In an asymmetric Au cubic trimer, influence of the rotation angle () and side length () on both plasmonic coupling features and corresponding enhancement factor of hyper-Raman scattering (HRS) process have been investigated comprehensively under the illumination of a longitudinally polarized light. The finite-difference time-domain (FDTD) electrodynamic simulation tool has been employed to calculate the optical cross-section and associated nearfield intensity of the irradiated coupled resonators. Asincreases, the polarization state that dominates the coupling phenomenon is gradually switched from facing sides into facing edges which results in (1) a dramatic change in the spectral response of the trimer and (2) a significant improvement in the nearfield intensity that is directly related to the improvement of HRS signal. Breaking size symmetry of the cubic trimer provides a novel approach to reach the desired spectral response that permits such trimer to be used as an active substrate for HRS procedures. After optimizing both the orientation angle and size of the interacting plasmonic characters forming of the trimer, the enhancement factor of HRS process can reach a value never reported before as high as 1 × 10.
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http://dx.doi.org/10.1088/1361-6528/acd646 | DOI Listing |
Nanotechnology
December 2024
Department of Physics, King Faisal University, King Faisal University P.O. 380 Ahsaa 31982, Al Ahsa, 31982, SAUDI ARABIA.
An anisotropic plasmonic trimer is proposed as an effective spectroscopic amplifier for the maximum signal enhancement of the Hyper-Raman Scattering (HRS) process. The three-particle system is composed of asymmetric Au nanorings arranged collinearly in a J-aggregate configuration and illuminated by a longitudinally polarized light. The optical properties of the considered trimer have been numerically simulated by the Finite-Difference Time-Domain (FDTD) method.
View Article and Find Full Text PDFJ Chem Phys
December 2024
Department of Chemistry, University of Wisconsin-Madison, Madison, Wisconsin 53706, USA.
Nonlinear, four-wave mixing vibrational spectroscopies are commonly used to probe electron-vibration coupling in isotropic media. Most of these methods rely on infrared and/or Raman transitions, but methods involving hyper-Raman transitions are also possible. Hyper difference frequency generation (HDFG) spectroscopy is an underdeveloped four-wave mixing vibrational spectroscopy based upon both infrared absorption and hyper-Raman scattering transitions.
View Article and Find Full Text PDFACS Nano
August 2024
Department of Chemistry and Biochemistry, University of Notre Dame, Notre Dame, Indiana 46556, United States.
In this Perspective, we provide a historical overview of the surface-enhanced hyper-Raman scattering (SEHRS) effect, describe its essential components, highlight the close connection between theory and experiment in several vignettes, and discuss recent analytical applications. SEHRS, the two-photon analog of surface-enhanced Raman scattering (SERS), is a spontaneous nonlinear scattering exhibited by molecules in a plasmonic field. Hyper Raman provides distinctive information on the molecular vibrations and electronic excited states of analytes.
View Article and Find Full Text PDFACS Nano
August 2024
Humboldt-Universität zu Berlin, Department of Chemistry, Brook-Taylor-Str. 2, 12489 Berlin, Germany.
Surface enhanced Raman scattering (SERS) is not restricted to the well-known one-photon excited spontaneous Raman process that gives information on molecular composition, structure, and interaction through vibrational probing with high sensitivity. The enhancement mainly originates in high local fields, specifically those provided by localized surface plasmon resonances of metal nanostructures. High local fields can particularly support nonlinear Raman scattering, as it depends on the fields to higher powers.
View Article and Find Full Text PDFJ Chem Phys
March 2024
Department of Physics and Astronomy, University of Nevada, Las Vegas, Nevada 89154-4002, USA.
The libration spectrum of liquid H2O is resolved into an octupolar twisting libration band at 485 cm-1 and dipolar rocking-wagging libration bands at 707 and 743 cm-1 using polarization analysis of the hyper-Raman scattering (HRS) spectrum. Dipole interactions and orientation correlation over distances less than 2 nm account for the 36 cm-1 splitting of the longitudinal and transverse polarized bands of the dipolar rocking-wagging libration mode, while the intensity difference observed for the bands is the result of libration correlation over distances larger than 200 nm. The coupled rock and wag libration in water is similar to libration modes in ice.
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