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Title: 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:
ORCiD logo [1]; ORCiD logo [2]; ORCiD logo [3]; ORCiD logo [3]; ORCiD logo [4]; ORCiD logo [3]
  1. North Dakota State Univ., Fargo, ND (United States); Los Alamos National Lab. (LANL), Los Alamos, NM (United States)
  2. Univ. of Southern California, Los Angeles, CA (United States); Los Alamos National Lab. (LANL), Los Alamos, NM (United States)
  3. Los Alamos National Lab. (LANL), Los Alamos, NM (United States)
  4. 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:
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},
journal = {Journal of Physical Chemistry Letters},
number = 10,
volume = 9,
place = {United States},
year = {2018},
month = {4}
}

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Works referenced in this record:

Helical microtubules of graphitic carbon
journal, November 1991


Physical Properties of Carbon Nanotubes
book, January 1998

  • Saito, R.; Dresselhaus, G.; Dresselhaus, M. S.
  • DOI: 10.1142/p080

Carbon nanotubes and organic solar cells
journal, January 2012

  • Cataldo, Sebastiano; Salice, Patrizio; Menna, Enzo
  • Energy Environ. Sci., Vol. 5, Issue 3
  • DOI: 10.1039/C1EE02276H

Single-Walled Carbon Nanotube Scaffolds for Dye-Sensitized Solar Cells
journal, March 2008

  • Brown, Patrick; Takechi, Kensuke; Kamat, Prashant V.
  • The Journal of Physical Chemistry C, Vol. 112, Issue 12
  • DOI: 10.1021/jp7107472

Recent developments in the photophysics of single-walled carbon nanotubes for their use as active and passive material elements in thin film photovoltaics
journal, January 2013

  • Arnold, Michael S.; Blackburn, Jeffrey L.; Crochet, Jared J.
  • Physical Chemistry Chemical Physics, Vol. 15, Issue 36
  • DOI: 10.1039/c3cp52752b

Semiconducting Single-Walled Carbon Nanotubes in Solar Energy Harvesting
journal, June 2017


Carbon Nanotube Sensors for Gas and Organic Vapor Detection
journal, July 2003


Carbon Nanotubes as Active Components for Gas Sensors
journal, January 2009


Electrochemically Functionalized Single-Walled Carbon Nanotube Gas Sensor
journal, June 2006

  • Zhang, Ting; Nix, Megan B.; Yoo, Bong-Young
  • Electroanalysis, Vol. 18, Issue 12
  • DOI: 10.1002/elan.200603527

A Review of Carbon Nanotubes-Based Gas Sensors
journal, January 2009


Highly enhanced gas sensing in single-walled carbon nanotube-based thin-film transistor sensors by ultraviolet light irradiation
journal, January 2012

  • Chen, Tingting; Wei, Liangming; Zhou, Zhihua
  • Nanoscale Research Letters, Vol. 7, Issue 1
  • DOI: 10.1186/1556-276X-7-644

Functionalized multiwalled carbon nanotubes based hydrogen gas sensor
journal, October 2013


Transparent, Conductive, and Flexible Carbon Nanotube Films and Their Application in Organic Light-Emitting Diodes
journal, September 2006

  • Zhang, Daihua; Ryu, Koungmin; Liu, Xiaolei
  • Nano Letters, Vol. 6, Issue 9, p. 1880-1886
  • DOI: 10.1021/nl0608543

Carbon nanotube-based organic light emitting diodes
journal, January 2009

  • Bansal, Malti; Srivastava, Ritu; Lal, C.
  • Nanoscale, Vol. 1, Issue 3
  • DOI: 10.1039/b9nr00179d

Efficient narrow-band light emission from a single carbon nanotube p–n diode
journal, November 2009

  • Mueller, Thomas; Kinoshita, Megumi; Steiner, Mathias
  • Nature Nanotechnology, Vol. 5, Issue 1
  • DOI: 10.1038/nnano.2009.319

High-Performance Carbon Nanotube Light-Emitting Diodes with Asymmetric Contacts
journal, January 2011

  • Wang, Sheng; Zeng, Qingsheng; Yang, Leijing
  • Nano Letters, Vol. 11, Issue 1
  • DOI: 10.1021/nl101513z

Plannar light source using a phosphor screen with single-walled carbon nanotubes as field emitters
journal, October 2014

  • Bahena-Garrido, Sharon; Shimoi, Norihiro; Abe, Daisuke
  • Review of Scientific Instruments, Vol. 85, Issue 10
  • DOI: 10.1063/1.4895913

Molecularly Tunable Fluorescent Quantum Defects
journal, May 2016

  • Kwon, Hyejin; Furmanchuk, Al’ona; Kim, Mijin
  • Journal of the American Chemical Society, Vol. 138, Issue 21
  • DOI: 10.1021/jacs.6b03618

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


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

Brightening of excitons in carbon nanotubes on dimensionality modification
journal, July 2013

  • Miyauchi, Yuhei; Iwamura, Munechiyo; Mouri, Shinichiro
  • Nature Photonics, Vol. 7, Issue 9
  • DOI: 10.1038/nphoton.2013.179

Photoluminescence imaging of solitary dopant sites in covalently doped single-wall carbon nanotubes
journal, January 2015

  • Hartmann, Nicolai F.; Yalcin, Sibel Ebru; Adamska, Lyudmyla
  • Nanoscale, Vol. 7, Issue 48
  • DOI: 10.1039/C5NR06343D

Tunable room-temperature single-photon emission at telecom wavelengths from sp3 defects in carbon nanotubes
journal, July 2017


Low-Temperature Single Carbon Nanotube Spectroscopy of sp 3 Quantum Defects
journal, September 2017


Optical Excitation of Carbon Nanotubes Drives Localized Diazonium Reactions
journal, September 2016

  • Powell, Lyndsey R.; Piao, Yanmei; Wang, YuHuang
  • The Journal of Physical Chemistry Letters, Vol. 7, Issue 18
  • DOI: 10.1021/acs.jpclett.6b01771

Photoluminescence Dynamics of Aryl sp 3 Defect States in Single-Walled Carbon Nanotubes
journal, August 2016

  • Hartmann, Nicolai F.; Velizhanin, Kirill A.; Haroz, Erik H.
  • ACS Nano, Vol. 10, Issue 9
  • DOI: 10.1021/acsnano.6b02986

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

Fluorescent Carbon Nanotube Defects Manifest Substantial Vibrational Reorganization
journal, May 2016

  • Kim, Mijin; Adamska, Lyudmyla; Hartmann, Nicolai F.
  • The Journal of Physical Chemistry C, Vol. 120, Issue 20
  • DOI: 10.1021/acs.jpcc.6b02538

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

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


A bright future for defects
journal, September 2013

  • Wang, Qing Hua; Strano, Michael S.
  • Nature Chemistry, Vol. 5, Issue 10
  • DOI: 10.1038/nchem.1768

Self-Trapping of Excitons, Violation of Condon Approximation, and Efficient Fluorescence in Conjugated Cycloparaphenylenes
journal, October 2014

  • Adamska, Lyudmyla; Nayyar, Iffat; Chen, Hang
  • Nano Letters, Vol. 14, Issue 11
  • DOI: 10.1021/nl503133e

Room-temperature single-photon generation from solitary dopants of carbon nanotubes
journal, July 2015

  • Ma, Xuedan; Hartmann, Nicolai F.; Baldwin, Jon K. S.
  • Nature Nanotechnology, Vol. 10, Issue 8
  • DOI: 10.1038/nnano.2015.136

Efficient near-infrared up-conversion photoluminescence in carbon nanotubes
journal, November 2015

  • Akizuki, Naoto; Aota, Shun; Mouri, Shinichiro
  • Nature Communications, Vol. 6, Issue 1
  • DOI: 10.1038/ncomms9920

Controlled Defects in Semiconducting Carbon Nanotubes Promote Efficient Generation and Luminescence of Trions
journal, March 2014

  • Brozena, Alexandra H.; Leeds, Jarrett D.; Zhang, Yin
  • ACS Nano, Vol. 8, Issue 5
  • DOI: 10.1021/nn500894p

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

Propagative Sidewall Alkylcarboxylation that Induces Red-Shifted Near-IR Photoluminescence in Single-Walled Carbon Nanotubes
journal, February 2013

  • Zhang, Yin; Valley, Nicholas; Brozena, Alexandra H.
  • The Journal of Physical Chemistry Letters, Vol. 4, Issue 5
  • DOI: 10.1021/jz400167d

First-Principles Studies on Carbon Nanotubes Functionalized with Azomethine Ylides
journal, July 2008

  • Cho, Eunseog; Shin, Seokmin; Yoon, Young-Gui
  • The Journal of Physical Chemistry C, Vol. 112, Issue 31
  • DOI: 10.1021/jp710938v

Theoretical predictions on efficiency of bi-exciton formation and dissociation in chiral carbon nanotubes
journal, October 2016

  • Kryjevski, Andrei; Gifford, Brendan; Kilina, Svetlana
  • The Journal of Chemical Physics, Vol. 145, Issue 15
  • DOI: 10.1063/1.4963735

Singlet fission in chiral carbon nanotubes: Density functional theory based computation
journal, July 2017

  • Kryjevski, Andrei; Mihaylov, Deyan; Gifford, Brendan
  • The Journal of Chemical Physics, Vol. 147, Issue 3
  • DOI: 10.1063/1.4992785

Photoinduced Charge Transfer at Interfaces of Carbon Nanotube and Lead Selenide Nanowire
journal, September 2016

  • Erck, Adam; Sapp, Wendi; Kilina, Svetlana
  • The Journal of Physical Chemistry C, Vol. 120, Issue 40
  • DOI: 10.1021/acs.jpcc.6b05571

Geometric derivatives of density functional theory excitation energies using gradient-corrected functionals
journal, January 2000


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


Exciton Localization and Optical Emission in Aryl-Functionalized Carbon Nanotubes
journal, November 2017

  • Gifford, Brendan J.; Kilina, Svetlana; Htoon, Han
  • The Journal of Physical Chemistry C, Vol. 122, Issue 3
  • DOI: 10.1021/acs.jpcc.7b09558

Tip Functionalization of Finite Single-Walled Carbon Nanotubes and Its Impact on the Ground and Excited State Electronic Structure
journal, April 2017

  • Sharma, Anurag; Gifford, Brendan J.; Kilina, Svetlana
  • The Journal of Physical Chemistry C, Vol. 121, Issue 15
  • DOI: 10.1021/acs.jpcc.7b00147

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

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


Self-Trapping of Charge Carriers in Semiconducting Carbon Nanotubes: Structural Analysis
journal, September 2015

  • Adamska, Lyudmyla; Nazin, George V.; Doorn, Stephen K.
  • The Journal of Physical Chemistry Letters, Vol. 6, Issue 19
  • DOI: 10.1021/acs.jpclett.5b01729

VMD: Visual molecular dynamics
journal, February 1996


A new hybrid exchange–correlation functional using the Coulomb-attenuating method (CAM-B3LYP)
journal, July 2004

  • Yanai, Takeshi; Tew, David P.; Handy, Nicholas C.
  • Chemical Physics Letters, Vol. 393, Issue 1-3, p. 51-57
  • DOI: 10.1016/j.cplett.2004.06.011

Self‐Consistent Molecular‐Orbital Methods. I. Use of Gaussian Expansions of Slater‐Type Atomic Orbitals
journal, September 1969

  • Hehre, W. J.; Stewart, R. F.; Pople, J. A.
  • The Journal of Chemical Physics, Vol. 51, Issue 6
  • DOI: 10.1063/1.1672392

Development of the Colle-Salvetti correlation-energy formula into a functional of the electron density
journal, January 1988


Adiabatic time-dependent density functional methods for excited state properties
journal, October 2002

  • Furche, Filipp; Ahlrichs, Reinhart
  • The Journal of Chemical Physics, Vol. 117, Issue 16
  • DOI: 10.1063/1.1508368

Geometries and properties of excited states in the gas phase and in solution: Theory and application of a time-dependent density functional theory polarizable continuum model
journal, March 2006

  • Scalmani, Giovanni; Frisch, Michael J.; Mennucci, Benedetta
  • The Journal of Chemical Physics, Vol. 124, Issue 9
  • DOI: 10.1063/1.2173258

Über das Absorptionsspektrum der Polyene
journal, January 1948


A Quantum‐Mechanical Theory of Light Absorption of Organic Dyes and Similar Compounds
journal, December 1949

  • Kuhn, Hans
  • The Journal of Chemical Physics, Vol. 17, Issue 12
  • DOI: 10.1063/1.1747143

Works referencing / citing this record:

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
  • DOI: 10.1039/c9cc05623h

Narrow-band single-photon emission through selective aryl functionalization of zigzag carbon nanotubes
journal, September 2018


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
  • DOI: 10.1038/s41570-019-0103-5

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
  • DOI: 10.1063/1.5055271