index - Méthodes et outils de la chimie quantique

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Methyl-p-benzoquinone (MpBQ, CH3C6H3(═O)2) is a prototypical molecule in the study of quinones, which are compounds of relevance in biology and several redox reactions. Understanding the electron attachment properties of MpBQ and its ability to form anions is crucial in elucidating its role in these reactions. In this study, we investigate electron attachment to MpBQ employing a crossed electron-molecular beam experiment in the electron energy range of approximately 0 to 12 eV, as well as theoretical approaches using quantum chemical and electron scattering calculations. Six anionic species were identified: C7H6O2–, C7H5O2–, C6H5O–, C4HO–, C2H2–, and O–. The parent anion is formed most efficiently, with large cross sections, through two resonances at electron energies between 1 and 2 eV. Potential reaction pathways for all negative ions observed are explored, and the experimental appearance energies are compared with calculated thermochemical thresholds. Although exhibiting similar electron attachment properties to pBQ, MpBQ’s additional methyl group introduces entirely new dissociative reactions, while quenching others, underscoring its distinctive chemical behavior.

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To expand the QUEST database of highly accurate vertical transition energies, we consider a series of large organic chromogens ubiquitous in dye chemistry, such as anthraquinone, azobenzene, BODIPY, and naphthalimide. We compute, at the CC3 level of theory, the singlet and triplet vertical transition energies associated with the low-lying excited states. This leads to a collection of more than 120 new highly accurate excitation energies. For several singlet transitions, we have been able to determine CCSDT transition energies with a compact basis set, finding minimal deviations from the CC3 values for most states. Subsequently, we employ these reference values to benchmark a series of lower-order wave function approaches, including the popular ADC(2) and CC2 schemes, as well as time-dependent density-functional theory (TD-DFT), both with and without applying the Tamm–Dancoff approximation (TDA). At the TD-DFT level, we evaluate a large panel of global, range-separated, local, and double hybrid functionals. Additionally, we assess the performance of the Bethe–Salpeter equation (BSE) formalism relying on both G0W0 and evGW quasiparticle energies evaluated from various starting points. It turns out that CC2 and ADC(2.5) are the most accurate models among those with respective O(N5) and O(N6) scalings with system size. In contrast, CCSD does not outperform CC2. The best performing exchange–correlation functionals include BMK, M06–2X, M06-SX, CAM-B3LYP, ωB97X-D, and LH20t, with average deviations of approximately 0.20 eV or slightly below. Errors on vertical excitation energies can be further reduced by considering double hybrids. Both SOS-ωB88PP86 and SOS-ωPBEPP86 exhibit particularly attractive performances with overall quality on par with CC2, whereas PBE0-DH and PBE-QIDH are only slightly less efficient. BSE/evGW calculations based on Kohn–Sham starting points have been found to be particularly effective for singlet transitions, but much less for their triplet counterparts.

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In this paper we examine the numerical approximation of the limiting invariant measure associated with Feynman-Kac formulae. These are expressed in a discrete time formulation and are associated with a Markov chain and a potential function. The typical application considered here is the computation of eigenvalues associated with non-negative operators as found, for example, in physics or particle simulation of rare-events. We focus on a novel lagged approximation of this invariant measure, based upon the introduction of a ratio of time-averaged Feynman-Kac marginals associated with a positive operator iterated l ∈ N times; a lagged Feynman-Kac formula. This estimator and its approximation using Diffusion Monte Carlo (DMC) have been extensively employed in the physics literature. In short, DMC is an iterative algorithm involving N ∈ N particles or walkers simulated in parallel, that undergo sampling and resampling operations. In this work, it is shown that for the DMC approximation of the lagged Feynman-Kac formula, one has an almost sure characterization of the L1-error as the time parameter (iteration) goes to infinity and this is at most of O(exp{-κl}/N ), for κ > 0. In addition a non-asymptotic in time, and time uniform L1-bound is proved which is O(l/ √ N ). We also prove a novel central limit theorem to give a characterization of the exact asymptotic in time variance. This analysis demonstrates that the strategy used in physics, namely, to run DMC with N and l small and, for long time enough, is mathematically justified. Our results also suggest how one should choose N and l in practice. We emphasize that these results are not restricted to physical applications; they have broad relevance to the general problem of particle simulation of the Feynman-Kac formula, which is utilized in a great variety of scientific and engineering fields.

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In a recent work we have proposed an original analytic expression for the partition function of the quartic oscillator. This partition function, which has a simple and compact form with {\it no adjustable parameters}, reproduces some key mathematical properties of the exact partition function and provides free energies accurate to a few percent over a wide range of temperatures and coupling constants. In this work, we present the derivation of the energy spectrum of this model. We also generalize our previous study limited to the quartic oscillator to the case of a general anharmonic oscillator. Numerical application for a potential of the form $V(x)=\frac{\omega^2}{2} x^2 + g x^{2m}$ show that the energy levels are obtained with a relative error of about a few percent, a precision which we consider to be quite satisfactory given the simplicity of the model, the absence of adjustable parameters, and the negligible computational cost.

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The era of exascale computing presents both exciting opportunities and unique challenges for quantum mechanical simulations. While the transition from petaflops to exascale computing has been marked by a steady increase in computational power, the shift towards heterogeneous architectures, particularly the dominant role of graphical processing units (GPUs), demands a fundamental shift in software development strategies. This review examines the changing landscape of hardware and software for exascale computing, highlighting the limitations of traditional algorithms and software implementations in light of the increasing use of heterogeneous architectures in high-end systems. We discuss the challenges of adapting quantum chemistry software to these new architectures, including the fragmentation of the software stack, the need for more efficient algorithms (including reduced precision versions) tailored for GPUs, and the importance of developing standardized libraries and programming models.

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Sujets

Biodegradation Approximation GW Anharmonic oscillator Atrazine AROMATIC-MOLECULES Electron electric moment Analytic gradient Green's function Molecular properties Relativistic corrections Xenon Mécanique quantique relativiste Acrolein Ion 3115ag Diffusion Monte Carlo Relativistic quantum chemistry Théorie des perturbations Ground states Diatomic molecules Path integral Anderson mechanism Atomic charges 3115am Corrélation électronique Auto-énergie Atrazine-cations complexes Chemical concepts 3115vj Hyperfine structure A posteriori Localization New physics Parity violation Rydberg states Quantum Chemistry Density functional theory Petascale Pesticides Metabolites Clustering Molecular modeling Environmental fate Partial least squares 3115vn Atomic charges chemical concepts maximum probability domain population Relativistic quantum mechanics Atomic and molecular collisions Adiabatic connection BENZENE MOLECULE Atom Carbon Nanotubes Abiotic degradation États excités CP violation Wave functions Argon Configuration interactions Atoms Numerical calculations Argile 3115bw ALGORITHM Configuration interaction Pesticide Atomic data Configuration Interaction Range separation Valence bond Spin-orbit interactions Ab initio calculation Line formation Electron electric dipole moment Dipole 3115aj Dirac equation Dispersion coefficients Aimantation Electron correlation Coupled cluster Azide Anion Time-dependent density-functional theory Atomic processes 3470+e Perturbation theory Parallel speedup Atomic and molecular structure and dynamics Fonction de Green Polarizabilities AB-INITIO Molecular descriptors CIPSI X-ray spectroscopy AB-INITIO CALCULATION Single-core optimization 3115ae Chimie quantique A priori Localization Quantum chemistry QSAR Coupled cluster calculations 3315Fm Large systems Time reversal violation Excited states Quantum Monte Carlo

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Nombre de fichiers déposés

248

Nombre de notices déposées

275