Diffusion quantum Monte Carlo approach to the polaritonic ground state

Physical review. A/Physical review, A, Год журнала: 2024, Номер 109(3)

Опубликована: Март 4, 2024

Making and using polaritonic states (i.e., hybrid electron-photon states) for chemical applications has recently become one of the most prominent active fields that connects communities chemistry quantum optics. Modeling such phenomena ab initio approaches calls new methodologies, leading to reinvention many commonly used electronic structure methods, as Hartree-Fock, density functional, coupled cluster theories. In this work, we explore formally exact diffusion Monte Carlo approach obtain numerical solutions ground state during dissociation ${\mathrm{H}}_{2}$ molecular system. We examine various electron-nuclear-photon properties throughout dissociation, changes minimum cavity Born-Oppenheimer surface, localization wave function, average mode occupation. Finally, directly compare our results obtained with state-of-the-art, yet approximate, approaches.

Язык: Английский

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The orientation dependence of cavity-modified chemistry

The Journal of Chemical Physics, Год журнала: 2024, Номер 161(6)

Опубликована: Авг. 12, 2024

Recent theoretical studies have explored how ultra-strong light-matter coupling can be used as a handle to control chemical transformations. Ab initio cavity quantum electrodynamics calculations demonstrate that large changes reaction energies or barrier heights realized by electronic degrees of freedom vacuum fluctuations associated with an optical mode, provided enough strengths achieved. In many cases, the effects display pronounced orientational dependence. Here, we highlight critical role geometry relaxation play in such studies. As example, consider recent work [Pavošević et al., Nat. Commun. 14, 2766 (2023)] influence on Diels-Alder cycloaddition reactions and reported enthalpies heights, well observation orientation inhibit select for one product another. Those fixed molecular geometries optimized absence relative orientations molecules mode polarization axis. show when given chance relax presence cavity, species reorient way eliminates Moreover, this case, find qualitatively different conclusions regarding impact thermodynamics drawn from relaxed vs unrelaxed structures.

Язык: Английский

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Cavity Quantum Electrodynamics Enables para- and ortho-Selective Electrophilic Bromination of Nitrobenzene

Journal of the American Chemical Society, Год журнала: 2024, Номер 146(23), С. 16184 - 16193

Опубликована: Май 30, 2024

Coupling molecules to a quantized radiation field inside an optical cavity has shown great promise modify chemical reactivity. In this work, we show that the ground-state selectivity of electrophilic bromination nitrobenzene can be fundamentally changed by strongly coupling reaction cavity, generating ortho- or para-substituted products instead meta product. Importantly, these are not obtained from same outside cavity. A recently developed ab initio approach was used theoretically compute relative energies cationic Wheland intermediates, which indicate kinetically preferred site for all products. Performing analysis electron density intermediates and demonstrate how strong induces reorganization molecular charge distribution, in turn leads different sites directly dependent on conditions. Overall, results presented here understand induced changes reactivity mechanistic perspective as well connect frontier theoretical simulations state-of-the-art, but realistic, experimental

Язык: Английский

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Analytical Evaluation of Ground State Gradients in Quantum Electrodynamics Coupled Cluster Theory

Journal of Chemical Theory and Computation, Год журнала: 2024, Номер 20(20), С. 8876 - 8885

Опубликована: Окт. 11, 2024

Analytical gradients of potential energy surfaces play a central role in quantum chemistry, allowing for molecular geometry optimizations and dynamics simulations. In strong coupling conditions, can account interactions between matter the quantized electromagnetic field. this paper, we derive expressions ground state analytical electrodynamics coupled cluster theory. We also present Cholesky-based implementation singles doubles model. report timings to show performance optimized geometries highlight cavity-induced orientation effects conditions.

Язык: Английский

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Light-induced electron dynamics of molecules in cavities: comparison of model Hamiltonians

Journal of the Optical Society of America B, Год журнала: 2024, Номер 41(8), С. C74 - C74

Опубликована: Май 9, 2024

The rapidly expanding field of polaritonic chemistry requires accurate theoretical simulations to understand new phenomena at the atomic scale. Computing optoelectronic properties molecules using established electronic structure methods is a careful balance accuracy and computational expense, these quantum electrodynamics describe coupled cavity-molecule systems an active topic development. Key are Hamiltonian operators representing photon cavity modes. recently introduced time-dependent configuration interaction (QED-TDCI) method allows for combination electron dynamics with electrodynamics, enabling simulation systems. Using this method, comparison two many-state QED Hamiltonians—the Pauli-Fierz Rabi model Hamiltonians—is presented, particular focus on in applied electric fields.

Язык: Английский

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Light–matter interaction Hamiltonians in cavity quantum electrodynamics

Chemical Physics Reviews, Год журнала: 2025, Номер 6(1)

Опубликована: Фев. 12, 2025

When matter is strongly coupled to an optical cavity, new hybrid light–matter states are formed, the so-called polariton states. These polaritons can qualitatively change physical properties of cavity by completely altering its energy eigenspectrum. Fueled experimental innovations in recent years, much progress has been made simulating intrinsic quantum behavior these At heart each simulation choice Hamiltonian represent total system. Even at this fundamental level, there significant developing gauges and representations for Hamiltonian, whether exact or under approximations. As such, review aims discuss several different forms Hamiltonians researcher trying enter field clearly concisely deriving representation from Minimal Coupling Hamiltonian. In addition, provides commentary on optimal usage extent approximations individual assist reader choosing appropriate their work.

Язык: Английский

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Toward Polaritonic Molecular Orbitals for Large Molecular Systems

Journal of Chemical Theory and Computation, Год журнала: 2024, Номер unknown

Опубликована: Сен. 30, 2024

A comprehensive understanding of electron-photon correlation is essential for describing the reshaping molecular orbitals in quantum electrodynamics (QED) environments. The strong coupling QED Hartree-Fock (SC-QED-HF) theory tackles these aspects by providing consistent regime. previous implementation, however, has significant convergence issues that limit applicability. In this work, we introduce two second-order algorithms significantly reduce computational requirements, thereby enhancing modeling large systems Furthermore, implementation will enable development correlated methods based on a reliable orbital framework as well multi-level methodologies able to model inclusion solvent effects kind complex systems.

Язык: Английский

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Polaritonic Chemistry Using the Density Matrix Renormalization Group Method

Journal of Chemical Theory and Computation, Год журнала: 2024, Номер 20(21), С. 9424 - 9434

Опубликована: Окт. 23, 2024

The emerging field of polaritonic chemistry explores the behavior molecules under strong coupling with cavity modes. Despite recent developments in

Язык: Английский

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Comparing parameterized and self-consistent approaches to ab initio cavity quantum electrodynamics for electronic strong coupling

The Journal of Chemical Physics, Год журнала: 2024, Номер 161(17)

Опубликована: Ноя. 1, 2024

Molecules under strong or ultra-strong light–matter coupling present an intriguing route to modify chemical structure, properties, and reactivity. A rigorous theoretical treatment of such systems requires handling matter photon degrees freedom on equal quantum mechanical footing. In the regime molecular electronic one a few molecules, it is desirable treat using tools ab initio chemistry, yielding approach referred as cavity electrodynamics (ai-QED), where are treated at level QED. We analyze two complementary approaches ai-QED: (1) parameterized ai-QED, two-step computed existing structure theories, enabling construction ai-QED Hamiltonians in basis many-electron eigenstates, (2) self-consistent one-step methods generalized include between freedom. Although these equivalent their exact limits, we identify disparity projection two-body dipole self-energy operator that appears its counterpart approach. provide argument this resolves only limit complete orbital for projection. numerical results highlighting resolution particularly simple system helium hydride cation, possible limits simultaneously. same system, examine compare practical issue computational cost required converge each toward bases limit. Finally, assess aspect photonic convergence polar charged species, finding comparable behavior approaches.

Язык: Английский

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Diagrams in Polaritonic Coupled Cluster Theory

The Journal of Physical Chemistry A, Год журнала: 2024, Номер 128(44), С. 9572 - 9586

Опубликована: Окт. 23, 2024

We present a diagrammatic notation to derive the quantum-electrodynamic coupled cluster (QED-CC) equations needed for description polaritonic ground and excited states. Our presented is generalization of existing standard electronic coupled-cluster theory. It used QED-CC QED-EOM-CC QED-CCSD-1-SD QED-CCSD-12-SD truncation schemes. Furthermore, we diagrams CC Λ-equations reduced density matrices which are calculation molecular properties.

Язык: Английский

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