Insights into the mechanisms of optical cavity-modified ground-state chemical reactions DOI Creative Commons
Yaling Ke, Jeremy O. Richardson

Published: Dec. 26, 2023

In this work, we systematically investigate the mechanisms underlying photon frequency-dependent rate modification of ground-state chemical reactions in an optical cavity, as well effects collective coupling two molecules to same cavity mode. Our analysis is grounded a symmetric double-well description molecular potential energy surface. To obtain reaction dynamics, employ numerically exact open quantum system approach, namely, hierarchical equations motion twin space with matrix product state solver. results reveal that can be modified when frequency closely matches transition between pair vibrational eigenstates. This arises due opening cavity-induced intra-molecular cotunneling pathway, and extent determined jointly by several kinetic factors. For anharmonic multiple energies, predict possibility observing peaks profile. Increasing light-matter strength not only enhances intensity width profile but may also lead fusion nearby peaks. Furthermore, find identical are simultaneously coupled resonant mode, intermolecular channel activated, contributing further alternation rate. It worth emphasizing that, these intramolecular cavity-promoted pathways remains unaffected regardless whether dipoles aligned or opposite direction light polarization. suggests persist isotropically disordered system, differing inherently from influence direct dipolar interaction, which shows tendency dipole orientations.

Language: Английский

Quantum nature of reactivity modification in vibrational polariton chemistry DOI Creative Commons
Yaling Ke, Jeremy O. Richardson

Published: May 29, 2024

In this work, we present a mixed quantum–classical open quantum system dynamics method for studying rate modifications of ground-state chemical reactions in an optical cavity under vibrational strong coupling conditions. approach, the radiation mode is treated classically with mean-field nuclear force averaging over remaining degrees freedom, both within and environment, which are handled mechanically hierarchical equations motion framework. Using conduct comparative analysis by juxtaposing results fully mechanical simulations. Through comparison, confirm crucial role nature reproducing resonant peak observed frequency-dependent profile. other words, it to explicitly consider quantized photonic states reactivity modification polariton chemistry, as these phenomena stem from cavity-induced reaction pathways involving energy exchanges between photons molecular transitions.

Language: Английский

Citations

2
Resonance Theory and Quantum Dynamics Simulations of Vibrational Polariton Chemistry DOI Creative Commons
Wenxiang Ying, Pengfei Huo

Published: July 18, 2023

We present numerically exact quantum dynamics simulations using the hierarchical equation of motion (HEOM) approach to investigate resonance enhancement chemical reactions due vibrational strong coupling (VSC) in polariton chemistry. The results reveal that cavity mode acts like a ``rate-promoting (RPV) mode" enhances ground state reaction rate constant when frequency matches transition frequency. simulation predicts VSC-modified will change quadratically as light-matter strength increases. When changing lifetime from lossy limit lossless limit, predict there be turnover constant. Based on numerical observations, we an analytic theory explain observed sharp peak profile tuning match excited states. This further explains origin broadening profile. agrees with under golden rule and short limit. To best our knowledge, this is first able behavior adiabatic cavity. envision both analysis offer invaluable theoretical insights into fundamental mechanism coupling-induced modifications

Language: Английский

Citations

5
Resonance Theory of Vibrational Strong Coupling Enhanced Polariton Chemistry DOI Creative Commons
Wenxiang Ying, Pengfei Huo

Published: May 3, 2024

We present a complete theory of vibrational strong coupling (VSC) modified rate constants in polariton chemistry when single molecule to an optical cavity. The analytic expression exhibits sharp resonance behavior, where the maximum constant is reached cavity frequency matches vibration frequency. also explains why VSC modification closely resembles spectra outside This expression, together with our previous under lossy regime, provides mechanistic picture for VSC-enhanced simple double well reactive model system. Our suggests that there will be turnover as one changes lifetime, and first scale quadratically respect light-matter strength then saturate. agree numerically exact hierarchical equations motion (HEOM) simulations all explored regimes. Further, we discussed temperature dependence VSC-modified constants, agrees numerical simulations. Finally, condition at normal incidence considering in-plane momentum inside Fabry-P\'erot

Language: Английский

Citations

1
Resonance Enhancement of Vibrational Polariton Chemistry Obtained from the Mixed Quantum-Classical Dynamics Simulations DOI Creative Commons
Deping Hu, Wenxiang Ying, Pengfei Huo

et al.

Published: Oct. 26, 2023

We applied a variety of mixed quantum-classical (MQC) approaches to simulate the VSC-influenced reaction rate constant. All these MQC simulations treat key vibrational levels associated with coordinate in quantum subsystem (as states), whereas all other degrees freedom (DOFs) are treated inside classical subsystem. find that as long we have state descriptions for DOFs, one can correctly describe VSC resonance condition when cavity frequency matches bond frequency. This correct behavior be obtained regardless detailed methods uses. The results suggest generate semi-quantitative agreement exact constant changes changing frequency, light-matter coupling strength, or lifetime. finding this work suggests use computationally economic explore collective scenario many molecules collectively coupled modes future.

Language: Английский

Citations

3
Insights into the mechanisms of optical cavity-modified ground-state chemical reactions DOI Creative Commons
Yaling Ke, Jeremy O. Richardson

Published: Dec. 26, 2023

In this work, we systematically investigate the mechanisms underlying photon frequency-dependent rate modification of ground-state chemical reactions in an optical cavity, as well effects collective coupling two molecules to same cavity mode. Our analysis is grounded a symmetric double-well description molecular potential energy surface. To obtain reaction dynamics, employ numerically exact open quantum system approach, namely, hierarchical equations motion twin space with matrix product state solver. results reveal that can be modified when frequency closely matches transition between pair vibrational eigenstates. This arises due opening cavity-induced intra-molecular cotunneling pathway, and extent determined jointly by several kinetic factors. For anharmonic multiple energies, predict possibility observing peaks profile. Increasing light-matter strength not only enhances intensity width profile but may also lead fusion nearby peaks. Furthermore, find identical are simultaneously coupled resonant mode, intermolecular channel activated, contributing further alternation rate. It worth emphasizing that, these intramolecular cavity-promoted pathways remains unaffected regardless whether dipoles aligned or opposite direction light polarization. suggests persist isotropically disordered system, differing inherently from influence direct dipolar interaction, which shows tendency dipole orientations.

Language: Английский

Citations

3