We analyze a new type of plasmon system arising from small metal nanoparticles linked by narrow conductive molecular bridges. In contrast to the well-known charge-transfer plasmons, the bridge in these systems consists only of a narrow conductive molecule or polymer in which the electrons move in a ballistic mode, showing quantum effects. The plasmonic system is studied by an original hybrid quantum-classical model accounting for the quantum effects, with the main parameters obtained from first-principles density functional theory simulations. We have derived a general analytical expression for the modified frequency of the plasmons and have shown that its frequency lies in the near-infrared (IR) region and strongly depends on the conductivity of the molecule, on the nanoparticle–molecule interface, and on the size of the system. As illustrated, we explored the plasmons in a system consisting of two small gold nanoparticles linked by a conjugated polyacetylene molecule terminated by sulfur atoms. It is argued that applications of this novel type of plasmon may have wide ramifications in the areas of chemical sensing and IR deep tissue imaging.
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28 December 2019
Research Article|
December 31 2019
Charge-transfer plasmons with narrow conductive molecular bridges: A quantum-classical theory
Special Collection:
Emerging Directions in Plasmonics
A. S. Fedorov
;
A. S. Fedorov
a)
1
Kirensky Institute of Physics, Federal Research Center KSC SB RAS
, 660036 Krasnoyarsk, Russia
2
Federal Siberian Research Clinical Center under FMBA of Russia
, 660037 Krasnoyarsk, Russia
3
Siberian Federal University
, 660041 Krasnoyarsk, Russia
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P. O. Krasnov
;
P. O. Krasnov
2
Federal Siberian Research Clinical Center under FMBA of Russia
, 660037 Krasnoyarsk, Russia
3
Siberian Federal University
, 660041 Krasnoyarsk, Russia
4
Reshetnev Siberian State University of Science and Technology
, 660037 Krasnoyarsk, Russia
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M. A. Visotin;
M. A. Visotin
1
Kirensky Institute of Physics, Federal Research Center KSC SB RAS
, 660036 Krasnoyarsk, Russia
3
Siberian Federal University
, 660041 Krasnoyarsk, Russia
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F. N. Tomilin
;
F. N. Tomilin
1
Kirensky Institute of Physics, Federal Research Center KSC SB RAS
, 660036 Krasnoyarsk, Russia
3
Siberian Federal University
, 660041 Krasnoyarsk, Russia
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S. P. Polyutov
;
S. P. Polyutov
b)
1
Kirensky Institute of Physics, Federal Research Center KSC SB RAS
, 660036 Krasnoyarsk, Russia
3
Siberian Federal University
, 660041 Krasnoyarsk, Russia
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H. Ågren
H. Ågren
2
Federal Siberian Research Clinical Center under FMBA of Russia
, 660037 Krasnoyarsk, Russia
5
Division of Theoretical Chemistry and Biology, Royal Institute of Technology
, SE-100 44 Stockholm, Sweden
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a)
Electronic mail: alex99@iph.krasn.ru
b)
Electronic mail: spolyutov@sfu-kras.ru
Note: This paper is part of the JCP Special Topic on Emerging Directions in Plasmonics.
J. Chem. Phys. 151, 244125 (2019)
Article history
Received:
October 15 2019
Accepted:
December 09 2019
Citation
A. S. Fedorov, P. O. Krasnov, M. A. Visotin, F. N. Tomilin, S. P. Polyutov, H. Ågren; Charge-transfer plasmons with narrow conductive molecular bridges: A quantum-classical theory. J. Chem. Phys. 28 December 2019; 151 (24): 244125. https://doi.org/10.1063/1.5131734
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