scholarly journals Polariton-Mediated Electron Transfer via Cavity Quantum Electrodynamics

2020 ◽  
Vol 124 (29) ◽  
pp. 6321-6340 ◽  
Author(s):  
Arkajit Mandal ◽  
Todd D. Krauss ◽  
Pengfei Huo
2020 ◽  
Author(s):  
Arkajit Mandal ◽  
Todd D. Krauss ◽  
Pengfei Huo

We investigate the polariton mediated electron transfer reaction in a model system. With analytic rate constant expression and direct quantum dynamical simulations, we demonstrate that charge transfer reactions can be significantly enhanced or suppressed by coupling the molecular system to the quantized radiation field inside an optical cavity. This is due to the fact that quantum light-matter interactions can mediate the effective driving force and electronic couplings between the hybrid light-matter excitation (so-called the polariton states). Under a resonance condition, the effective driving force can be tuned by changing the light-matter coupling strength; for an off-resonant condition, the same effect can be accomplished by changing the molecule-cavity detuning. Forming polaritons thus provides new possibilities to control the fundamental photo-redox chemistry. Further, we find that both the counter-rotating terms and the dipole self-energy in the quantum electrodynamics Hamiltonian play a crucial role for obtaining an accurate polariton eigenenergy and the polariton mediated charge transfer rate constant, especially in the ultra-strong coupling regime. These investigations significantly complement the previous theoretical developments that ignore both terms, and bring interesting concepts from quantum optics into the field of photochemistry


2020 ◽  
Author(s):  
Arkajit Mandal ◽  
Todd D. Krauss ◽  
Pengfei Huo

We investigate the polariton mediated electron transfer reaction in a model system. With analytic rate constant expression and direct quantum dynamical simulations, we demonstrate that charge transfer reactions can be significantly enhanced or suppressed by coupling the molecular system to the quantized radiation field inside an optical cavity. This is due to the fact that quantum light-matter interactions can mediate the effective driving force and electronic couplings between the hybrid light-matter excitation (so-called the polariton states). Under a resonance condition, the effective driving force can be tuned by changing the light-matter coupling strength; for an off-resonant condition, the same effect can be accomplished by changing the molecule-cavity detuning. Forming polaritons thus provides new possibilities to control the fundamental photo-redox chemistry. Further, we find that both the counter-rotating terms and the dipole self-energy in the quantum electrodynamics Hamiltonian play a crucial role for obtaining an accurate polariton eigenenergy and the polariton mediated charge transfer rate constant, especially in the ultra-strong coupling regime. These investigations significantly complement the previous theoretical developments that ignore both terms, and bring interesting concepts from quantum optics into the field of photochemistry


2020 ◽  
Author(s):  
Sutirtha N. Chowdhury ◽  
Arkajit Mandal ◽  
Pengfei Huo

We use the ring-polymer (RP) representation to quantize the radiation field inside an optical cavity to investigate polariton quantum dynamics. Using a charge transfer model coupled to an optical cavity, we demonstrate that the RP quantization of the photon field provides accurate rate constants of the polariton mediated electron transfer (PMET) reaction compared to the Fermi's Golden rule. Because RP quantization uses extended phase space to describe the photon field, it significantly reduces the computational costs compared to the commonly used Fock states description of the radiation field. Compared to the other quasi-classical descriptions of the photon field, such as the classical Wigner model, the RP representation provides a much more accurate description of the polaritonic quantum dynamics, because it properly preserves the quantum distribution of the photonic DOF throughout the quantum dynamics propagation of the molecule-cavity hybrid system, whereas the classical Wigner model fails to do so. This work demonstrates the possibility of using the ring-polymer description to treat the quantized radiation field in polariton chemistry, offering an accurate and efficient approach for future investigations in cavity quantum electrodynamics.


2020 ◽  
Author(s):  
Sutirtha N. Chowdhury ◽  
Arkajit Mandal ◽  
Pengfei Huo

We use the ring-polymer (RP) representation to quantize the radiation field inside an optical cavity to investigate polariton quantum dynamics. Using a charge transfer model coupled to an optical cavity, we demonstrate that the RP quantization of the photon field provides accurate rate constants of the polariton mediated electron transfer (PMET) reaction compared to the Fermi's Golden rule. Because RP quantization uses extended phase space to describe the photon field, it significantly reduces the computational costs compared to the commonly used Fock states description of the radiation field. Compared to the other quasi-classical descriptions of the photon field, such as the classical Wigner model, the RP representation provides a much more accurate description of the polaritonic quantum dynamics, because it properly preserves the quantum distribution of the photonic DOF throughout the quantum dynamics propagation of the molecule-cavity hybrid system, whereas the classical Wigner model fails to do so. This work demonstrates the possibility of using the ring-polymer description to treat the quantized radiation field in polariton chemistry, offering an accurate and efficient approach for future investigations in cavity quantum electrodynamics.


iScience ◽  
2021 ◽  
Vol 24 (1) ◽  
pp. 101892
Author(s):  
Yaniv Shlosberg ◽  
Benjamin Eichenbaum ◽  
Tünde N. Tóth ◽  
Guy Levin ◽  
Varda Liveanu ◽  
...  

2020 ◽  
Vol 153 (18) ◽  
pp. 185101
Author(s):  
Nirmalendu Acharyya ◽  
Roman Ovcharenko ◽  
Benjamin P. Fingerhut

2016 ◽  
Vol 82 (16) ◽  
pp. 5026-5038 ◽  
Author(s):  
Erick M. Bosire ◽  
Lars M. Blank ◽  
Miriam A. Rosenbaum

ABSTRACTPseudomonas aeruginosais an important, thriving member of microbial communities of microbial bioelectrochemical systems (BES) through the production of versatile phenazine redox mediators. Pure culture experiments with a model strain revealed synergistic interactions ofP. aeruginosawith fermenting microorganisms whereby the synergism was mediated through the shared fermentation product 2,3-butanediol. Our work here shows that the behavior and efficiency ofP. aeruginosain mediated current production is strongly dependent on the strain ofP. aeruginosa. We compared levels of phenazine production by the previously investigated model strainP. aeruginosaPA14, the alternative model strainP. aeruginosaPAO1, and the BES isolatePseudomonassp. strain KRP1 with glucose and the fermentation products 2,3-butanediol and ethanol as carbon substrates. We found significant differences in substrate-dependent phenazine production and resulting anodic current generation for the three strains, with the BES isolate KRP1 being overall the best current producer and showing the highest electrochemical activity with glucose as a substrate (19 μA cm−2with ∼150 μg ml−1phenazine carboxylic acid as a redox mediator). Surprisingly,P. aeruginosaPAO1 showed very low phenazine production and electrochemical activity under all tested conditions.IMPORTANCEMicrobial fuel cells and other microbial bioelectrochemical systems hold great promise for environmental technologies such as wastewater treatment and bioremediation. While there is much emphasis on the development of materials and devices to realize such systems, the investigation and a deeper understanding of the underlying microbiology and ecology are lagging behind. Physiological investigations focus on microorganisms exhibiting direct electron transfer in pure culture systems. Meanwhile, mediated electron transfer with natural redox compounds produced by, for example,Pseudomonas aeruginosamight enable an entire microbial community to access a solid electrode as an alternative electron acceptor. To better understand the ecological relationships between mediator producers and mediator utilizers, we here present a comparison of the phenazine-dependent electroactivities of threePseudomonasstrains. This work forms the foundation for more complex coculture investigations of mediated electron transfer in microbial fuel cells.


2003 ◽  
Vol 26 (2) ◽  
pp. 187-196 ◽  
Author(s):  
L. Bade ◽  
E. G. Petrov ◽  
V. May

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