SERS phenomenon as a manifestation of quadrupole interaction of light with molecules

Polubotko, A. M.

doi:10.1016/0375-9601(90)90034-l

Cited by 24 publications

(21 citation statements)

References 1 publication

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“…Due to the high localization of the optical near-field, the molecules in the tip-sample gap experience a large field gradient and different Raman symmetry selection rules can come into play [168][169][170]. The relevant terms of the dipole moment μ a of a molecule situated in the presence of a high field-gradient are:…”

Section: Ters Of Molecular Adsorbatesmentioning

confidence: 99%

Tip-Enhanced Raman Imaging and Nanospectroscopy: Sensitivity, Symmetry, and Selection Rules

2007

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The fundamental mechanisms of tipenhanced Raman spectroscopy (TERS) have been investigated, including the role of the plasmonic excitation of the metallic tips, the nature of the optical tip-sample coupling, and the resulting local-field enhancement and confinement responsible for ultrahigh resolution imaging down to just several nanometers. Criteria for the distinction of near-field signature from far-field imaging artifacts are addressed. TERS results of molecules are presented. With enhancement factors as high as 10 9 , single-molecule spectroscopy is demonstrated. Spatially resolved vibrational mapping of crystalline nanostructures and determination of crystallographic orientation and domains is discussed making use of the symmetry properties of the tip scattering response and the intrinsic Raman selection rules.

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Section: Ters Of Molecular Adsorbatesmentioning

confidence: 99%

Tip-Enhanced Raman Imaging and Nanospectroscopy: Sensitivity, Symmetry, and Selection Rules

2007

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“…12 -14 On the basis of the quadrupole theory, it has been demonstrated that owing to the strong polarization at the tips of the particles, molecules are attracted to these areas where the electric field strength strongly increases, resulting in increased EF. It should be mentioned that strong electric fields can cause significantly altered selection rules 12,13 leading to the appearance of forbidden Raman lines, explaining some of the changes observed in the SER spectra compared to regular Raman spectra. The relaxation of the selection rules can also be explained by the gradient field effect.…”

Section: Introductionmentioning

confidence: 99%

SERS intensity optimization by controlling the size and shape of faceted gold nanoparticles

Sabur

Havel

Gogotsi

2007

J Raman Spectroscopy

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In this work, we experimentally investigated the surface-enhanced Raman spectroscopy (SERS) activity of faceted gold nanoparticles, which have been theoretically predicted to yield giant enhancements. Glycine was used to determine the SERS activity as a function of pH and ionic strength and to estimate the corresponding enhancement factor (EF). By optimizing the synthesis conditions of the flat prismatic nanoparticles, it was possible to control their size and shape. We demonstrate that the maximum SERS intensity increases with the edge length of the triangle, reaching a maximum EF of ∼10 13 for 1.9 µm triangles (the largest tested). The corresponding glycine detection limit was as low as 10 −12 M, close to the single-molecule threshold.

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“…As was demonstrated in Refs1–4, the enhancement of the dipole and quadrupole interactions arises owing to the huge increase of the E z ′ component of the electric field, which is perpendicular to the surface, and derivatives of this field ∂ E α /∂ x α near sharp features of the surface. Another essential reason for the enhancement of the quadrupole interaction is a quantum mechanical feature of matrix elements of the quadrupole moments Q αα with a constant sign.…”

Section: Estimation Of the Enhancement Of The Dipole And Quadrupole Imentioning

confidence: 83%

Cross‐section and selection rules in surface‐enhanced hyper Raman scattering

Polubotko

Smirnov

2011

J Raman Spectroscopy

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The expression for the SEHR cross-section of symmetrical molecules within the framework of the dipole-quadrupole theory is obtained. It is formed by contributions, which depend on various dipole and quadrupole moments. Estimation of the enhancement coefficients for the quadrupole enhancement mechanism in some limited case can achieve the value 30 10 . It is demonstrated that the contributions follow some selection rules. Qualitative classification of the contributions after the enhancement degree is given.

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SERS phenomenon as a manifestation of quadrupole interaction of light with molecules

Cited by 24 publications

References 1 publication

Tip-Enhanced Raman Imaging and Nanospectroscopy: Sensitivity, Symmetry, and Selection Rules

Tip-Enhanced Raman Imaging and Nanospectroscopy: Sensitivity, Symmetry, and Selection Rules

SERS intensity optimization by controlling the size and shape of faceted gold nanoparticles

Cross‐section and selection rules in surface‐enhanced hyper Raman scattering

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