Investigate New Reactivities Enabled by Polariton Photochemistry

2019 ◽  
Author(s):  
Arkajit Mandal ◽  
Pengfei Huo
Keyword(s):  
Excited State ◽  
Quantum Electrodynamics ◽  
Quantum Dynamics ◽  
Optical Cavity ◽  
Cavity Quantum Electrodynamics ◽  
Photochemical Reactions ◽  
Isomerization Reaction ◽  
Resonance Case ◽  
Radiation Mode ◽  
Dynamics Simulations

We perform quantum dynamics simulations to investigate new chemical reactivities enabled by cavity quantum electrodynamics. The quantum light-matter interactions between the molecule and the quantized radiation mode inside an optical cavity create a set of hybridized electronic-photonic states, so-called polaritons. The polaritonic states adapt the curvatures from both the ground and the excited electronic states, opening up new possibilities to control photochemical reactions by exploiting intrinsic quantum behaviors of light-matter interactions. With direct quantum dynamics simulations, we demonstrate that the selectivity of a model photo-isomerization reaction can be controlled by tuning the photon frequency of the cavity mode or the light-matter coupling strength, providing new ways to manipulate chemical reactions via light-matter interaction. We further investigate collective quantum effects enabled by coupling quantized radiation mode to multiple molecules. Our results suggest that in the resonance case, a photon is recycled among molecules to enable multiple excited state reactions, thus effectively functioning as a catalyst. In the non-resonance case, molecules emit and absorb virtual photons to initiate excited state reactions through fundamental quantum electrodynamics processes. These results from direct quantum dynamics simulations reveal basic principles of polariton photochemistry as well as promising reactivities that take advantage of intrinsic quantum behaviors of photons.

Investigate New Reactivities Enabled by Polariton Photochemistry

2019 ◽  
Author(s):  
Arkajit Mandal ◽  
Pengfei Huo
Keyword(s):  
Excited State ◽  
Quantum Electrodynamics ◽  
Quantum Dynamics ◽  
Optical Cavity ◽  
Cavity Quantum Electrodynamics ◽  
Photochemical Reactions ◽  
Isomerization Reaction ◽  
Resonance Case ◽  
Radiation Mode ◽  
Dynamics Simulations

We perform quantum dynamics simulations to investigate new chemical reactivities enabled by cavity quantum electrodynamics. The quantum light-matter interactions between the molecule and the quantized radiation mode inside an optical cavity create a set of hybridized electronic-photonic states, so-called polaritons. The polaritonic states adapt the curvatures from both the ground and the excited electronic states, opening up new possibilities to control photochemical reactions by exploiting intrinsic quantum behaviors of light-matter interactions. With direct quantum dynamics simulations, we demonstrate that the selectivity of a model photo-isomerization reaction can be controlled by tuning the photon frequency of the cavity mode or the light-matter coupling strength, providing new ways to manipulate chemical reactions via light-matter interaction. We further investigate collective quantum effects enabled by coupling quantized radiation mode to multiple molecules. Our results suggest that in the resonance case, a photon is recycled among molecules to enable multiple excited state reactions, thus effectively functioning as a catalyst. In the non-resonance case, molecules emit and absorb virtual photons to initiate excited state reactions through fundamental quantum electrodynamics processes. These results from direct quantum dynamics simulations reveal basic principles of polariton photochemistry as well as promising reactivities that take advantage of intrinsic quantum behaviors of photons.

scholarly journals Ring-Polymer Quantization of Photon Field in Polariton Chemistry

2020 ◽  
Author(s):  
Sutirtha N. Chowdhury ◽  
Arkajit Mandal ◽  
Pengfei Huo
Keyword(s):  
Radiation Field ◽  
Quantum Electrodynamics ◽  
Quantum Dynamics ◽  
Optical Cavity ◽  
Cavity Quantum Electrodynamics ◽  
Transfer Model ◽  
Quantum Distribution ◽  
Photon Field ◽  
Mediated Electron Transfer ◽  
Ring Polymer

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.

scholarly journals Mode-Selective Chemistry through Polaritonic Vibrational Strong Coupling

2021 ◽  
Author(s):  
Xinyang Li ◽  
Arkajit Mandal ◽  
Pengfei Huo
Keyword(s):  
Quantum Electrodynamics ◽  
Optical Cavity ◽  
Cavity Quantum Electrodynamics ◽  
Reaction Coordinate ◽  
Vacuum Fluctuations ◽  
Radiation Mode ◽  
Competitive Reactions ◽  
Photon Frequency ◽  
Theoretical Results ◽  
Fundamental Mechanism

Recent experiments have demonstrated remarkable mode-selective reactivities by coupling molecular vibrations with vacuum fluctuations inside an optical cavity. The fundamental mechanism behind such effects, on the other hand, remains elusive. In this work, we theoretically demonstrate the basic principle of how cavity photon frequency can be tuned to achieve mode-selective reactivities. We find that the non-Markovian nature of the radiation mode leads to a cavity frequency-dependent dynamical caging effect of a reaction coordinate, resulting in a suppression of the rate constant. In the presence of multiple competitive reactions, it is possible to preferentially cage a reaction coordinate when the barrier frequencies for competing reaction paths are different. Our theoretical results illustrate the cavity-induced mode-selective chemistry through polaritonic vibrational-strong couplings, revealing the fundamental mechanism for changing chemical selectivities through cavity quantum electrodynamics.

scholarly journals Mode-Selective Chemistry through Polaritonic Vibrational Strong Coupling

2021 ◽  
Author(s):  
Xinyang Li ◽  
Arkajit Mandal ◽  
Pengfei Huo
Keyword(s):  
Quantum Electrodynamics ◽  
Optical Cavity ◽  
Cavity Quantum Electrodynamics ◽  
Reaction Coordinate ◽  
Vacuum Fluctuations ◽  
Radiation Mode ◽  
Competitive Reactions ◽  
Photon Frequency ◽  
Theoretical Results ◽  
Fundamental Mechanism

Recent experiments have demonstrated remarkable mode-selective reactivities by coupling molecular vibrations with vacuum fluctuations inside an optical cavity. The fundamental mechanism behind such effects, on the other hand, remains elusive. In this work, we theoretically demonstrate the basic principle of how cavity photon frequency can be tuned to achieve mode-selective reactivities. We find that the non-Markovian nature of the radiation mode leads to a cavity frequency-dependent dynamical caging effect of a reaction coordinate, resulting in a suppression of the rate constant. In the presence of multiple competitive reactions, it is possible to preferentially cage a reaction coordinate when the barrier frequencies for competing reaction paths are different. Our theoretical results illustrate the cavity-induced mode-selective chemistry through polaritonic vibrational-strong couplings, revealing the fundamental mechanism for changing chemical selectivities through cavity quantum electrodynamics.

scholarly journals Ring-Polymer Quantization of Photon Field in Polariton Chemistry

2020 ◽  
Author(s):  
Sutirtha N. Chowdhury ◽  
Arkajit Mandal ◽  
Pengfei Huo
Keyword(s):  
Radiation Field ◽  
Quantum Electrodynamics ◽  
Quantum Dynamics ◽  
Optical Cavity ◽  
Cavity Quantum Electrodynamics ◽  
Transfer Model ◽  
Quantum Distribution ◽  
Photon Field ◽  
Mediated Electron Transfer ◽  
Ring Polymer

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.

Magneto-Optical Cavity Quantum Electrodynamics Effects in Quantum Dot Micropillar Systems

2010 ◽  
Author(s):  
Stephan Reitzenstein ◽  
Steffen Munch ◽  
Philipp Franeck ◽  
Arash Rahimi-Iman ◽  
Tobias Heindel ◽  
...  
Keyword(s):  
Quantum Dot ◽  
Quantum Electrodynamics ◽  
Optical Cavity ◽  
Cavity Quantum Electrodynamics

scholarly journals Micro-Solvated DMABN: Excited State Quantum Dynamics and Dual Fluorescence Spectra

Molecules ◽  
2021 ◽  
Vol 26 (23) ◽  
pp. 7247
Author(s):  
Sandra Gómez ◽  
Esra N. Soysal ◽  
Graham A. Worth
Keyword(s):  
Electronic Structure ◽  
Excited State ◽  
Quantum Dynamics ◽  
Computational Study ◽  
Water Solution ◽  
Fluorescence Emission ◽  
Spectroscopic Properties ◽  
Complete Analysis ◽  
Solvent Molecules ◽  
Dynamics Simulations

In this work, we report a complete analysis by theoretical and spectroscopic methods of the short-time behaviour of 4-(dimethylamino)benzonitrile (DMABN) in the gas phase as well as in cyclohexane, tetrahydrofuran, acetonitrile, and water solution, after excitation to the La state. The spectroscopic properties of DMABN were investigated experimentally using UV absorption and fluorescence emission spectroscopy. The computational study was developed at different electronic structure levels and using the Polarisable Continuum Model (PCM) and explicit solvent molecules to reproduce the solvent environment. Additionally, excited state quantum dynamics simulations in the diabatic picture using the direct dynamics variational multiconfigurational Gaussian (DD-vMCG) method were performed, the largest quantum dynamics “on-the-fly” simulations performed with this method until now. The comparison with fully converged multilayer multiconfigurational time-dependent Hartree (ML-MCTDH) dynamics on parametrised linear vibronic coupling (LVC) potentials show very similar population decays and evolution of the nuclear wavepacket. The ring C=C stretching and three methyl tilting modes are identified as the responsible motions for the internal conversion from the La to the Lb states. No major differences are observed in the ultrafast initial decay in different solvents, but we show that this effect depends strongly on the level of electronic structure used.

Competition between the heavy atom effect and vibronic coupling in donor–bridge–acceptor organometallics

2020 ◽  
Vol 22 (8) ◽  
pp. 4659-4667 ◽  
Author(s):  
Julien Eng ◽  
Stuart Thompson ◽  
Heather Goodwin ◽  
Dan Credgington ◽  
Thomas James Penfold
Keyword(s):  
Excited State ◽  
Quantum Dynamics ◽  
Heavy Atom ◽  
Vibronic Coupling ◽  
Intersystem Crossing ◽  
Heavy Atom Effect ◽  
Metal Amides ◽  
Coinage Metals ◽  
Dynamics Simulations ◽  
Atom Effect

The excited state properties and intersystem crossing dynamics of a series of donor–bridge–acceptor carbene metal-amides based upon the coinage metals Cu, Ag, Au, are investigated using quantum dynamics simulations and supported by photophysical characterisation.

Genuine vacuum-induced geometric phases

2015 ◽  
Vol 29 (11) ◽  
pp. 1550043 ◽  
Author(s):  
Minghao Wang ◽  
L. F. Wei ◽  
J. Q. Liang
Keyword(s):  
Excited State ◽  
Quantum Electrodynamics ◽  
Geometric Phase ◽  
Berry Phase ◽  
Cavity Quantum Electrodynamics ◽  
Vacuum Field ◽  
Geometric Phases ◽  
Field System ◽  
The One

Since a pioneer work on vacuum-induced Berry phase (VIBP) was done by Fuentes-Guridi et al. [Phys. Rev. Lett. 89 (2002) 220404], much attention has been paid to the geometric phase effects of vacuum field. However, all the so-called VIBPs investigated previously are not purely vacuum-induced (i.e. the nonvacuum components of the field are also involved). In this paper, we discuss how to deliver geometric phases from the evolution of a genuine vacuum field in a standard cavity quantum electrodynamics (QED) system. First, we design a cyclic evolution of an atom–field system with the atom being initially prepared at the excited state and the field at the genuine vacuum. Then, we calculate the geometric phases acquired during such a cyclic evolution. It is found that such geometric phases are really induced by an evolution of the genuine vacuum field. Specifically, our generic proposal is demonstrated with both the one- and two-mode Jaynes–Cummings model interactions (JCM).

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