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Raman Spectroscopy: Overview01:20

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The underlying principle of Raman spectroscopy is based on the interaction between light and matter, specifically molecules' inelastic scattering of photons. When a monochromatic beam of light, typically from a laser source, interacts with a sample, most scattered light has the same frequency as the incident light. This is known as Rayleigh scattering.
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A conventional Raman spectrophotometer includes a laser source, a sample holding system, a wavelength selector, and a detector.
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Double resonance techniques in Nuclear Magnetic Resonance (NMR) spectroscopy involve the simultaneous application of two different frequencies or radiofrequency pulses to manipulate and observe two distinct nuclear spins. One important application of double resonance is spin decoupling, which selectively suppresses coupling with one type of nucleus while observing the NMR signal from another nucleus, simplifying the spectrum and enhancing resolution.
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Multiplex Chemical Imaging Based on Broadband Stimulated Raman Scattering Microscopy
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Tip-Enhanced Multipolar Raman Scattering.

Chih-Feng Wang1, Zhihua Cheng2, Brian T O'Callahan3

  • 1Physical Sciences Division, Pacific Northwest National Laboratory, P.O. Box 999, Richland, Washington 99352, United States.

The Journal of Physical Chemistry Letters
|March 12, 2020
PubMed
Summary
This summary is machine-generated.

We observed multipolar Raman scattering in tip-enhanced Raman spectroscopy (TERS) of gold nanocubes. This reveals previously unseen chemical information at the nanoscale, crucial for advanced chemical imaging.

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Area of Science:

  • Plasmonics
  • Nanophotonics
  • Chemical Imaging

Background:

  • Tip-enhanced Raman spectroscopy (TERS) is a powerful technique for nanoscale chemical analysis.
  • Conventional TERS signals are primarily dipolar.
  • Understanding higher-order scattering is essential for advanced TERS applications.

Purpose of the Study:

  • To investigate and identify multipolar Raman scattering contributions in TERS.
  • To analyze the role of electric field gradients in TERS spectra.
  • To explore the potential of multipolar TERS for chemical reaction mapping.

Main Methods:

  • TERS measurements on thiobenzonitrile (TBN)-functionalized gold nanocubes.
  • Analysis of spectral signatures in the 1225-1500 cm-1 region.
  • Assignment of Raman-forbidden transitions to multipolar scattering phenomena.

Main Results:

  • Observed and assigned weak spectral signatures to multipolar Raman scattering (electric dipole-magnetic dipole and electric dipole-electric quadrupole).
  • Demonstrated that multipolar scattering can dominate single-pixel TERS spectra.
  • Correlated multipolar scattering with spatially varying enhanced electric field gradients.

Conclusions:

  • Multipolar Raman scattering is a significant, often overlooked, component of TERS.
  • Accurate interpretation of TERS spectral images requires accounting for both dipolar and multipolar contributions.
  • This finding is critical for advancing TERS-based chemical reaction mapping.