Quantum Mechanical Description Research Articles

Do regular quantum black holes exist?

Regular black holes do not exist in any classical theory of gravity including Einstein's general relativity. This unappealing feature is due to the appearance of a singularity in the interior of the black hole described by any classical theory. As Hawking argued, all known laws of physics must break down at the singularity. It is thus an important question whether this singularity can disappear in a quantum mechanical description of spacetime. In this letter, we therefore quantize the black hole interior in a Kantowski-Sachs minisuperspace representation in the presence of spontaneous Klein-Gordon matter field fluctuations. This leads to a Wheeler-DeWitt equation whose solution yields the interior wave function of the black hole. The regular part of this wave function satisfies the DeWitt boundary condition in that it vanishes at the singularity. Moreover, the wave function is regular and well behaved in the region around the singularity. These features of the wave function suggest that regular black holes do exist in quantum gravity.

Topological dynamics of adiabatic cat states

We consider a quantum topological frequency converter, realized by coupling a qubit to two slow harmonic modes. The dynamics of such a system is the quantum analog of topological pumping. Our quantum mechanical description shows that an initial state generically evolves into a superposition of two adiabatic states. The topological nature of the coupling between the qubit and the modes splits these two components apart in energy: for each component, an energy transfer at a quantized rate occurs between the two quantum modes, in opposite directions for the two components, reminiscent of the topological pumping. We denote such a superposition of two quantum adiabatic states distinguishable through measures of the modes’ energy an adiabatic cat state. We show that the topological coupling enhances the entanglement between the qubit and the modes, and we unveil the role of the quantum or Fubini-Study metric in the characterization of this entanglement.

Scalable quantum detector tomography by high-performance computing

Abstract At large scales, quantum systems may become advantageous over their classical counterparts at performing certain tasks. Developing tools to analyze these systems at the relevant scales, in a manner consistent with quantum mechanics, is therefore critical to benchmarking performance and characterizing their operation. While classical computational approaches cannot perform like-for-like computations of quantum systems beyond a certain scale, classical high-performance computing (HPC) may nevertheless be useful for precisely these characterization and certification tasks. By developing open-source customized algorithms using high-performance computing, we perform quantum tomography on a megascale quantum photonic detector covering a Hilbert space of 106. This requires finding 108 elements of the matrix corresponding to the positive operator valued measure (POVM), the quantum description of the detector, and is achieved in minutes of computation time. Moreover, by exploiting the structure of the problem, we achieve highly efficient parallel scaling, paving the way for quantum objects up to a system size of 1012 elements to be reconstructed using this method. In general, this shows that a consistent quantum mechanical description of quantum phenomena is applicable at everyday scales. More concretely, this enables the reconstruction of large-scale quantum sources, processes and detectors used in computation and sampling tasks, which may be necessary to prove their nonclassical character or quantum computational advantage.

Next-generation cathodes for calcium-ion batteries: Leveraging NASICON structures for enhanced stability and energy density

This study focuses on developing a high-performance, stable cathode for calcium-ion batteries (CIBs) using a sodium superionic conductor (NASICON) structure to match the energy density and safety standards of current lithium- and sodium-ion batteries. Given the relatively sparse database of CIB materials compared with their lithium and sodium counterparts, expanding the range of new candidates is essential for developing high-performance batteries. To address this, we employed density functional theory (DFT) calculations, which provide a quantum-mechanical description of the electronic properties of materials, to construct a highly reliable database. To improve the accuracy and efficiency, we integrated machine learning interatomic potential with DFT to stabilize the NASICON-type structures, CaxNaV’yV’’2-yBzP3-zO12, where x = 0.8, 0.5, 0; y = 1, 0.5; z = 0.5, 0; V’ and V’’ are transition metals that support stable doped configurations at the V- and P-sites. From the initial 176 candidates, the top 10 materials that facilitate stable structures were identified based on selection criteria focusing on formation energy < 0 eV/atom, energy above hull = 0 eV/atom, gravimetric capacity ≥ 150 mAh/g, -1% ≤ volume change ≤ 1%, and 3 ≤ average voltage ≤ 4.5 V. This approach advances CIB technology and outlines effective strategies for dopant selection to optimize battery cathodes, configuring a framework for future advancements in battery technology.

Assessing the Accuracy of Quantum Dynamics Performed in the Time-Dependent Basis Representation.

A full quantum-mechanical (QM) description of large amplitude nuclear motion, associated with chemical reactions or isomerization of high-dimensional molecular systems, is inherently challenging due to the exponential scaling of the QM complexity with system size. To ameliorate the scaling bottleneck in studies of realistic systems, typically modeled in the configuration space, the nuclear wave functions are represented in terms of time-dependent basis functions. Such bases are expected to give an accurate description with a modest number of basis functions employed, by adapting them to the wave function solving the time-dependent Schrödinger equation. It is not, however, straightforward to estimate the accuracy of the resulting solution: in QM the energy conservation, a convenient such measure for a classical trajectory evolving in a time-independent potential, is not a sufficient criterion of the dynamics' accuracy. In this work, we argue that the expectation value of the Hamiltonian's "variance", quantifying the basis completeness, is a suitable practical measure of the quantum dynamics' accuracy. Illustrations are given for several chemistry-relevant test systems, modeled employing time-independent as well as time-dependent bases, including the coupled and variational coherent states methods and the quantum-trajectory guided adaptable Gaussians (QTAG) as the latter basis type. A novel semilocal definition of the QTAG basis time-evolution for placing the basis functions "in the right place at the right time" is also presented.

Axion detection via superfluid 3He ferromagnetic phase and quantum measurement techniques

We propose to use the nuclear spin excitation in the ferromagnetic A1 phase of the superfluid 3He for the axion dark matter detection. This approach is striking in that it is sensitive to the axion-nucleon coupling, one of the most important features of the QCD axion introduced to solve the strong CP problem. We review a quantum mechanical description of the nuclear spin excitation and apply it to the estimation of the axion-induced spin excitation rate. We also describe a possible detection method of the spin excitation in detail and show that the combination of the squeezing of the final state with the Josephson parametric amplifier and the homodyne measurement can enhance the sensitivity. It turns out that this approach gives good sensitivity to the axion dark matter with the mass of O\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$$ \\mathcal{O} $$\\end{document}(1) μeV depending on the size of the external magnetic field. We estimate the parameters of experimental setups, e.g., the detector volume and the amplitude of squeezing, required to reach the QCD axion parameter space.

Non-Markovian quantum mechanics on comb.

Quantum dynamics of a particle on a two-dimensional comb structure is considered. This dynamics of a Hamiltonian system with a topologically constrained geometry leads to the non-Markovian behavior. In the framework of a rigorous analytical consideration, it is shown how a fractional time derivative appears for the relevant description of this non-Markovian quantum mechanics in the framework of fractional time Schrödinger equations. Analytical solutions for the Green functions are obtained for both conservative and periodically driven in time Hamiltonian systems.

Loophole-Free Test of Local Realism via Hardy's Violation.

Bell's theorem states that the quantum mechanical description of physical quantities cannot be fully explained by local realistic theories, laying a solid basis for various quantum information applications. Hardy's paradox is celebrated as the simplest form of Bell's theorem concerning its "All versus Nothing" approach to test local realism. However, due to experimental imperfections, existing tests of Hardy's paradox require additional assumptions of the experimental systems, and these assumptions constitute potential loopholes for faithfully testing local realistic theories. Here, we experimentally demonstrate Hardy's nonlocality through a photonic entanglement source. By achieving a detection efficiency of 82.2%, a quantum state fidelity of 99.10%, and applying high-speed quantum random number generators for the measurement setting switching, the experiment is implemented in a loophole-free manner. During 6h of running, a strong violation of P_{Hardy}=4.646×10^{-4} up to 5 standard deviations is observed with 4.32×10^{9} trials. A null hypothesis test shows that the results can be explained by local realistic theories with an upper bound probability of 10^{-16348}. These testing results provide affirmative evidence against local realism, and establish an advancing benchmark for quantum information applications based on Hardy's paradox.

Time-dependent surface-enhanced Raman scattering: A theoretical approach.

A new procedure for computing the time-dependent Raman scattering of molecules in the proximity of plasmonic nanoparticles (NPs) is proposed, drawing inspiration from the pioneering Lee and Heller's theory. This strategy is based on a preliminary simulation of the molecular vibronic wavefunction in the presence of a plasmonic nanostructure and an incident light pulse. Subsequently, the Raman signal is evaluated through an inverse Fourier Transform of the coefficients' dynamics. Employing a multiscale approach, the system is treated by coupling the quantum mechanical description of the molecule with the polarizable continuum model for the NP. This method offers a unique advantage by providing insights into the time evolution of the plasmon-enhanced Raman signal, tracking the dynamics of the incident electric field. It not only provides for the total Raman signal at the process's conclusion but also gives transient information. Importantly, the flexibility of this approach allows for the simulation of various incident electric field profiles, enabling a closer alignment with experimental setups. This adaptability ensures that the method is relevant and applicable to diverse real-world scenarios.

Quantum nature of spacetime near the black hole singularity

The concept of spacetime loses its usual interpretation at the essential singularity of a black hole. In consequence, all laws of physics must fail at this classical singularity. This unphysical behavior of spacetime at the singularity originates from general relativity. In order to have a consistent description of spacetime, this singularity must disappear in a quantum mechanical description of spacetime which is expected to be given by a quantum theory of gravity. In this paper, we therefore attempt to describe the quantum nature of spacetime in the vicinity of the (classical) singularity of a black hole. We take the Kantowsi–Sachs representation for the interior spacetime of a black hole and include inevitable vacuum fluctuations of matter field in the Klein–Gordon representation. Hence we obtain the Wheeler–DeWitt equation for the black hole interior and solve this equation exactly yielding a general expression for the interior wave function of the black hole. Admissible wave functions consistent with the DeWitt boundary condition implies that the Hilbert space has three nonoverlapping sectors distinguished by the relative character of the eigenvalues. Regular quantum black holes with admissible and well-behaved wave function having no singularity can exist only in two of those sectors. However, the remaining sector does not contain any regular quantum black hole.

The Radiation Field, at the Origin of the Quantum Canonical Operators

We show that the electromagnetic radiation field, conventionally introduced as a perturbation in quantum mechanics, is actually at the basis of the operator formalism. We first analyze the linear resonant response of the (continuous) variables x(t), p(t) of a harmonic oscillator to the full radiation field, i.e. the zero-point field plus an applied field playing the role of the driving force, and then extend the analysis to the response of a charged particle bound by a non-linear force, typically an atomic electron. This leads to the establishment of a one-to-one correspondence between the response functions and the respective quantum operators, and to the identification of the quantum commutator with the Poisson bracket of the response functions with respect to the normalized variables of the driving field. To complete the quantum description, a similar procedure is used to obtain the field operators as the response functions to the same normalized variables. The results allow us to draw important conclusions about the physical content of the quantum formalism, in particular about the meaning of the quantum expectation values and the coarse-grained nature of the quantum-mechanical description.

Modeling the conditions for obtaining nanostructures during ion-plasma processing taking into account the quantum-mechanical properties of electrode material

The subject matter of the article is the thermophysical and mechanical properties of surface layers of structural materials using a quantum-mechanical approach. The aim of the article is to adjust the parameters of the heat conductivity and thermoelasticity problem, considering all possible external and internal thermal effects and the quantum-mechanical description of the material structure, for electrodes in vacuum-arc nanostructuring. The task to be solved is to perform calculations using the developed model for a copper cathode considering the energy spent on the formation of nanoparticles during ion-plasma processing with oxygen ions. The methods used are methods for solving nonlinear problems. The following results were obtained. 1. The nature of the dependencies of the maximum temperature, the expected volume of nanostructures, and the maximum depth of their formation on the energy of oxygen ions with charges z = 1 and z = 2 matches previously known dependencies obtained by the classical model, but under quantum-mechanical consideration, the maximum temperature values increase by 15%, the volume of the nanocluster increases by 50%, and the maximum depth of its occurrence increases by 1.5 times. 2. When selecting the parameters of ion-plasma processing for obtaining nanostructures with ion energies 100...500 eV, the previously proposed model with general thermophysical and mechanical properties of structural materials can be used. 3. For technologies with ion energies in the range of 103...2∙103 eV, the previously proposed model can be used but with quantum-mechanical effects of structural materials considered. 4) For technologies with ion energies above 104 eV, calculations should be performed using both approaches (the classical approach and the approach considering the quantum-mechanical properties of structural materials), and after comparison, the variant whose calculation results are closest to the experimental results should be used. Conclusions. The proposed theoretical model using the thermophysical, mechanical, and quantum-mechanical properties of structural materials can be used to adjust the technological parameters of ion-plasma processing to assess the formation of nanostructures in protective and strengthening coatings.

The role of axial angular momentum in exact non-linear solutions of multipolar spherical and cylindrical vortices

The time-dependent acceleration of fluid particles in an arbitrary superposition of multipolar spherical and cylindrical vortices in presence of a background rotational rigid flow is the gradient of the difference between their kinetic energy and the product of their total axial angular momentum times the angular velocity of the background flow. If the potential energy is defined as the time-dependent field whose minus gradient equals the acceleration of the flow, then the total energy, defined as the sum of kinetic and potential energies, equals the total axial angular momentum times the angular velocity of the background flow. The total energy of a fluid particle has therefore a linear relationship with the azimuthal velocity field. The role of the axial angular momentum in these oscillating flows is explained also in the classical Lagrangian and Hamiltonian descriptions of motion. The linear relation between total energy and angular momentum makes possible that the free parameters of these flows may be obtained, in a way similar to that developed in the quantum mechanics description of motion, as the eigenvalues of linear operators acting on some components of the spherical modes. Beltrami flow solutions in prolate spheroidal geometry for axisymmetric flows are also discussed.

Derivation of Morse potential

The Morse potential is widely used in chemistry, physics, and material science to describe interatomic interactions. We show that the Morse potential can be derived from a simple screened charge model accounting for the shielding of the nuclear charge by electron density. In this model, the parameter governing the width of the potential is related to the average shielding strength and the exponents of the atomic orbitals used in electronic structure calculations. The parameter representing the bond dissociation energy of a diatomic molecule is derived by combining the quantum mechanical covalent and classical electrostatic interactions. Moreover, the revealed connection between the parameters of the Morse potential and Pauling’s bond order and electronegativity provides insight into the relation between the classical and quantum mechanical descriptions of chemical bonds. This derivation of the Morse potential from the atomic quantities is expected to contribute to the development of the new basis sets incorporating Slater-type orbitals for electronic structure calculations and the transferable reactive force fields for molecular dynamics simulations. Furthermore, this interpretation of the Morse potential helps to understand the relationships between widely used chemical concepts, including effective atomic charge, bond dissociation energy, electronegativity, and bond order.

Effective description of a quantum particle constrained to a catenoid

We describe a quantum particle constrained on a catenoid, employing an effective description of quantum mechanics based on expected values of observables and quantum dispersions. We obtain semiclassical trajectories for particles, displaying general features of the quantum behavior; most interestingly, particles present tunneling through the throat of the catenoid, a characteristic having important physical applications.

Subradiant plasmonic cavities make bright polariton states dark

Abstract Nanostructured plasmonic surfaces allow for precise tailoring of electromagnetic modes within sub-diffraction mode volumes, boosting light–matter interactions. This study explores vibrational strong coupling (VSC) between molecular ensembles and subradiant “dark” cavities that support infrared quadrupolar plasmonic resonances (QPLs). The QPL mode exhibits a dispersion characteristic of bound states in the continuum (BIC). That is, the mode is subradiant or evanescent at normal incidence and acquires increasing “bright” dipole character with larger in-plane wavevectors. We deposited polymethyl methacrylate (PMMA) thin films on QPL substrates to induce VSC with the carbonyl stretch in PMMA and measured the resulting infrared (IR) spectra. Our computational analysis predicts the presence of “dark” subradiant polariton states within the near-field of the QPL mode, and “bright” collective molecular states. This finding is consistent with classical and quantum mechanical descriptions of VSC that predict hybrid polariton states with cavity-like modal character and N−1 collective molecular states with minimal cavity character. However, the behaviour is opposite of what is standardly observed in VSC experiments that use “bright” cavities, which results in “bright” polariton states that can be spectrally resolved as well as N−1 collective molecular states that are spectrally absent. Our experiments confirm a reduction of molecular absorption and other spectral signatures of VSC with the QPL mode. In comparison, our experiments promoting VSC with dipolar plasmonic resonances (DPLs) reproduce the conventional behavior. Our results highlight the significance of cavity mode symmetry in modifying the properties of the resultant states from VSC, while offering prospects for direct experimental probing of the N−1 molecule-like states that are usually spectrally “dark”.

Maximising the consistency of the presentation of the molecular level with its quantum mechanical description: challenges and opportunities

Abstract Reasoning in terms of molecules has since long become fully embedded in any chemistry discourse. On the other hand, students’ familiarization with the molecular level in pre-university instruction is not always satisfactory, and their ability to view chemical phenomena in terms of what molecules do may not reach the extent and quality that would be needed to ensure effective conceptual understanding. Students may remain uncertain about the interpretation of the molecular features of a number of phenomena even through undergraduate instruction. Removing uncertainties and promoting comfortable familiarization is increasingly becoming an imperative for chemistry education, in view of the novel central role that the molecular level is acquiring not only for the customary interpretation of phenomena, but for the high variety of applications that have been blooming in recent years. Consequently, learners’ familiarization with the world of molecules needs to become more informative and complete. It is equally important that the information that they acquire about molecules be consistent with the modern descriptions, which are based on quantum mechanics. This requires accurate search for optimal balances between the need to simplify the terms of the descriptions in order to make them accessible to leaners according to the different levels of chemistry learning, and the simultaneous need to maintain adequate conceptual rigour. The present work outlines approaches which have proved viable and effective, and which rely on accurate use of language and visualization as the major explanation resources.

Integrating subsystem embedding subalgebras and coupled cluster Green’s function: a theoretical foundation for quantum embedding in excitation manifold

In this study, we introduce a novel approach to coupled-cluster Green’s function (CCGF) embedding by seamlessly integrating conventional CCGF theory with the state-of-the-art sub-system embedding sub-algebras coupled cluster (SES-CC) formalism. This integration focuses primarily on delineating the characteristics of the sub-system and the corresponding segments of the Green’s function, defined explicitly by active orbitals. Crucially, our work involves the adaptation of the SES-CC paradigm, addressing the left eigenvalue problem through a distinct form of Hamiltonian similarity transformation. This advancement not only facilitates a comprehensive representation of the interaction between the embedded sub-system and its surrounding environment but also paves the way for the quantum mechanical description of multiple embedded domains, particularly by employing the emergent quantum flow algorithms. Our theoretical underpinnings further set the stage for a generalization to multiple embedded sub-systems. This expansion holds significant promise for the exploration and application of non-equilibrium quantum systems, enhancing the understanding of system–environment interactions. In doing so, the research underscores the potential of SES-CC embedding within the realm of quantum computations and multi-scale simulations, promising a good balance between accuracy and computational efficiency.

Quantum Mechanics of One-Dimensional Three-Body Contact Interactions

The quantum mechanical description of topologically nontrivial three-body contact interactions in one dimension is not well understood. This study explores the Hamiltonian description of these interactions using the path-integral formalism.

Wandering through quantum-mechanochemistry: from concepts to reactivity and switches.

Mechanochemistry has experienced a renaissance in recent years witnessing, at the molecular level, a remarkable interplay between theory and experiment. Molecular mechanochemistry has welcomed a broad spectrum of quantum-chemical methods to evaluate the influence of an external mechanical force on molecular properties. In this contribution, an overview is given on recent work on quantum mechanochemistry in the Brussels Quantum Chemistry group (ALGC). The effect of an external force was scrutinized both in fundamental topics, like reactivity descriptors in Conceptual DFT, and in applied topics, such as designing molecular force probes and tuning the stereoselectivity of certain types of reactions. In the conceptual part, a brief overview of the techniques introducing mechanical forces into a quantum-mechanical description of a molecule is followed by an introduction to conceptual DFT. The evolution of the electronic chemical potential (or electronegativity), chemical hardness and electrophilicity are investigated when a chemical bond in a series of diatomics is put under mechanical stress. Its counterpart, the influence of mechanical stress on bond angles, is analyzed by varying the strain present in alkyne triple bonds by applying a bending force, taking the strain promoted alkyne-azide coupling cycloaddition as an example. The increase of reactivity of the alkyne upon bending is probed by Fukui functions and the local softness. In the applied part, a new molecular force probe is presented based on an intramolecular 6π-electrocyclization in constrained polyenes operating under thermal conditions. A cyclic process is conceived where ring opening and closure are triggered by applying or removing an external pulling force. The efficiency of mechanical activation strongly depends on the magnitude of the applied force and the distance between the pulling points. The idea of pulling point distances as a tool to identify new mechanochemical processes is then tested in [28]hexaphyrins with an intricate equilibrium between Möbius aromatic and Hückel antiaromatic topologies. A mechanical force is shown to trigger the interconversion between the two topologies, using the distance matrix as a guide to select appropriate pulling points. In a final application, the Felkin-Anh model for the addition of nucleophiles to chiral carbonyls under the presence of an external mechanical force is scrutinized. By applying a force for restricting the conformational freedom of the chiral ketone, otherwise inaccessible reaction pathways are promoted on the force-modified potential energy surfaces resulting in a diastereoselectivity different from the force-free reaction.