arXiv subjects

Yassir El Moutaoukal

Publications and source records attributed to Yassir El Moutaoukal.

6 recordsLinked to original sources

arXiv2026

Non-equilibrium cavity pumping of electronic molecular polaritons

Strong light-matter coupling in optical cavities offers a non-invasive route to modify molecular properties, and it is usually reached by collectively coupling many molecules to the same mode. Here we consider the photonic counterpart of the collective regime, in which a single molecule interacts with a cavity mode holding many photons, a steady state of the pumped cavity. Since the eigenstates of the Pauli-Fierz Hamiltonian carry no transverse electric field, such a state cannot be described as an excited state of the light-matter system. We therefore constrain the photon number of the strong coupling QED Hartree-Fock wave function with a Lagrange multiplier and self consistently minimize the energy with respect to all parameters. The constrained reference carries the field of a coherent state with an average number of photons, generated by a cavity mode whose effective free-field frequency is lowered by the multiplier. We apply this framework to benzene and a benzene-water complex, where the pumped cavity polarizes the molecules and modifies their interaction as with a static classical field. For hydrogen peroxide, the field can reshape the torsional potential and the far-infrared torsional spectrum. The classical driven field limit thus emerges from a quantized mean field description, and the photon density becomes a control parameter for cavity-modified chemistry.

physics.chem-ph↗

arXiv2025

eT 2.0: An efficient open-source molecular electronic structure program

The eT program is an open-source electronic structure program with emphasis on performance and modularity. As its name suggests, the program features extensive coupled cluster capabilities, performing well compared to other electronic structure programs, and, in some cases, outperforming commercial alternatives. However, eT is more than a coupled cluster program; other models based on wave function theory (such as full and reduced space configuration interaction and a variety of self-consistent field models) and density functional theory are supported. The second major release of the program, eT 2.0, has specialized functionality for strong light-matter coupling conditions. In addition, it includes a wide range of optimizations and algorithmic improvements, as well as new capabilities for exploring potential energy surfaces and for modeling experiments in the UV and X-ray regimes. Molecular gradients are now available at the coupled cluster level, and high-accuracy spectroscopic simulations are available at reduced computational cost within the multilevel coupled cluster and multiscale frameworks. We present the modifications to the program since its first major release, eT 1.0, highlighting some notable new features and demonstrating the performance of the new version relative to the first release and to other established electronic structure programs.

physics.chem-ph↗

arXiv2025

Unveiling chiral electron-photon correlation effects in circularly polarized optical devices

Strong coupling with circularly polarized vacuum fluctuations offers a viable route to manipulate molecular chirality. While experiments are advancing toward the realization of chiral cavities, a mean-field theoretical framework for describing electron-photon interaction in this platform has been missing. Here, we present a mean-field theory that can be systematically improved to capture the chiral correlation effects responsible for the enantioselective power of chiral light. We use strong coupling Møller-Plesset perturbation theory for accessing the excitation manifold of electrons and chiral virtual photons. We apply the developed methods to selected chiral systems and show that the mean-field theory captures cavity frequency dispersion, but fails to describe the chiral discrimination arising from coupled electron-photon excitations.

physics.chem-ph↗

arXiv2025

Strong coupling Møller-Plesset perturbation theory

Perturbative approaches are methods to efficiently tackle many-body problems, offering both intuitive insights and analysis of correlation effects. However, their application to systems where light and matter are strongly coupled is non-trivial. Specifically, the definition of suitable orbitals for the zeroth-order Hamiltonian represents a significant theoretical challenge. While reviewing previously investigated orbital choices, this work presents an alternative polaritonic orbital basis suitable for the strong coupling regime. We develop a quantum electrodynamical (QED) Møller-Plesset perturbation theory using orbitals obtained from the strong coupling QED Hartree-Fock. We assess the strengths and limitations of the different approaches and emphasize the essential role of using a consistent molecular orbital framework to achieve an accurate description of cavity-induced electron-photon correlation effects.

physics.chem-ph↗

arXiv2025

Strong coupling quantum electrodynamics Hartree-Fock response theory

The development of reliable ab initio methods for light-matter strong coupling is necessary for a deeper understanding of molecular polaritons. The recently developed strong coupling quantum electrodynamics Hartree-Fock model (SC-QED-HF) provides cavity-consistent molecular orbitals, overcoming several difficulties related to the simpler QED-HF wave function. In this paper, we further develop this method by implementing the response theory for SC-QED-HF. We compare the derived linear response equations with the time-dependent QED-HF theory and discuss the validity of equivalence relations connecting matter and electromagnetic observables. Our results show that electron-photon correlation induces an excitation redshift compared to the time-dependent QED-HF energies, and we discuss the effect of the dipole self-energy on the ground and excited state properties with different basis sets.

physics.chem-ph↗

arXiv2024

Towards polaritonic molecular orbitals for large molecular systems

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

physics.chem-ph↗