Resonance Enhancement of Vibrational Polariton Chemistry Obtained from the Mixed Quantum-Classical Dynamics Simulations

Hu, Deping; Ying, Wenxiang; Huo, Pengfei

doi:10.1021/acs.jpclett.3c02985

Cited by 10 publications

(3 citation statements)

References 56 publications

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“…For example, the super-Ohmic spectral density is usually adopted for the CdSe nanoplatelet systems [40,68,69]. To overcome the computational difficulties, the mixed-quantumclassical (MQC) dynamics methods [49,70,71] could be potentially very useful. Last but not least, the polariton linewidth at general detuned cases needs to be derived basing on the first principle.…”

Section: Discussionmentioning

confidence: 99%

Theory and Quantum Dynamics Simulations of Exciton-Polariton Motional Narrowing

Ying,

Mondal,

Huo

2024

Preprint

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The motional narrowing effect has been extensively studied for cavity exciton-polariton systems in recent decades both experimentally and theoretically, which is featured by (1) the subaverage behavior, and (2) the asymmetric linewidths for the upper polariton (UP) and the lower polariton (LP). However, a minimal theoretical model that is clear and adequate to address all these effects, as well as the linewidth scaling relations remains missing. In this work, based on the single mode 1D Holstein-Tavis-Cummings (HTC) model, we studied the motional narrowing effect of the polariton linear absorption (LA) spectra via both semi-analytic derivations and numerically exact quantum dynamics simulations using the hierarchical equations of motion (HEOM) approach. The results reveal that under collective light-matter coupling between a cavity mode and $N$ molecules, the polariton linewidth scales as $1/\sqrt{N}$ under the slow limit, while scales as $1/N$ under the fast limit, due to the polaron decoupling effect. Further, by varying the detunings, the polariton linewidths exhibit significant motional narrowing, covering both characters mentioned above. Our analytic linewidth expressions agree well with the numerical exact simulations in all the parameter regimes we explored. These results indicate that the physics of motional narrowing is adequately accounted for by the single-mode 1D HTC model. We envision that both the numerical results and the analytic polariton linewidths expression presented in this work will offer great theoretical value for providing a better understanding of the exciton-polariton motional narrowing based on the HTC model.

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Section: Discussionmentioning

confidence: 99%

Theory and Quantum Dynamics Simulations of Exciton-Polariton Motional Narrowing

Ying,

Mondal,

Huo

2024

Preprint

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“…There are at least two complementary approaches to this problem: so-called parametrized CQED methods and self-consistent CQED methods. The former parametrized approach involves solving two Schrödinger equations in series: a first for the molecular system alone using traditional tools of ab initio quantum chemistry, and the second for the coupled molecular-photonic system that is parametrized by the solutions to the molecular problem. ,, On the other hand, the self-consistent approach involves augmenting ab initio quantum chemistry methods to directly include coupling to photonic degrees of freedom. Such approaches have included quantum electrodynamics generalizations of density functional theory (QEDFT ,− and QED-DFT − ), real-time ,,− and linear-response ,, formulations of QED-TDDFT, configuration interaction (QED-CIS), cavity QED extension of second-order Møller-Plesset perturbation theory and the algebraic diagrammatic construction, , coupled cluster (QED-CC), ,− variational QED-2-RDM methods, and diffusion Monte Carlo .…”

Section: Introductionmentioning

confidence: 99%

Cavity Quantum Electrodynamics Complete Active Space Configuration Interaction Theory

Vu,

Mejia-Rodriguez,

Bauman

et al. 2024

J. Chem. Theory Comput.

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Polariton chemistry has attracted great attention as a potential route to modify chemical structure, properties, and reactivity through strong interactions among molecular electronic, vibrational, or rovibrational degrees of freedom. A rigorous theoretical treatment of molecular polaritons requires the treatment of matter and photon degrees of freedom on equal quantum mechanical footing. In the limit of molecular electronic strong or ultrastrong coupling to one or a few molecules, it is desirable to treat the molecular electronic degrees of freedom using the tools of ab initio quantum chemistry, yielding an approach we refer to as ab initio cavity quantum electrodynamics, where the photon degrees of freedom are treated at the level of cavity quantum electrodynamics. Here, we present an approach called Cavity Quantum Electrodynamics Complete Active Space Configuration Interaction theory to provide ground-and excited-state polaritonic surfaces with a balanced description of strong correlation effects among electronic and photonic degrees of freedom. This method provides a platform for ab initio cavity quantum electrodynamics when both strong electron correlation and strong light−matter coupling are important and is an important step toward computational approaches that yield multiple polaritonic potential energy surfaces and couplings that can be leveraged for ab initio molecular dynamics simulations of polariton chemistry.

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“…[22,23] A few theoretical studies are available suggesting the collective nature and resonance effect in polaritonic chemistry. [24][25][26][27][28] Recent reviews are also available for the readers to glimpse interesting advances in polaritonic chemistry. [2,[29][30][31] Fabry-Perot (FP) cavity is the simplest configuration available and is used in almost all polaritonic chemistry experiments (including solid-state) reported in the literature.…”

Section: Introductionmentioning

confidence: 99%

Cavity Catalysis of an Enantioselective Reaction under Vibrational Strong Coupling

Singh,

Garg,

Anand

et al. 2024

Chemistry A European J

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Strong light‐matter interaction is emerging as an exciting tool for controlling chemical reactions. Here, we demonstrate an L‐proline‐catalyzed direct asymmetric Aldol reaction under vibrational strong coupling. Both the reactants (4‐nitrobenzaldehyde and acetone) carbonyl bands are coupled to an infrared photon and react in the presence of L‐proline. The reaction mixture is eluted from the cavity, and the conversion yields and enantiomeric excess are quantified using NMR and chiral HPLC. The conversion yields increase by up to 90% in ON‐resonance conditions. Interestingly, a large increase in the conversion yield does not affect the enantiomeric excess. Further control experiments were carried out by varying the temperature, and we propose that the rate‐limiting step may not be the deciding factor in enantioselectivity. Whereas the formation of the enamine intermediate is modified by cavity coupling experiments. For this class of enantioselective reactions, strong coupling does not change the enantiomeric excess, possibly due to the large energy difference in chiral transition states. Strong coupling can boost the formation of enamine intermediate, thereby favouring the product yield. This gives more hope to test polaritonic chemistry based on enantioselective reactions in which the branching ratios can be controlled.

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Resonance Enhancement of Vibrational Polariton Chemistry Obtained from the Mixed Quantum-Classical Dynamics Simulations

Cited by 10 publications

References 56 publications

Theory and Quantum Dynamics Simulations of Exciton-Polariton Motional Narrowing

Theory and Quantum Dynamics Simulations of Exciton-Polariton Motional Narrowing

Cavity Quantum Electrodynamics Complete Active Space Configuration Interaction Theory

Cavity Catalysis of an Enantioselective Reaction under Vibrational Strong Coupling

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