A perspective on ab initio modeling of polaritonic chemistry: The role of non-equilibrium effects and quantum collectivity

Sidler, Dominik; Ruggenthaler, Michael; Schäfer, Christian; Ronca, Enrico; Rubio, Angel

doi:10.48550/arxiv.2108.12244

Cited by 6 publications

(8 citation statements)

References 64 publications

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“…In the case that we increase the light-matter coupling into the ultra-strong or deep-strong coupling regime, this will further result to an increase efficiency of the SHG and THG from polaritonic states. For the case of collective strong coupling of an ensemble of molecules where the Rabi splitting is proportional to the squareroot of the number of emitters [45,54], we expect to get an increased enhancement of these nonlinear processes as reported in experiments for SHG [23] and THG [25,26]. Nevertheless, the single-molecule strong coupling studied here already sheds light on how the nonlinear conversion efficiency increases for increasing coupling strength.…”

Section: B Thg From Polaritonic Statessupporting

confidence: 64%

Tunable Nonlinearity and Efficient Harmonic Generation from a Strongly Coupled Light-Matter System

Welakuh¹,

Narang²

2022

Preprint

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Strong light-matter coupling within electromagnetic environments provides a promising path to modify and control chemical and physical processes. The origin of the enhancement of nonlinear optical processes such as second-harmonic and third-harmonic generation (SHG and THG) due to strong light-matter coupling is attributed to distinct physical effects which questions the relevance of strong coupling in these processes. In this work, we leverage a first-principles approach to investigate the origins of the experimentally observed enhancement of resonant SHG and THG under strong light-matter coupling. We find that the enhancement of the nonlinear conversion efficiency has its origins in a modification of the associated nonlinear optical susceptibilities as polaritonic resonances emerge in the nonlinear spectrum. Further, we find that the nonlinear conversion efficiency can be tuned by increasing the light-matter coupling strength. Finally, we provide a general framework to compute the harmonic generation spectra from the displacement field as opposed to the standard approach which computes the harmonic spectrum from the matter-only induced polarization. Our results address a key debate in the field, and pave the way for predicting and understanding quantum nonlinear optical phenomena in strongly coupled light-matter systems.

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Section: B Thg From Polaritonic Statessupporting

confidence: 64%

Tunable Nonlinearity and Efficient Harmonic Generation from a Strongly Coupled Light-Matter System

Welakuh¹,

Narang²

2022

Preprint

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“…The electron-photon Sternheimer method presented here is a suitable approach for studying excited-state properties of large systems coupled to a single mode or to the electromagnetic continuum. In the fast-growing field of polaritonic chemistry where there is an ongoing debate about the mesoscopic scale of quantum-collectively of coupled molecules [16,62], ab-initio methods such as the electron-photon Sternheimer method become desirable to capture intricate details of the complex interactions between the coupled subsystems. Another important property of the Sternheimer approach is that it can be generalized to higher orders to obtain higher order polarizabilities by solving a hierarchy of Sternheimer equations [37].…”

Section: Discussionmentioning

confidence: 99%

Frequency-dependent Sternheimer linear-response formalism for strongly coupled light-matter systems

Welakuh¹,

Ruggenthaler²,

Appel³

et al. 2022

Preprint

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“…In a newly emerging field of polaritonic chemistry, such strong light-matter coupling effects are utilized to catalyze, 1-3 inhibit, 4,5 or modify the overall reaction path 6,7 of a given chemical reaction. Naturally, these experimental advances have been accompanied by various theoretical developments 2,6,[8][9][10][11][12][13] that attempt to provide an insight into fundamental understanding of the strong light-matter interaction as well as for guiding design principles of processes inside cavities. 8 Like in the case of the conventional electronic structure methods, there are two main approaches to solve the Schrödinger equation that accounts for the strong light-matter interaction.…”

Section: Introductionmentioning

confidence: 99%

Wavefunction Embedding for Molecular Polaritons

Pavošević,

Rubio

2022

Preprint

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Polaritonic chemistry relies on the strong light-matter interaction phenomena for altering the chemical reaction rates inside optical cavities. To explain and to understand these processes, the development of reliable theoretical models is essential. While computationally efficient quantum electrodynamics self-consistent field (QED-SCF) methods, such as quantum electrodynamics density functional theory (QEDFT) needs accurate functionals, quantum electrodynamics coupled cluster (QED-CC) methods provide a systematic increase in accuracy but at much greater cost. To overcome this computational bottleneck, herein we introduce and develop the QED-CC-in-QED-SCF projection-based embedding method that inherits all the favorable properties from the two worlds, computational efficiency and accuracy. The performance of the embedding method is assessed by studying some prototypical but relevant reactions, such as methyl transfer reaction, proton transfer reaction, as well as protonation reaction in a complex environment. The results obtained with the new embedding method are in excellent agreement with more expensive QED-CC results. The analysis performed on these reactions indicate that the strong light-matter interaction is very local in nature and that only a small region should be treated at the QED-CC level for capturing important effects due to cavity. This work sets the stage for future developments of polaritonic quantum chemistry methods and it will serve as a guideline for development of other polaritonic embedding models.

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A perspective on ab initio modeling of polaritonic chemistry: The role of non-equilibrium effects and quantum collectivity

Cited by 6 publications

References 64 publications

Tunable Nonlinearity and Efficient Harmonic Generation from a Strongly Coupled Light-Matter System

Tunable Nonlinearity and Efficient Harmonic Generation from a Strongly Coupled Light-Matter System

Frequency-dependent Sternheimer linear-response formalism for strongly coupled light-matter systems

Wavefunction Embedding for Molecular Polaritons

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