchoosuk, Chatchawal; Udomvech, Anurak; Kerdcharoen, Teerakiat
  • Current Applied Physics, Vol. 9, Issue 2
  • DOI: 10.1016/j.cap.2008.03.003

IR Characterization of Tip-Functionalized Single-Wall Carbon Nanotubes
journal, November 2010

  • Kar, Tapas; Scheiner, Steve; Patnaik, Soumya S.
  • The Journal of Physical Chemistry C, Vol. 114, Issue 49
  • DOI: 10.1021/jp104883e

Theoretical Study of Structure and Raman Spectra for Models of Carbon Nanotubes in Their Pristine and Oxidized Forms
journal, November 2002

  • Irle, Stephan; Mews, Alf; Morokuma, Keiji
  • The Journal of Physical Chemistry A, Vol. 106, Issue 49
  • DOI: 10.1021/jp026582j

Development and use of quantum mechanical molecular models. 76. AM1: a new general purpose quantum mechanical molecular model
journal, June 1985

  • Dewar, Michael J. S.; Zoebisch, Eve G.; Healy, Eamonn F.
  • Journal of the American Chemical Society, Vol. 107, Issue 13
  • DOI: 10.1021/ja00299a024

Real-time observation of nonlinear coherent phonon dynamics in single-walled carbon nanotubes
journal, July 2006

  • Gambetta, A.; Manzoni, C.; Menna, E.
  • Nature Physics, Vol. 2, Issue 8
  • DOI: 10.1038/nphys345

Excitonic effects in a time-dependent density functional theory
journal, September 2007

  • Igumenshchev, Kirill I.; Tretiak, Sergei; Chernyak, Vladimir Y.
  • The Journal of Chemical Physics, Vol. 127, Issue 11
  • DOI: 10.1063/1.2773727

Exciton sizes of conducting polymers predicted by time-dependent density functional theory
journal, January 2005

Natural transition orbitals
journal, March 2003

  • Martin, Richard L.
  • The Journal of Chemical Physics, Vol. 118, Issue 11
  • DOI: 10.1063/1.1558471
    Sort by:
    [ × clear filter / sort ]

    Works referencing / citing this record:

    Molecular dynamics of reactions between (4,0) zigzag carbon nanotube and hydrogen peroxide under extreme conditions
    journal, January 2018

      Sort by:
      [ × clear filter / sort ]

      Similar Records in DOE PAGES and OSTI.GOV collections: