The idea of utilizing the second-order plasmon resonance of the gold nanorod π-dimers for plasmon rulers is introduced. We report on a qualitatively different dependence of the plasmon resonance shift on the interparticle distance for the first-and second-order longitudinal modes, extending the working range of plasmon rulers up to the distance values of 400 nm.PACS numbers: 36.40. Gk, 73.20.Mf, 78.67.Bf, 78.20.Ci Optical properties of gold nanoparticles have contributed to many areas of science and technology, such as drug delivery 1 , cell imaging 2 , photothermal therapy 3 and others. In particular, a possibility of measuring nanoscale length utilizing pairs of gold nanoparticles-i.e., plasmonic dimers-was demonstrated 4,5 producing the idea of so-called plasmon ruler. Operating principles of plasmon rulers are based on the fact that the spectral position of the surface plasmon resonance (SPR) of a plasmonic dimer strongly depends on the distance between the particles forming the dimer 6 . This phenomenon makes it possible, e.g., to measure length of a sub-100-nm macromolecule with gold nanoparticles bound to its ends by measuring the SPR position and comparing it to one of the uncoupled nanoparticles 4 . Tailorable nature of SPR allows flexible tuning of plasmonic dimer optical properties by changing the shape, mutual arrangement, or polarization of the incoming light and, hence, the type of the resonance 7-9 . In plasmon rulers, however, the maximum measurable distance is still limited to roughly 100 nm.Nanorods are one of the frequently used shapes to analyze the physics behind the near-field coupling of plasmonic nanoparticles 10 . One distinguishes between two types of nanorod dimers-the so-called π-dimer and σ-dimer, referring to the analogy from the orientation of coupled atom p-orbitals. Providing subwavelength field localization in the gap between the inline arranged nanoparticles, the σ-dimer is used in nanoantenna research 11 and applications, such as improved surfaceenhanced Raman scattering 12 . The π-dimer, on the other hand, is a system conventionally considered for observation of optical magnetism happening when the freeelectron currents are out of phase in the nanorods forming the dimer 13 . Finally, for nanorods long enough it is possible to excite several longitudinal SPR modes 14 . Nevertheless considered theoretically 15,16 , the coupling properties of the higher-order resonances were neither provided experimentally so far, nor were they considered as a basis for a qualitatively different plasmon ruler-type a) Electronic mail: fedyanin@nanolab.phys.msu.ru system.In this contribution, we obtain the dependence of the SPR position λ 0 on the distance between the rods d for a set of π-dimers by means of microspectroscopy of gold nanorod samples and corresponding numerical calculations. The first-and second-order longitudinal dipolar plasmon resonances are considered. It is shown that one can use the λ 0 (d) dependence for the second-order resonance to form a plasmon ruler with working dist...
The idea of utilizing the second-order plasmon resonance of the gold nanorod π-dimers for plasmon rulers is introduced. We report on a qualitatively different dependence of the plasmon resonance shift on the interparticle distance for the first-and second-order longitudinal modes, extending the working range of plasmon rulers up to the distance values of 400 nm.
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