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Selection-rule breakdown in plasmon-induced electronic excitation of an isolated single-walled carbon nanotube

Nature Photonics volume 7, pages 550–554 (2013)Cite this article

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Abstract

Optical transitions between electronic levels are restricted according to the selection rules governed by the parities of electronic wavefunctions1. If this restriction can be removed, then drastic improvements in the efficiency and diversity of photoreactions may be realized. Because the selection rules are based on the long wavelength approximation, wherein the field amplitude is assumed to be constant within a molecule, a localized plasmon that has an electromagnetic field with a significantly high gradient is expected to violate the conventional limitations of the optical response2. Here, we demonstrate the possibility of controlling the optical electronic transitions of a single-walled carbon nanotube (SWNT) using metal nanodimers with a controlled nanogap distance. Highly systematic identification of the excitations of individual SWNTs through well-resolved Raman signals implies a breakdown of the selection rules due to the strong field gradient in the radial direction of the SWNTs.

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Figure 1: Energy bands and optical transitions of a semiconducting SWNT.
Figure 2: Enhancement in Raman intensity for an SWNT in a nanogap.
Figure 3: Kataura plots.
Figure 4: Characteristic SERS spectra at ωRBM ≈ 160 cm−1.
Figure 5: Selection-rule breakdown as revealed by an EDDA calculation.

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Acknowledgements

The authors thank R. Saito (Tohoku University) for helpful discussions on Raman spectral analysis. This work was partially supported by Grants-in-Aid for scientific research from the Ministry of Education, Science and Culture, Japan. Support from the Priority Area ‘Strong Photon–Molecule Coupling Fields (no. 470)’ is particularly acknowledged.

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Author notes

  1. Mai Takase & Hideki Nabika

    Present address: Present address: Catalysis Research Center, Hokkaido University, Sapporo, Hokkaido 001-0021, Japan (M.T.); Department of Material and Biological Chemistry, Faculty of Science, Yamagata University, 1-4-12, Kojirakawa, Yamagata 990-8560, Japan (H.N.),

Authors and Affiliations

  1. Department of Chemistry, Faculty of Science, Hokkaido University, North 10 West 8, Kita-ku, Sapporo, 060-0810, Hokkaido, Japan

    Mai Takase, Keiichiro Komeda, Masanobu Nara, Hideki Nabika, Satoshi Yasuda & Kei Murakoshi

  2. Photon Pioneers Center, Osaka University, 2-8 Yamadaoka, Suita, 565-0871, Osaka, Japan

    Hiroshi Ajiki

  3. Department of Physics and Electronics, Osaka Prefecture University, 1-1 Gakuen-cho, Naka-ku, Sakai, 599-8531, Osaka, Japan

    Yoshihiko Mizumoto & Hajime Ishihara

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Contributions

M.T., H.A., Y.M., K.K., M.N., H.N., S.Y., H.I. and K.M. performed experiments and data analysis. H.A. carried out calculations on the electronic structure of SWNTs. Y.M. and H.I. developed the EDDA and performed calculations with this method. M.T., H.A., Y.M., S.Y., H.I. and K.M. contributed to writing the paper.

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Correspondence to Hajime Ishihara or Kei Murakoshi.

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Takase, M., Ajiki, H., Mizumoto, Y. et al. Selection-rule breakdown in plasmon-induced electronic excitation of an isolated single-walled carbon nanotube. Nature Photon 7, 550–554 (2013). https://doi.org/10.1038/nphoton.2013.129

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