A.R. Gazizova,b*, S.S. Kharintseva,b, M.Kh. Salakhova,c
aKazan Federal University, Kazan, 420008 Russia
bTatarstan Academy of Sciences, Institute of Applied Research, Kazan, 420111 Russia
cTatarstan Academy of Sciences, Kazan, 420111 Russia
E-mail: *equus.meteores@gmail.com
Received September 12, 2017
Abstract
This paper is devoted to modeling of the Raman scattering in the ``antenna – sample'' system. The system consists of an anisotropic azo-dye molecule attached covalently to a polymer chain and a plasmonic antenna located near the molecule. A model of near-field interaction in a system of dipoles has been proposed. The model takes into account changes in the polarizabilities of both the antenna and the molecule due to the mutual influence of their near field on each other. Based on the proposed model, the spectra of the tip-enhanced Raman scattering in longitudinally and transversely polarizied field for both isomers of azo-chromophore have been simulated. The static polarizability of the molecule and the Raman-tensors of the vibration modes have been determined by the quantum chemical calculations of a molecule with one monomer according to the density functional theory.
Keywords: azo-chromophore, azo-polymer film, plasmonic antenna, tip-enhanced Raman scattering, near-field polarization, density functional theory, polarizability tensor, Raman tensor
Acknowledgments. We are grateful to K.L. Shukhina and Prof. A.I. Fishman (Kazan Federal University) for their help in the analysis of oscillation modes of the molecule and for obtaining and providing us with the experimental spectra of IR absorption and Raman scattering for the studied molecule.
The study was supported by the Ministry of Education and Science of the Russian Federation (state assignment no. 3.7737.2017/7.8) and performed by using the equipment of the Center of Shared Facilities of Kazan Federal University. The work was funded by the Ministry of Education and Science of the Russian Federation (contract no. 14.575.21.0149 (RFMEFI57517X0149)).
Figure Captions
Fig. 1. The structure of the Disperse Orange 3 (DO3) molecule attached to the CFAO polymer.
Fig. 2. The calculated spectra of IR absorption ( a) and non-resonance Raman scattering ( b) for the cis-isomer and spectra of IR absorption ( c) and non-resonance Raman scattering ( d) for trans-isomer of the DO3 molecule. Scale factor x = 0.981.
Fig. 3. The simulated tip-enhanced Raman spectra of the DO3 molecule attached to the polymer repeat unit: a) cis-isomer in z-polarization of the scattered light, b) cis-isomer in transversal polarization, c) trans-isomer in z-polarization, d) trans-isomer in transversal polarization. Scale factor x = 0.981.
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For citation: Gazizov A.R., Kharintsev S.S., Salakhov M.Kh. Self-consistent model for enhancement of the Raman scattering of polarized light in azo-polymer film with a plasmonic nanoantenna. Uchenye Zapiski Kazanskogo Universiteta. Seriya Fiziko-Matematicheskie Nauki, 2018, vol. 160, no. 1, pp. 61–71. (In Russian)
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