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A. M. Polubotko

Publications and source records attributed to A. M. Polubotko.

At least 19 recordsLinked to original sources
arXiv2018

Investigation of the SERS spectra of copper phthalocianine adsorbed on gallium phosphide substrates

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.

physics.chem-ph↗
arXiv2017

Peculiarities of the SERS Spectra of the Hydroquinone Molecule Adsorbed on Titanium Dioxid

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.

physics.chem-ph↗
arXiv2017

Peculiarities of the SERS Spectra of 4,4-Bipyridine Molecule in a Single Molecule Detection Regime

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 .

physics.chem-ph↗
arXiv2017

SERS Mechanism on Graphene

The paper presents briefly some general points of the theory of Surface Enhanced Raman Scattering on metals, semiconductors, dielectrics and graphene. It is pointed out that the reason of SERS on graphene and some other 2D materials is not the chemical enhancement mechanism as it is widely accepted in literature, but ripples, which are necessarily present on a graphene surface and are analogues of the surface roughness, which is a reason of SERS. In addition, it is indicated that the quadrupole interaction, which arises in strong SERS is practically absent in the system with graphene. The results are confirmed by the analysis of the SERS, usual Raman and IR spectra of phthalocyanine molecule and by some other experimental data.

physics.optics↗
arXiv2016

Electrodynamical Forbiddance of the Strong Quadrupole Light-Molecule Interaction and Its Experimental Manifestation in Fullerene C60

It is demonstrated that the forbidden lines, which must be present in the SERS, TERS and SEIRA spectra of molecules with sufficiently high symmetry, associated with a strong quadrupole light-molecule interaction, are absent in the fullerene C60. This result is an experimental manifestation of an electrodynamical forbiddance of the strong quadrupole light-molecule interaction, which must be not only in molecules with cubic symmetry groups, but in the fullerene C60 also.

physics.optics↗
arXiv2015

Analysis of Peculiarities of the SEHRS Spectrum of - Bipyridine Molecule on the Base of the Dipole-Quadrupole Theory

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.

physics.chem-ph↗
arXiv2014

The Theory of Surface Enhanced Hyper Raman Scattering

The Dipole-Quadrupole theory of Surface Enhanced Hyper Raman Scattering (SEHRS), created by the authors is expounded in details. Peculiarities of the behavior of electromagnetic field on rough metal surfaces are considered. It is demonstrated that there is an enhancement of the dipole and quadrupole light-molecule interaction near the places with a large curvature. The expression for the SEHRS cross-section of symmetrical molecules, which consists of several contributions is obtained. Selection rules for the scattering contributions are obtained and a qualitative classification of the contributions after an enhancement degree is performed. Analysis of experimental spectra of pyrazine and phenazine, and also some another molecules is performed too. It is demonstrated a full coincidence of experimental regularities in these spectra with the theory suggested.

physics.optics↗
arXiv2014

Electrodynamical Forbiddance of Strong Quadrupole Light-Molecule Interaction in the Methane Molecule and its Manifestation in Surface Enhanced Hyper Raman Scattering Spectra

It is demonstrated in the framework of the Dipole-Quadrupole theory, that strong quadrupole light-molecule interaction, which is responsible for the most enhancement of SEHRS in the methane molecule, which belongs to the symmetry group, experiences so-called electrodynamical forbiddance due to electrodynamical law, and does not influence on the formation of the SEHRS spectra. This forbiddance results in the fact that the lines, caused by the totally symmetric vibrations, transforming after the unit irreducible representation, which are observed in symmetrical molecules with another sufficiently high groups of the point symmetry, such as pyrazine and phenazine, with symmetry group, must be slight, or be absent at all. In this case in methane the most enhanced lines are those, caused by vibrations, transforming by the irreducible representation, or .

physics.chem-ph↗
arXiv2013

The dipole-quadrupole theory of surface-enhanced Raman scattering

The review is devoted to explanation of SERS in terms of the dipole and quadrupole light-molecule interactions arising in surface fields strongly varying in space in the region of the strongly irregular surface roughness. The main SERS characteristics, the theory of electromagnetic fields near some model kinds of rough surfaces and some other systems, the theory of SERS Raman tensor for arbitrary and symmetrical molecules, selection rules and analysis of the SER spectra, some anomalies in the SER spectra of symmetrical molecules for some specific conditions, electrodynamic forbiddance of the quadrupole scattering mechanism for the methane molecule and molecules with cubic symmetry groups are considered. The huge enhancement and blinking of the SERS signal arising in the phenomenon of Single Molecule detection by the SERS method are explained. The above theory is compared with some another SERS mechanisms, and the phenomena accompanying SERS are accounted for. It is demonstrated that the theory is in a good agreement with the experiment and explains quite a number of characteristics related to the SERS phenomenon.

physics.chem-ph↗
arXiv2013

Some Features of Raman Scattering by Molecules Adsorbed on Metal Crystal Faces and a Fine Light Structure

The paper analyzes some experiments on Raman scattering by molecules adsorbed on the face (111) of silver monocrystals performed by A. Campion et al. From the existence of the forbidden line of benzene, the conclusion about existence of the surface field, caused by atomic structure of the surface is made. The relatively large intensity of this line allows to make a conclusion about large influence of the electromagnetic field spatial inhomogeneity in crystals on their optical properties. The difference between this field and a regular plane wave, which usually describes propagation of electromagnetic field in solids is named as a fine light structure. The influence of this structure on optical properties of solids is pointed out.

physics.optics↗
arXiv2012

Dipole-Quadrupole Theory of Surface Enhanced Infrared Absorption and Appearance of Forbidden Lines in the SEIRA Spectra of Symmetrical Molecules

The paper presents main aspects of the Dipole-Quadrupole theory of Surface Enhanced Infrared Absorption (SEIRA). It is pointed out the possibility of appearance of the lines, caused by totally symmetric vibrations transforming after the unit irreducible representation, which are forbidden in usual infrared absorption spectra in molecules with sufficiently high symmetry. Observation of such lines in the SEIRA spectra of diprotonated and ethylene, adsorbed on and on mordenites is pointed out. The results well agree with our ideas about surface enhanced optical processes, based on the conception of a strong quadrupole light-molecule interaction, which allows us to develop the SERS and SEHRS theories.

physics.optics↗
arXiv2011

Analysis of the SEHR Spectra of Symmetrical Molecules on the Base of the Dipole-Quadrupole Theory

The paper analyses the SEHR spectra of symmetrical molecules on the base of the dipole-quadrupole SEHRS theory. Existence of the bands, caused by vibrations transforming after the unit irreducible representations of corresponding symmetry groups is demonstrated. As it follows from the theoretical group analysis, these bands are forbidden in phenazine, pyrazine and in usual HRS in molecules belonging to a large number of groups (Cnh, D and higher symmetry groups for example). Their appearance strongly confirms the dipole-quadrupole SEHRS theory, which is able to explain other features of the SEHR spectra of these molecules also. Investigation of the SEHR spectra of pyridine and crystal violet demonstrates that they can be explained by this theory too. All these results point out the existence of the strong quadrupole light-molecule interaction, which is the reason of surface-enhanced optical processes.

physics.chem-ph↗
arXiv2011

Manifestation of the strong quadrupole light-molecule interaction in the SEHR spectra of phenazine and pyrazine

The paper demonstrates possibility of giant enhancement of Surface Enhanced Hyper Raman Scattering on the base of qualitative consideration of electromagnetic field near some models of rough metal surfaces and of some features of the dipole and quadrupole light-molecule interaction, such as it was made in the dipole-quadrupole SERS theory. Consideration of symmetrical molecules allows to obtain selection rules for their SEHR spectra and establish such regularity as appearance of the lines, caused by totally symmetric vibrations, transforming after the unit irreducible representation in molecules with the groups, where the elements of symmetry change z on -z . These lines are forbidden in usual HRS spectra. Analysis of literature data on phenazine and pyrazine molecules demonstrates that their SEHR spectra can be explained by the SEHRS dipole-quadrupole theory. Analysis of the SEHR spectra of these molecules reveals appearance of strong forbidden bands, caused by vibrations transforming after the unit irreducible representation that strongly confirms this theory which allows to interpret the whole SEHR spectra in detail. The results corroborate this common mechanism of Surface Enhanced optical processes on molecules adsorbed on rough metal surfaces.

physics.optics↗
arXiv2011

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

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 . It is demonstrated that the contributions follow some selection rules. Qualitative classification of the contributions after the enhancement degree is given.

physics.chem-ph↗
arXiv2011

Manifestation of Strong Quadrupole Light-Molecule Interaction in the SER and SEHR Spectra of Pyrazine and Phenazine

It is demonstrated that explanation of appearance of strong forbidden lines in the SEHR spectra of pyrazine and phenazine, caused by totally symmetric vibrations and also other details of their SER and SEHR spectra can be made on the base of the dipole-quadrupole theory. The main point of this theory is conception of a strong quadrupole light molecule interaction, arising in surface fields strongly varying in space near a rough metal surface. Existence of the pointed lines is a good corroboration of existence of the strong quadrupole light-molecule interaction.

physics.optics↗
arXiv2011

Manifestation of the strong quadrupole light-molecule interaction in the SEHR spectra of symmetrical molecules

The paper demonstrates possibility of giant enhancement of Surface Enhanced Hyper Raman Scattering on the base of qualitative consideration of electromagnetic field near some models of rough metal surfaces and of some features of the dipole and quadrupole light-molecule interaction, such as it was made in the dipole-quadrupole SERS theory. Consideration of symmetrical molecules allows to obtain selection rules for their SEHR spectra and establish such regularity as appearance of the bands, caused by the totally symmetric vibrations, transforming after the unitary irreducible representation in molecules with C2h,D and higher symmetry groups, which are forbidden in usual HRS spectra. Analysis of literature data on trans-1,2-bis (4-pyridyle) ethylene and pyridine molecules demonstrates that their SEHR spectra can be explained by the SEHRS dipole-quadrupole theory, while analysis of the SEHR spectrum of pyrazine reveals appearance of the strong forbidden bands, caused by vibrations transforming after the unitary irreducible representation that strongly confirms this theory which permits to interpret the whole SEHR spectrum in detail. The results corroborate this common mechanism of Surface Enhanced optical processes on molecules adsorbed on rough metal surfaces.

physics.optics↗