Near-field manipulation of spectroscopic selection rules on the nanoscale

  • Prashant K. Jain
    Department of Chemistry, University of California, Berkeley, CA 94720;
  • Debraj Ghosh
    Department of Chemistry, University of California, Berkeley, CA 94720;
  • Roi Baer
    Fritz Haber Center for Molecular Dynamics, The Chaim Weizmann Institute of Chemistry, Hebrew University of Jerusalem, Jerusalem 91904, Israel; and
  • Eran Rabani
    School of Chemistry, The Sackler Faculty of Sciences, Tel Aviv University, Tel Aviv 69978, Israel
  • A. Paul Alivisatos
    Department of Chemistry, University of California, Berkeley, CA 94720;

抄録

<jats:p>In conventional spectroscopy, transitions between electronic levels are governed by the electric dipole selection rule because electric quadrupole, magnetic dipole, and coupled electric dipole-magnetic dipole transitions are forbidden in a far field. We demonstrated that by using nanostructured electromagnetic fields, the selection rules of absorption spectroscopy could be fundamentally manipulated. We also show that forbidden transitions between discrete quantum levels in a semiconductor nanorod structure are allowed within the near-field of a noble metal nanoparticle. Atomistic simulations analyzed by an effective mass model reveal the breakdown of the dipolar selection rules where quadrupole and octupole transitions are allowed. Our demonstration could be generalized to the use of nanostructured near-fields for enhancing light-matter interactions that are typically weak or forbidden.</jats:p>

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