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Register a new userPeculiarities of the SERS Spectra of the Hydroquinone Molecule Adsorbed on Titanium Dioxid
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The SERS spectrum of hydroquinone, adsorbed on nanoparticles of titanium dioxide is analyzed. It is pointed out that the enhancement is stronger for larger mean size of nanoparticles that is in an agreement with the electrostatic approximation. In addition it is found that there are the lines, which are forbidden in usual Raman spectra. Along with this there is the enhancement, caused both by the normal and tangential components of the electric field. This result is in agreement with the theory of SERS on semiconductor and dielectric substrates. Discovery of the forbidden lines indicates sufficiently large role of the strong quadrupole light-molecule interaction in such a system.
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The SEHRS and SERS spactra of 4,4 - Bipyridine are analyzed on the base of the Dipole-Quadrupole theory for two possible geometries of the molecule. It is demonstrated that there appear strong lines caused by vibrations transforming after a unit irreducible representation both for the geometry with D2 and D2h symmetry groups, which may probably describe the symmetry properties of the molecule. Appearance of these lines is associated with a strong quadrupole light-molecule interaction, which arises in nano size rregions of sharp roughness of the metal. In addition, there are the lines caused by contributions from both the vibrations transforming after the unit irredicible representations A or Ag and the representations B1 or B1u, respectively, which describe transformational properties of the Ez component of the dipole moment, which is perpendicular to the surface for both geometries. This result is associated with a specific geometry of the molecule, when the indicated vibrations can be nearly degenerated and can not be resolved by the SEHRS and SERS spectra analysis. This issue is in a full compliance with the results of the SEHRS and SERS Dipole-Quadrupole theory.
The paper briefly describes main statements of the theory of the SERS spectra with regards to the single molecule regime, when the enhancement achieves the values . Analysis of the spectra of 4,4-bypyridine, obtained on the dimer lattice of sharp nanoparticles points out that the observed enhancement is caused exclusively by a strong quadrupole light-molecule interaction, which manifests in the presence of lines, caused by vibrations with the unit irreducible representations of the and symmetry groups, which apparently describe the symmetry properties of the molecule. The study of the spectra, obtained by Tip enhanced spectroscopy demonstrates that the strong quadrupole light-molecule interaction still plays a leading role, however the strong dipole interaction still manifests in the existence of very weak forbidden lines. This result apparently is associated with another experimental geometry .
The SERS spectra of the phthalocianine molecule, adsorbed on the gallium phosphide substrate are investigated. It is demonstrated that there appear strong lines, which are forbidden in usual Raman scattering. Analysis of the spectra indicates that these lines are associated with a strong quadrupole light-molecule interaction and also by a strong enhancement of the tangential components of the electric field on the surface. As it was demonstrated earlier, the last effect is characteristic for SERS on semiconductor and dielectric substrates, where there is the enhancement not only of the normal, but of the tangential components of the electric field on the surface.
The SEHRS spectrum of 4,4 Bipyridine is analyzed on the base of the Dipole Quadrupole theory. It is demonstrated that there appear strong lines caused by vibrations transforming after a unit irreducible representation of the D2 symmetry group. which is most probably describes the symmetry properties of the molecule. These lines are nearly forbidden for the molecule, adsorbed on rough metal surface. Appearance of these lines is associated with a strong quadrupole light molecule interaction, which exists in this system. In addition, there are lines, caused by contributions from both the vibrations transforming after the unit irreducible representation A and the representation B1, which describes transformational properties of the dz component of the dipole moment, which is perpendicular to the surface. This result is associated with the specific geometry of the molecule, when the indicated vibrations can be nearly degenerated and cannot be resolved by the SEHRS spectra analysis. Analysis of the SEHRS spectra for the possible geometry of the molecule with the D2h symmetry group leads to similar results. This issue is in a full coincidence with the results of the SEHRS Dipole Quadrupole theory.
It is demonstrated that the reason of SERS on dielectric and semiconductor substrates is the enhancement of the electric field in the regions of the tops of the surface roughness with very small radius, or a very large curvature. The enhancement depends on the dielectric constant of the substrate and is stronger for a larger dielectric constant. It is indicated that the enhancement on dielectrics and semiconductors is weaker than on metals with the same modulus of the dielectric constant. The result obtained is confirmed by experimental data on the enhancement coefficients obtained for various semiconductor and dielectric substrates.
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