Utilizing Microcavities To Suppress Third-Order Cascades in Fifth-Order Raman Spectra

Zhang, Zhedong; Bennett, Kochise; Chernyak, Vladimir; Mukamel, Shaul

doi:10.1021/acs.jpclett.7b01129

Cited by 8 publications

(7 citation statements)

References 44 publications

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“…Optical chirality, [117] twisted light and exotic forms of electromagnetic radiation [118], [119], [120], [121] offer the possibility of new advances in cutting-edge imaging and information processing technologies. Recently there has been interest in the use of quantum light as a way of probing electrodynamical couplings in chemical systems (such as in FRET systems) [122], [123]. The development of such theory, along with its experimental realization, could open new windows into understanding dynamical processes occurring in condensed phase quantum systems.…”

Section: The Power-zienau-woolley Transformationmentioning

confidence: 99%

Perspective: Quantum Hamiltonians for optical interactions

Andrews

Jones

Salam

et al. 2018

The Journal of Chemical Physics

116

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The multipolar Hamiltonian of quantum electrodynamics is extensively employed in chemical and optical physics to treat rigorously the interaction of electromagnetic fields with matter. It is also widely used to evaluate intermolecular interactions. The multipolar version of the Hamiltonian is commonly obtained by carrying out a unitary transformation of the Coulomb gauge Hamiltonian that goes by the name of Power-Zienau-Woolley (PZW). Not only does the formulation provide excellent agreement with experiment, and versatility in its predictive ability, but also superior physical insight. Recently, the foundations and validity of the PZW Hamiltonian have been questioned, raising a concern over issues of gauge transformation and invariance, and whether observable quantities obtained from unitarily equivalent Hamiltonians are identical. Here, an in-depth analysis of theoretical foundations clarifies the issues and enables misconceptions to be identified. Claims of non-physicality are refuted: the PZW transformation and ensuing Hamiltonian are shown to rest on solid physical principles and secure theoretical ground.

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Section: The Power-zienau-woolley Transformationmentioning

confidence: 99%

Perspective: Quantum Hamiltonians for optical interactions

Andrews

Jones

Salam

et al. 2018

The Journal of Chemical Physics

116

View full text Add to dashboard Cite

show abstract

“…Given the uncertainty in the cause of changes to chemical properties caused by strong cavity coupling, research on molecule-based polaritons has recently focused on the changes to the molecular structure caused by polariton formation. − Theoretical prediction of the optical spectra of these systems has been central to understanding such changes. Researchers have predicted linear electronic and vibrational spectra − , in addition to multidimensional vibrational spectra − for molecule–cavity systems in the strong coupling limit.…”

Section: Introductionmentioning

confidence: 99%

Interrogating the Structure of Molecular Cavity Polaritons with Resonance Raman Scattering: An Experimentally Motivated Theoretical Description

Avramenko

Rury

2019

J. Phys. Chem. C

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The formation of exciton polaritons by strongly coupling molecular electronic transitions to spatially confined photons may change photochemical processes. However, the fundamental physical drivers of these proposed changes remain unclear. To understand the role of changes to the molecular structure caused by polariton formation in these photochemical processes, we develop an experimentally motivated theoretical description of resonance Raman scattering from exciton polaritons. By modeling the structural parameters of light absorption in zinc tetraphenyl porphyrin and exciton polaritons formed from this molecule in nanostructured Fabry–Pérot cavities, we simulate resonance Raman scattering excitation spectra from exciton polaritons and assess how these spectra depend on the polariton characteristics. We find that the detuning of the cavity mode energy from that of the molecular transition can affect the structure of the resulting polaritonic states, as inferred from our simulated spectra. We also find previously unreported interference effects between the quantum paths contributing to the resonance Raman scattering pathways changes in the presence of exciton polaritons. Finally, we discuss possible experimental configurations capable of extracting the predicted polariton spectral signatures from the background of the signal from molecules not participating in strong cavity–molecule coupling. These results suggest resonance Raman spectroscopy could be a powerful tool to assess the role changes to the molecular structure plays in the amended photophysics and photochemistry of exciton polaritons.

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“…The most recent experiment demonstrated in BSA protein the remarkable absorption feature around 0.314THz, when driving the system by optical pumping [27]. Understanding these interesting and intriguing experiments will lead us to the deep thinking about Fröhlich's mechanism, since the cooperativity has been shown to exist in some non-physical systems [28,29]. On the other hand, this out-of-equilibrium cooperativity manifests its analogy even at classical level, such that the long-survived limit cycle oscillation in gene network when increasing the binding of active protein to the gene [30,31].…”

mentioning

confidence: 97%

Quantum Fluctuations in the Fröhlich Condensate of Molecular Vibrations Driven Far From Equilibrium

2019

Self Cite

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Fröhlich discovered the remarkable condensation of polar vibrations into the lowest frequency mode when the system is pumped externally. For a full understanding of the Fröhlich condensate one needs to go beyond the mean field level to describe critical behavior as well as quantum fluctuations. The energy redistribution among vibrational modes with nonlinearity included is shown to be essential for realizing the condensate and the phonon-number distribution, revealing the transition from quasi-thermal to super-Poissonian statistics with the pump. We further study the spectroscopic properties of the Fröhlich condensate, which are especially revealed by the narrow linewidth. This gives the long-lived coherence and the collective motion of the condensate. Finally we show that the proteins such as Bovine Serum Albumin (BSA) and lysozyme are most likely the candidates for observing such collective modes in THz regime by means of Raman or infrared (IR) spectroscopy.This supplementary material will provide the derivations for some equations in main text and also some detail analysis of Fröhlich condensate in support of the main text. DESCRIPTION OF MOLECULES IMMERSED IN SOLVENTWhen the molecules are placed in dense medium, i.e., solvent, the full description usually includes the energy of electrons, nucleis of molecules and nucleis of the medium, as well as their interactions. In practice, however, modeling to include so many degrees of freedoms is overwhelmly complicated, which makes the theory elusive and unaccessible. Fortunately, thank to their distinct energy and time scales, we do not have to deal with such a large amount of DOF in practice. This enables us to simplify the model which contains certain DOF of interests. Since we are focusing on the low-frequency (THz) vibrations of molecules where the electron motions will not be altered much in experiments, the effective description of the system contains only the nucleis of molecules and surrounding medium (solvent), dropping the electron energy. In this sense, the Hamiltonian of our interest reads

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Utilizing Microcavities To Suppress Third-Order Cascades in Fifth-Order Raman Spectra

Cited by 8 publications

References 44 publications

Perspective: Quantum Hamiltonians for optical interactions

Perspective: Quantum Hamiltonians for optical interactions

Interrogating the Structure of Molecular Cavity Polaritons with Resonance Raman Scattering: An Experimentally Motivated Theoretical Description

Quantum Fluctuations in the Fröhlich Condensate of Molecular Vibrations Driven Far From Equilibrium

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