Quantum Theory Research Articles

Delocalization-ratio analysis of 3-center bonding in position-space for closo-boranes and related systems: Approaching the styx picture and beyond.

Closo-boron hydrides BnHn 2- (n = 5-12) are a conceptually well understood class of compounds. For these and a few related prototype compounds, both the local and the global picture of 3-center bonding are extracted from position-space quantities based on the electron density and the pair density. For this purpose, three-center delocalization indices between quantum theory of atoms in molecules (QTAIM) atoms in position space are used to develop a consistent set of local bond and triangle, and global cluster delocalization ratios (DRs), which are quantitatively compared with conceptual Γ values derived from the styx code for each cluster. Combination of the cluster DRs with associated effective numbers of skeletal electron sharing (SES) for selected cluster surface edges, triangles, or the whole cluster yields effective styx type values describing the trend and even the size of the conceptual styx codes for closo-boranes BnHn 2- and related systems with increasing cluster size n reasonably well. For nonuniform cluster topologies, the different vertex degrees are shown to cause systematic 3-center wise bond delocalization effects for the associated edges and triangles of different average vertex degrees. Extension of DR analysis beyond the styx type triangular cluster-surface bonding corresponds to a triangulation of multicentric bonding. The cluster-wise results keep indicating consistency with the mixed 2- and 3-center bonding approach. The successfully established chemical meaning of the local edge, triangle, and global cluster DRs and their associated SES values constitutes the basis for systematic investigations of mixed 2- and 3-center bonding scenarios in particular in intermetallic and related (endohedral) cluster compounds in the future.

Quantum Topological Atomic Properties of 44K molecules

We present a data set of quantum topological properties of atoms of 44K randomly selected molecules from the GDB-9 data set. These atomic properties were obtained as defined by the quantum theory of atoms in molecules (QTAIM) within an atomic basin, a region of real space bounded by zero-flux surfaces in the electron density gradient vector field. The wave function files were generated through DFT static calculations (B3LYP/6-31G), and the atomic properties were calculated using QTAIM. The calculated atomic properties include the energy of the atomic basin, the electronic population, the magnitude of the total dipole moment, and the magnitude of the total quadrupole moment. The atomic properties allow one to understand the chemical structure, reactivity, and molecular recognition. They can be incorporated into force fields for molecular dynamics or for predicting reactive sites. We believe that this data set could facilitate new studies in chemical informatics, machine learning applied to chemistry, and computational molecular design.

Operators of quantum theory of Dirac's free field

The Pryce (e) spin and position operators of the quantum theory of Dirac's free field were re-defined and studied recently with the help of a new spin symmetry and suitable spectral representations [Eur. Phys. J. C 82, 1073 (2022)]. This approach is generalized here, associating a pair of integral operators acting directly on particle and antiparticle wave spinors in momentum representation to any integral operator in configuration representation, acting on mode spinors. This framework allows an effective quantization procedure, giving a large set of one-particle operators with physical meaning as the spin and orbital parts of the isometry generators, the Pauli-Lubanski and position operators, or other spin-type operators proposed to date. Special attention is paid to the operators that mix the particle and antiparticle sectors whose off-diagonal associated operators have oscillating terms producing Zitterbevegung. The principal operators of this type, including the usual coordinate operator, are derived here for the first time. As an application, it is shown that an apparatus measuring these new observables may prepare and detect one-particle wave packets moving uniformly without Zitterbewegung or spin dynamics, spreading in time normally as any other relativistic or even non-relativistic wave packet.

Self-assembled belt[12]pyridine nanotube for the adsorption and removal of anti-TB drugs from wastewater

Environmental safety is a major concern of today's world, and it has attracted the attention of the scientific research community. The environment gets contaminated due to various toxic drugs and pharmaceutical toxins coming from different sources. Therefore, removing these toxins is necessary for making the environment greener and safer. Nanomaterials are excellent candidates for adsorption and removal of harmful materials due to their unique properties. Herein we have studied self-assembled nanotube based on belt[12]pyridine (2-(12BPy)) as an adsorbent for the removal of antituberculosis drugs i.e. isoniazid (INZ) and pyrazinamide (PZA). The adsorption ability is studied by considering the adsorption energy (Eads), non-covalent interaction index analysis (NCI), quantum theory of atoms in molecules (QTAIM), energy decomposition analysis (EDA), charge transfer via natural bond orbital analysis (NBO) and electron localization function (ELF), and dipole moment. The results indicate strong adsorption of selected drugs with self-assembled nanotube without altering the electronic properties. Recovery time of the complexes is also calculated to understand the regeneration of the nanotube. Results also demonstrate that van der Waals forces are major contributor in the adsorption of drug molecules within the nanotube. Our results indicate that belt[12]pyridine (2-(12BPy)) nanotube can be used as an adsorbent for the removal of toxic drug molecules from the environment. This research will benefit the scientists working in the field of new sensors for biological components and materials.

Exploring Nano-optical Molecular Switch Systems for Potential Electronic Devices: Understanding Electric and Electronic Properties through DFT-QTAIM Assembly.

The design and synthesis of molecular nanoswitches using organic molecules represent a crucial research field within molecular electronics. To understand the switching mechanisms, it is essential to investigate various factors, such as charge/energy transfer, electron transfer, nonlinear optical properties (NLO), current-voltage (I-V) curves, Joule-like (LJL) and Peltier-like (LPL) intramolecular phenomenological coefficients, as well as the energy levels of the highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO) boundary orbitals. In this Article, a novel approach to designing a molecular nanoswitch and understanding its ON/OFF mechanism is presented, utilizing the quantum theory of atoms in molecules (QTAIM), density functional theory (DFT), and Landauer theory (LT). These analyses contribute significantly to a deep understanding of switching effects within molecular electronic systems.

Generalized parity-oblivious communication games powered by quantum preparation contextuality

Abstract The parity-oblivious random-access-code (PORAC) is a class of communication games involving a sender (Alice) and a receiver (Bob). In such games, Alice’s amount of communication to Bob is constraint by the parity-oblivious (PO) conditions, so that the parity information of her inputs remains oblivious to Bob. The PO condition in an operational theory is equivalently represented in an ontological model that satisfies the preparation noncontextuality. In this paper, we provide a nontrivial generalization of the existing two-level PORAC and derive the winning probability of the game in the preparation noncontextual ontological model. We demonstrate that the quantum theory outperforms the preparation noncontextual model by predicting higher winning probability in our generalized PORAC.

Generalized Einstein–Podolsky–Rosen steering paradox

Abstract Quantum paradoxes are essential means to reveal the incompatibility between quantum and classical theories, among which the Einstein–Podolsky–Rosen (EPR) steering paradox offers a sharper criterion for the contradiction between local-hidden-state model and quantum mechanics than the usual inequality-based method. In this work, we present a generalized EPR steering paradox, which predicts a contradictory equality “2Q = (1 + δ)C” (0 ≤ δ < 1) given by the quantum (Q) and classical (C) theories. For any N-qubit state in which the conditional state of the steered party is pure, we test the paradox through a two-setting steering protocol, and find that the state is steerable if some specific measurement requirements are satisfied. Moreover, our construction also enlightens the building of EPR steering inequality, which may contribute to some schemes for typical quantum teleportation and quantum key distributions.

Insights into the adsorption of thiophene and fluorinated-thiophenes on the Mg4O4 cluster: a quantum chemical investigation

In this work, the adsorption of thiophene on the Mg4O4 cluster was examined at the LC-ωPBE/6-311G(d,p) level of theory. The influence of replacing hydrogen atoms of thiophene with fluorine atoms was considered. The comparison of relative stabilities of possible isomers indicated most stable isomers were 3-FT … Mg4O4, 3,4-DFT … Mg4O4, 2,3,4-TFT … Mg4O4 structures in the mono, di and tri-fluorinated thiophenes, respectively. Corrected adsorption energy and thermodynamic parameter values of these systems were evaluated and the substituent effect on the adsorption was explored. 2-FT … Mg4O4, 3,4-DFT … Mg4O4, 2,3,4-TFT … Mg4O4 structures indicated the most significant adsorptions in the mono, di and tri-fluorinated thiophenes, respectively. Electrophilicity-based charge transfer (ECT) was employed to illustrate charge transfer between aromatic systems and the Mg4O4 cluster. Quantum theory of atoms in molecule (QTAIM) and interaction region indicator (IRI) were used to deeply investigate two fragments.

Looking for Carroll Particles in the Two-Time Spacetime

We make an attempt to describe Carroll particles with a non-vanishing value of energy (i.e., the Carroll particles which always stay in rest) in the framework of two-time physics, developed in the series of papers by I. Bars and his co-authors. In the spacetime with one additional time dimension and one additional space dimension, where one can localize the symmetry which exists between generalized coordinates and their conjugate momenta. Such a localization implies the introduction of the gauge fields, which, in turn, implies the appearance of some first-class constraints. Choosing different gauge-fixing conditions and solving the constraints, we obtain different time parameters, Hamiltonians, and, generally, physical systems in the standard one-time spacetime. We find a set of gauge fixing conditions which gives the description of a Carroll particle in the one-time world. We construct the quantum theory of such a particle using an unexpected correspondence between our parametrization and that obtained by Bars for the hydrogen atom in 1999.

A novel Co(II) complex with sulfamethoxazole ligand: Isostructuralism, non-covalent interactions, Hirshfeld surfaces, crystal voids and energy calculations

The crystal structure of [Co(H2O)6][Co(SMX)3]2 complex (SMX = sulfamethoxazole), hereafter CoSMXW, has been solved by X-ray diffraction methods. The complex CoSMXW was characterized by Infrared (IR), Raman, and UV-Vis spectroscopies. A comparison with the analogous Mn(II) complex, [Mn(H2O)6][Mn(SMX)3]2 (CSD refcode AJIFUW), indicates 3D isostructurality and packing similarity, as evident from X-ray diffraction and geometric descriptors such as dissimilarity index (X = 2.0 from XPac) and packing similarity (PSab = 0.3070 from CrystalCMP), respectively. This represents the first case of isostructurality observed among eleven metal complexes of sulfamethoxazole reported in the literature. A study of non-covalent interactions shows presence of structural motifs involving N-H…O and N-H…S (Motif I), N-H…O (Motif II), O-H…O and O-H…N (Motif III) H-bonds, as well as C-H…π contacts (Motif IV) for [Co(H2O)6][Co(SMX)3]2 and AJIFUW. Energy analysis using CrystalExplorer indicates that the strongest dimer involves Motifs I and II with total energy of -70.3 kcal/mol for CoSMXW, which is only 2.1 kcal/mol longer than that for AJIFUW. Hirshfeld surface (HS) analysis reveals meaningless effect of metal replacement on the intermolecular contacts, confirming the energetic results. The volume of the crystal voids and the percentage of free space were calculated as 862.35 Å3 and 11.8 % for CoSMXW, and 911.42 Å3 and 12.2 % for AJIFUW. 3D topology and hierarchy of interactions were analyzed with energy framework diagrams. Further, structural motifs, HS, crystal voids and intermolecular energies for the SMX free ligand (CSD refcode SLFNMB08) were also studied. Finally, the present study was complemented with DFT calculations to evaluate the strength and nature of the non-covalent interactions by using the quantum theory of atoms in molecules (QTAIM) and NCIplots computational tools. In addition, we have used the potential energy density predictor obtained from QTAIM analysis to investigate the relative contribution of each interaction to the formation of the assemblies.

Time-dependent scalings and Fock quantization of a massless scalar field in Kantowski–Sachs

Abstract We address the issue of inequivalent Fock representations in quantum field theory in a curved homogenous and anisotropic cosmological background, namely Kantowski–Sachs spacetime, which can also be used to describe the interior of a nonrotating black hole. A family of unitarily equivalent Fock representations that are invariant under the spatial isometries and implement a unitary dynamics can be achieved by means of a field redefinition that consists of a specific anisotropic scaling of the field configuration and a linear transformation of its momentum. Remarkably, we show that this kind of field redefinition is in fact unique under our symmetry and unitary requirements. However, the physical properties of the Hamiltonian dynamics that one obtains in this way are not satisfactory, inasmuch as the action of the Hamiltonian on the corresponding particle states is ill defined. To construct a quantum theory without this problem, we need a further canonical transformation that is time- and mode-dependent and is not interpretable as an anisotropic scaling. The old and new Fock representations, nevertheless, are unitarily equivalent. The freedom that is introduced when allowing for this further canonical transformation can be fixed by demanding an asymptotic diagonalization of the Hamiltonian and a minimal absorption of dynamical phases. In this way, the choice of vacuum and the associated Fock representation are asymptotically determined.

Kink phenomena of the time-space fractional Sharma-Tasso-Olver (STO) equation

Abstract This paper aims to obtain exact solutions of solitary waves for the conformable fractional Sharma-Tasso-Olver (STO) equation which plays an important role in nuclear physics to describe the physical occurrences such as the fission and fusion processes. Solitary waves operate central parts in different areas of study such as electromagnetism, atomic quantum theory, as well as special relativity. By means of sub-ode approach with the aid of the modified fractional Riccati-Bernoulli equation, the exact forms of generalized solitary solution of the fractional (STO) equation are found and specified in hyperbolic, trigonometric, and rational functions. This makes the visualization of the fractional effects and the dynamic behaviors of these solutions in 3D and 2D help in establishing practicality for application of the results. The novel analytical results benefit general engineering and mathematical physics in demonstrating that the proposed employment of the given technique allows solving nonlinear problem analytically. These findings are significant for the progress of wave proceedings in the number of applications.

Vacancy defect in boron nitride nanotube improves CO2 uptake from the gaseous mixture

Boron Nitride Nanotubes (BNNTs), 1-D nanomaterials, having extraordinary mechanical properties, are similar to carbon nanotubes. The structure of BNNT consists of alternative boron and nitrogen atoms, arranged in hexagonal lattice. In the current study, we have investigated the defected boron nitride nanotube (defBNNT) capability to capture CO2 from a mixture of greenhouse gases such as CH4, CO2, CO, and H2. The deep understanding of analytes@defBNNT complexation is acquired by interaction energies, quantum theory of atoms in molecules (QTAIM), noncovalent interaction (NCI), natural bond orbital (NBO), and frontier molecular orbital (FMO) analysis etc. It is evident from the results of interaction energies that all the analytes are physiosorbed over the defBNNT. The observed interaction energies are in the range of −2.09 to −6.43 kcal/mol. All the topological parameters, in QTAIM analysis, show that analyte@defBNNT complexes are stabilized through non-covalent interactions, particularly van der Waal's interactions. Results obtained from NCI analysis are strongly corroborated with the QTAIM analysis. The case of CO@defBNNT gives the highest charge transfer (0.031 e−), in natural bond orbital (NBO) analysis. Overall, there is a transfer of charge from analyte to the surface. Through electron density difference (EDD) analysis, the results of NBO charge transfer are also confirmed. We firmly believe that these findings could help experimentalists to design a well-suited surface for CO2 capture using defective boron nitride nanotubes (defBNNTs).

Quantum entanglement of optical photons: the first experiment, 1964–67

The first experimental observation of entangled visible light was achieved by optically exciting free atoms of calcium and detecting pairs of photons emitted in a two-stage cascade. The polarizations of the entangled photons were observed to be correlated, in agreement with quantum theory. This review describes the rationale, methodology, challenges, and results, including experimental details not previously published.

Real-time methods in JT/SYK holography

Abstract We study the conventional holographic recipes and its real-time extensions in the context of the correspondence between SYK quantum mechanics and JT gravity. We first observe that only closed contours are allowed to have a 2d space-time holographic dual. Thus, in any real-time formulation of the duality, the boundaries of a classical connected geometry are a set of closed curves, parameterized by a complex \emph{closed} time contour as in the Schwinger-Keldysh framework. Thereby, a consistent extension of the standard holographic formulas is proposed, in order to describe the correspondence between gravity and boundary quantum models that include averaging on the coupling constants. We investigate our prescription in different AdS
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 solutions with Schwinger-Keldysh boundary condition, dual to a boundary quantum theory at finite temperature defined on a complex time contour, and consider also classical, asymptotically AdS solutions (wormholes) with two disconnected boundaries. In doing this, we revisit the so-called factorization problem, and its resolution in conventional holography by virtue of some (non-local) coupling between disconnected boundaries, and we show how in specific contexts, the averaging proposal by-passes the paradox as well, since it induces a similar effective coupling.

Is There an Adduct of Pyridine N-Oxide and Boron Trifluoride in the Gaseous State? Gas Electron Diffraction vs Mass Spectrometry.

A study of saturated vapor over the pyridine N-oxide-boron trifluoride (PyO-BF3) adduct was carried out at T = 448(5) K by a synchronous gas electron diffraction/mass spectrometry (GED/MS) experiment. Due to the absence of ions in the mass spectrum, indicating the presence of a structure with an O-B dative bond, several models of vapor composition were tested by the GED method. It was found that the dominant molecular form (up to 100%) in vapor is the PyO-BF3 adduct. Using the DFT/M06-2X/aug-cc-pVTZ method, geometric optimization of the molecular ion [PyO-BF3]+ was carried out, which showed its intrinsic instability and dissociation into a [PyO]+ cation and a BF3 molecule. This study certainly demonstrates the significant advantage of the GED method to determine the qualitative and quantitative gas-phase composition of dative-bonded adducts and other noncovalent complexes as well, whereas the interpretation of mass spectra may be ambiguous due to the possible intrinsic instability of ions containing a dative bond. The nature of the O-B bond is discussed in terms of the natural bond orbitals (NBOs) and the quantum theory of atoms in molecules (QTAIM). A comparison of structural and energetic parameters for PyO-BF3 and the previously studied BF3 adducts allows the theoretical comprehension of the nature of the O-B bond to be extended and to explain the different thermal stabilities of these compounds.

Incompatible observables in classical physics: A closer look at measurement in Hamiltonian mechanics.

Quantum theory famously entails the existence of incompatible measurements, pairs of system observables which cannot be simultaneously measured to arbitrary precision. Incompatibility is widely regarded to be a uniquely quantum phenomenon, linked to failure to commute of quantum operators. Even in the face of deep parallels between quantum commutators and classical Poisson brackets, no connection has been established between the Poisson algebra and any intrinsic limitations to classical measurement. Here I examine measurement in classical Hamiltonian physics as a process involving the joint evolution of an object-system and a finite-temperature measuring apparatus. Instead of the ideal measurement capable of extracting information without disturbing the system, I find a Heisenberg-like precision-disturbance relation: Measuring an observable leaves all Poisson-commuting observables undisturbed but inevitably disturbs all non-Poisson-commuting observables. In this classical uncertainty relation the role of h-bar is played by an apparatus-specific quantity, q-bar. While this is not a universal constant, the analysis suggests that q-bar takes a finite positive value for any apparatus that can be built. (Specifically: q-bar vanishes in the model only in the unreachable limit of zero absolute temperature.) I show that a classical version of Ozawa's model of quantum measurement [Ozawa, Phys. Rev. Lett. 60, 385 (1988)0031-900710.1103/PhysRevLett.60.385], originally proposed as a means to violate Heisenberg's relation, does not violate the classical relation. If this result were to generalize to all models of measurement, then incompatibility would prove to be a feature not only of quantum, but of classical physics too. Put differently: The approach presented here points the way to studying the (Bayesian) epistemology of classical physics, which was until now assumed to be trivial. It now seems possible that it is nontrivial and bears a resemblance to the quantum formalism. The present findings may be of interest to researchers working on foundations of quantum mechanics, particularly for ψ-epistemic interpretations. More practically, there may be applications in the fields of precision measurement, nanoengineering, and molecular machines.

Experimental and theoretical investigations into the surface chemical properties and separation of serpentine from quartz using xanthomonas campestris as a selective flocculant

Separation of fine serpentine (SPT) from quartz (QZ) both of d80 close to 20 µm using an eco-friendly microbial exo-polysaccharide, xanthomonas campestris (XCT), as a selective flocculant for SPT was conducted experimentally and substantiated theoretically. The adsorption of XCT onto SPT was observed to decrease with increase in pH, whereas that of QZ was nearly nil beyond pH 2.1. Zeta potential of SPT in presence of XCT decreased with increase in pH further attesting to the adsorption and anionicity of XCT. The FTIR studies confirmed the interaction of XCT with SPT in presence of sodium hexametaphosphate. The nature of intermolecular interactions present in complexes formed on SPT surface was revealed by quantum theory of atoms in molecules to be non-covalent. The electron density difference plot conducted on formed complexes indicated that electrons drifted from XCT to the surface of SPT. Selective flocculation SPT-QZ (1:1) mixture conducted at pH 6 and pH 7.5 in presence of 4 mg/L and 2 mg/L of sodium hexametaphosphate coupled with 100 mg/L of XCT yielded separation efficiency and selectivity ratio of 96.5 % and 71.2, respectively, after three desliming stages. Therefore, XCT is a potential selective flocculant for serpentine.

Effect of dipolar state on J-type aggregation of acceptor group modified pyrene-based push-pull systems

The present work demonstrates the ground and excited state aggregation behavior of two pyrene-based push–pull systems (Pyr-MC and Pyr-PyA) both in solid and solution state. The UV–Vis spectra of these molecules show a unique broaden spectral pattern at lower energy region (400–600 nm) in both H2O and solid state. Further, along with the local (intense) emission band, a new (less intense) band is appeared at higher wavelength region (∼550 nm) in water, which is due to the formation of aggregates. Interestingly, it is the lowest energy emission out of all previously reported emission by pyrene derivatives. The experimental results suggest the formation of J-type aggregation in solid and solution. The average lifetime of these molecules is also measured in different solvents. Intriguingly, the ground/excited state J-type aggregation in solid and solution are similar in nature in spite of different mode of intermolecular interactions, and are supported by experimental results. The dipolar state plays an important role on the J-type aggregation process. The QTAIM (quantum theory of atom in molecule) theoretical framework is applied to analyze and understand the properties of molecules in terms of the distribution of electrons and the topological features of the electron density within a molecule. Importantly, bond paths provide information about the nature of chemical bonds, including their strength and directionality.

Recurrent Supramolecular Patterns in a Series of Salts of Heterocyclic Polyamines and Heterocyclic Dicarboxylic Acids: Synthesis, Single-Crystal X-ray Structure, Hirshfeld Surface Analysis, Energy Framework, and Quantum Chemical Calculations

A series of novel salts based on aromatic polyamines and 2,3-pyrazinedicarboxylic acid, such as C10H12N6O5 (1), C10H9ClN6O4 (2), C11H10N8O4 (3), and C14H17N16O5.5 (4) or 3,4-thiophenedicarboxylic acid, such as C10H10N4O4S (5), C10H9ClN4O4S (6), and C10H10N4O4S2 (7), were synthesized and characterized by single-crystal X-ray diffraction. All compounds crystallize in a monoclinic space group. The structure was subjected to complex Hirshfeld surface analysis, molecular electrostatic potential, enrichment ratio, and energy framework calculations. The influence of different cations on the packing of 3-carboxypyrazine-2-carboxylate and 4-carboxythiophene-3-carboxylate anions in the crystal lattice was studied. O…H/H…O interactions are the main contributor in all crystals. In addition, in a series of pyrazine-containing structures, N(C)…H/H…N(C) interactions have relevance, while in a series of thiophene-based compounds, C…H/H…C and S…H(O)/H(O)…S. In addition, Cl-based interactions are observed in compound 2. According to the enrichment ratio calculations, O…H/H…O and C…C are the most preferable interactions in all structures. The energy frameworks are dominated by the dispersive contribution, only in compound 3 is the electrostatic term dominant. The analyzed structures reveal intra- and intermolecular recurrent supramolecular synthons. In both series of crystals, the robust H-bonded centrosymmetric dimer R22(8) as homo- or as heterosynthon (in compounds 2, 3, 6, and 7) and the intramolecular synthon S(7) generated by O-H…O interactions (in compounds 2, 6, and 7) are present. The supramolecular patterns formed by π…π (C…C) and C-O(Cl,S)…C are also noticeable. Notably, a dual synthon linking the supramolecular chain via π…π interactions and the homosynthon R22(8) via N-H…N interactions is visible in both series of new salts. A library of H-bonding motifs at diverse levels of supramolecular architecture is provided. We extended the analysis of intramolecular H-bonding motifs to similar structures deposited in the Cambridge Structural Database. Another important feature is the existence of an intramolecular O…H…O bridge between two neighboring carboxylic groups as substituents in anions in compounds 3 and 5. In this context, we performed quantum theory of atoms-in-molecule calculations to reveal more details.