Exchange-correlation effects in interatomic energies for pure density functionals and their application to the molecular energy prediction.

In this proof-of-concept paper, we show how exchange-correlation effects can be simply recovered for interatomic energies within the interacting quantum atoms decomposition when local, gradient generalized, or meta-gradient generalized approximations are used in density functional theory (DFT) calculations. We also demonstrate how inhomogeneity and non-local effects can be introduced even from a pure local scheme, without resorting to any orbital information. Finally, we provide numerical evidence on a database of selected energetic molecules that this decomposition scheme can be efficiently used to build accurate models for the prediction of molecular energies from an initial "cheap" DFT calculation.

Does Aromaticity Play a Role in Electronic and Structural Properties of YBn (n=2-14) Clusters?

Nanoclusters exhibit electronic, optical, and magnetic properties that differ significantly from those of extended and molecular systems with comparable stoichiometries. In this work, we examined the structural, energetic, and electronic characteristics of yttrium-doped boron clusters (YBn,  n =2-14) with robust wavefunction analysis tools. Special emphasis is placed on the elucidation of the potential aromatic character exhibited by the resultant molecules and how it can affect their chemical bonding and stability. Our results revealed that the YBn stability is governed by the maximization of the ionic Y-B interactions. This is evidenced from the lowest-energy conformations, which manifest as half-sandwich structures wherein the majority of boron atoms are bonded to yttrium. The stabilization of such chemical contacts comes at the expense of a notorious depletion of the Y local electron density, crystallizing in a considerable ionic character, close to Y2+ + Bn2-. Such a  charge transfer is coupled to the enhancement of the electron delocalization within the YBn lattice, resulting in quite remarkable local and global aromatic characters. Altogether, this study shows how the toolkit of real space chemical bonding descriptors can offer valuable insights into the structural and electronic properties,  of YBn clusters, contributing to a better understanding of their behavior.

Non-separability, locality and criteria of reality: a reply to Waegell and McQueen.

Using a 'reformulation of Bell's theorem', Waegell and McQueen, (2020) argue that any local theory which does not involve retro-causation or fine-tuning must be a many-worlds theory. Moreover they argue that non-separable many-worlds theories whose ontology is given by the wavefunction involve superluminal causation, as opposed to separable many-worlds theories (e.g. Waegell, 2021; Deutsch and Hayden 2000). I put forward three claims. (A) I challenge their argument for relying on a non-trivial, unquestioned assumption about elements of reality which allows Healey's approach (Healey, 2017b) to evade their claim. In an attempt to respond to (A), Waegell and McQueen may restrict their claim to theories which satisfy such an assumption, however, I also argue that (B) their argument fails to prove even the so weakened claim, as exemplified by theories that are both non-separable and local. Finally, (C) by arguing for the locality of the decoherence-based Everettian approach (Wallace, 2012) I refute Waegell and McQueen's claim that wavefunction-based ontologies, and more generally non-separable ontologies, involve superluminal causation. I close with some doubtful remarks about separable Everettian interpretations as compared to non-separable ones.

Determining the Factors Accounting for Reaction Selectivity: A Relative Energy Gradient - Interacting Quantum Atoms and Natural Bonding Orbitals Study.

Identifying the main physicochemical properties accounting for the course of a reaction is of utmost importance to rationalize chemical syntheses. To this aim, the relative energy gradient (REG) method is an appealing approach because it is an unbiased and automatic process to extract the most relevant pieces of energy information. Initially formulated within the interacting quantum atoms (IQA) framework for a single reaction, here we extend the REG method to natural bond orbitals (NBO) analysis and to the case of two competitive processes. This development enables the determination of the driving forces of any chemical selectivity. We illustrate the extended REG method on the case study of ring opening in cyclobutenes, which is an important instance of the so-called torquoselectivity.

Quantumness speeds up quantum thermodynamics processes.

Quantum thermodynamic process involves manipulating and controlling quantum states to extract energy or perform computational tasks with high efficiency. There is still no efficient general method to theoretically quantify the effect of the quantumness of coherence and entanglement in work extraction. In this work, we propose a thermodynamics speed to quantify the extracting work. We show that the coherence of quantum systems can speed up work extracting with respect to some cyclic evolution beyond all incoherent states. We further show the genuine entanglement of quantum systems may speed up work extracting beyond any bi-separable states. This provides a new thermodynamic method to witness entangled systems with physical quantities.

Exploring the Efficiency of Algerian Kaolinite Clay in the Adsorption of Cr(III) from Aqueous Solutions: Experimental and Computational Insights.

The current study comprehensively investigates the adsorption behavior of chromium (Cr(III)) in wastewater using Algerian kaolinite clay. The structural and textural properties of the kaolinite clay are extensively characterized through a range of analytical methods, including XRD, FTIR, SEM-EDS, XPS, laser granulometry, N2 adsorption isotherm, and TGA-DTA. The point of zero charge and zeta potential are also assessed. Chromium adsorption reached equilibrium within five minutes, achieving a maximum removal rate of 99% at pH 5. Adsorption equilibrium is modeled using the Langmuir, Freundlich, Temkin, Elovich, and Dubinin-Radushkevitch equations, with the Langmuir isotherm accurately describing the adsorption process and yielding a maximum adsorption capacity of 8.422 mg/g for Cr(III). Thermodynamic parameters suggest the spontaneous and endothermic nature of Cr(III) sorption, with an activation energy of 26.665 kJ/mol, indicating the importance of diffusion in the sorption process. Furthermore, advanced DFT computations, including COSMO-RS, molecular orbitals, IGM, RDG, and QTAIM analyses, are conducted to elucidate the nature of adsorption, revealing strong binding interactions between Cr(III) ions and the kaolinite surface. The integration of theoretical and experimental data not only enhances the understanding of Cr(III) removal using kaolinite but also demonstrates the effectiveness of this clay adsorbent for wastewater treatment. Furthermore, this study highlights the synergistic application of empirical research and computational modeling in elucidating complex adsorption processes.

Chemical bonding in phase-change chalcogenides.

Almost all phase-change memory materials (PCM) contain chalcogen atoms, and their chemical bonds have been denoted both as 'electron-deficient' [sometimes referred to as 'metavalent'] and 'electron-rich' ['hypervalent', multicentre]. The latter involve lone-pair electrons. We have performed calculations that can discriminate unambiguously between these two classes of bond and have shown that PCM have electron-rich, 3c-4e ('hypervalent') bonds. Plots of charge transferred between (ET) and shared with (ES) neighbouring atoms cannot on their own distinguish between 'metavalent' and 'hypervalent' bonds, both of which involve single-electron bonds. PCM do not exhibit 'metavalent' bonding and are not electron-deficient; the bonding is electron-rich of the 'hypervalent' or multicentre type.

Two-color electromagnetically induced transparency generated slow light in double-mechanical-mode coupling carbon nanotube resonators.

We theoretically propose a multiple-mode-coupling hybrid quantum system comprising two-mode-coupling nanomechanical carbon nanotube (CNT) resonators realized by a phase-dependent phonon-exchange interaction interacting with the same nitrogen-vacancy (NV) center in diamond. We investigate the coherent optical responses of the NV center under the condition of resonance and detuning. In particular, two-color electromagnetically induced transparency (EIT) can be achieved by controlling the system parameters and coupling regimes. Combining the spin-phonon interactions and phonon-phonon coupling with the modulation phase, the switching of one and two EIT windows has been demonstrated, which generates a light delay or advance. The slow-to-fast and fast-to-slow light transitions have been studied in different coupling regimes, and the switch between slow and fast light can be controlled periodically by tuning the modulation phase. The study can be applied to phonon-mediated optical information storage or information processing with spin qubits based on multiple-mode hybrid quantum systems.

A theoretical study on 1H-indole-2,3-dione complexes with lithium, sodium, and potassium cations.

CONTEXT: A comparative study of the change in different properties of electronic and structural of the free 1H-indole-2,3-dione molecule and its complexes has been obtained. HOMA analysis was performed to investigate the effects of lithium sodium and potassium cations on the aromaticity of lithium sodium and potassium complexes of 1H-indole-2,3-dione. METHODS: Several 1H-indole-2,3-dione complexes with lithium, sodium, and potassium cations were optimized at the B3LYP/6-311G(d,p) level. The cation and π interaction has been investigated from different aspects, including interaction energy calculations, charge transfer values, and changes in the aromaticity of the ring upon complexation. The charge transfer and natural population analysis for the complexes were performed with the natural bond orbital (NBO) analysis. The properties of bond critical points in complexes were studied by applying the quantum theory of atoms in molecules (QTAIM). Finally, the aromaticity change of phenyl induced upon complex formation was evaluated by applying the harmonic oscillator model of aromaticity (HOMA). [Li-INa]+ and [[Li-INb]+ were optimized with the wB97XD function using a version of Grimme's D2 dispersion model, and the absorption energy was compared with the calculation made with the B3LYP functional.

Secure image encryption algorithm using chaos-based block permutation and weighted bit planes chain diffusion.

Aiming at the problem of insufficient security of image encryption technology, a secure image encryption algorithm using chaos-based block permutation and weighted bit planes chain diffusion is proposed, which is based on a variant structure of classical permutation-diffusion. During the permutation phase, the encryption operations of dividing an image into sub-block, block scrambling, block rotation and block inversion, negative-positive transformation, color component shuffling are performed sequentially with chaotic sequences of plaintext association. In the chain diffusion stage, different encryption strategies are adopted for the high and low 4-bit planes according to the weight of image information. Theoretical analyses and empirical results substantiate that the algorithm conforms to the cryptographic requirements of confusion, diffusion, and avalanche effects, while possessing excellent numerical statistical properties with a large cryptographic space. Therefore, the cryptanalysis-propelled security enhancement mechanism proposed in this paper effectively amplifies the aptitude of the algorithm to withstand cryptographic attacks.

Theoretical Insights into Bifurcated Intramolecular Dihydrogen Bonds.

Two-ring intramolecular π-electron delocalization assisted dihydrogen bonds existing in (1Z,4Z)-1,4-dipentene-3-bora-1,5-diol and its symmetrically substituted derivatives have been analysed here since the MP2/6-311++G(d,p) calculations on these systems were performed. The influence of the coexistence of two intramolecular dihydrogen bonded rings in these molecular structures on properties of intramolecular dihydrogen bonds as well as on the π-electron delocalization within these rings was investigated. The comparison with corresponding structures of typical two-ring, so-called resonance-assisted, RAHB, systems was performed. The results of calculations show that such rings' coexistence leads to the weakening of dihydrogen bonds, similarly as for the typical two-ring RAHB systems. The Quantum Theory of ''Atoms in Molecules'' (QTAIM) was also applied here to get more details about the nature of dihydrogen bonds. Correlations between dihydrogen bond strength measures and other energetic, geometrical and topological parameters were also analysed. It was found that characteristics of bond critical points as well as of ring critical points are useful to estimate the strength of intramolecular dihydrogen bonds in two-ring dihydrogen bonded systems discussed here. The Natural Bond Orbital, NBO, approach parameters are also discussed as useful ones to describe properties of dihydrogen bonded systems.

Response of the mechanical and chiral character of ethane to ultra-fast laser pulses.

A pair of simulated left and right circularly polarized ultra-fast laser pulses of duration 20 femtoseconds that induce a mixture of excited states are applied to ethane. The response of the electron dynamics is investigated within the next generation quantum theory of atoms in molecules (NG-QTAIM) using third-generation eigenvector-trajectories which are introduced in this work. This enables an analysis of the mechanical and chiral properties of the electron dynamics of ethane without needing to subject the C-C bond to external torsions as was the case for second-generation eigenvector-trajectories. The mechanical properties, in particular, the bond-flexing and bond-torsion were found to increase depending on the plane of the applied laser pulses. The bond-flexing and bond-torsion, depending on the plane of polarization, increases or decreases after the laser pulses are switched off. This is explainable in terms of directionally-dependent effects of the long-lasting superpositions of excited states. The chiral properties correspond to the ethane molecule being classified as formally achiral consistent with previous NG-QTAIM investigations. Future planned investigations using ultra-fast circularly polarized lasers are briefly discussed.

Implementation of machine learning protocols to predict the hydrolysis reaction properties of organophosphorus substrates using descriptors of electron density topology.

Prediction of catalytic reaction efficiency is one of the most intriguing and challenging applications of machine learning (ML) algorithms in chemistry. In this study, we demonstrated a strategy for utilizing ML protocols applied to Quantum Theory of Atoms In Molecules (QTAIM) parameters to predict the ability of the A17 L47K catalytic antibody to covalently capture organophosphate pesticides. We found that the novel "composite" DFT functional B97-3c could be effectively employed for fast and accurate initial geometry optimization, aligning well with the input dataset creation. QTAIM descriptors proved to be well-established in describing the examined dataset using density-based and hierarchical clustering algorithms. The obtained clusters exhibited correlations with the chemical classes of the input compounds. The precise physical interpretation of the QTAIM properties simplifies the explanation of feature impact for both supervised and unsupervised ML protocols. It also enables acceleration in the search for entries with desired properties within large databases. Furthermore, our findings indicated that Ridge Regression with Laplacian kernel and CatBoost Regressor algorithms demonstrated suitable performance in handling small datasets with non-trivial dependencies. They were able to predict the actual reaction barrier values with a high level of accuracy. Additionally, the CatBoost Classifier proved reliable in discriminating between "active" and "inactive" compounds.

Aza-Michael Addition in Explicit Solvent: A Relative Energy Gradient-Interacting Quantum Atoms Study.

Aza-Michael additions are key reactions in organic synthesis. We investigate, from a theoretical and computational point of view, several examples ranging from weak to strong electrophiles in dimethylsulfoxide treated as explicit solvent. We use the REG-IQA method, which is a quantum topological energy decomposition (Interacting Quantum Atoms, IQA) coupled to a chemical-interpretation calculator (Relative Energy Gradient, REG). We focus on the rate-limiting addition step in order to unravel the different events taking place in this step, and understand the influence of solvent on the reaction, with an eye on predicting the Mayr electrophilicity. For the first time, a link is established between an REG-IQA analysis and experimental values.

Theoretical investigation of anion perfluorocubane.

CONTEXT: In this work, we did a theoretical exploration of C8F8 (Ib) and its anion radical analogue (IIb) in this work. By investigating the thermochemistry of electron capture, we find that the free energy associated with the conversion of C8H8 (Ia) into its anion radical analogue IIa is of the order of + 92.83 kcal.mol-1, while the conversion of Ib into IIb is - 6.42 kcal.mol-1. Therefore, species IIb is thermodynamically more stable than its neutral analogue. Natural bond orbitals (NBO) analyses revealed that compound Ib exhibits a relative electronic stability as a function of intramolecular delocalisations of the type [Formula: see text] of the order of 2.70 kcal.mol-1. Similar delocalizations for Ia are energetically lower (1.45 kcal.mol-1). Topological analyses of compounds Ib and IIb indicate that the addition of an electron to Ib enhances the covalency of the C-C bond, as can be seen by the reduction in the ellipticity of the C-C bond. The opposite is observed for Ia, whose addition of the electron (leading to IIa) reduces the covalency of the C-C bond. By comparing the free and packaged forms of the species, it is found that, in the crystalline form, the system will present greater relative stability due to the dispersive interactions involved, as evidenced by non-covalent interactions (NCI) analysis. Finally, it was possible to verify that the manifestation of the current density with a lower paratropic and less antiaromatic character in Ib and IIb point to C8F8 as a strong candidate for electron capture. METHODS: Geometry optimization calculations were carried out, for all monomer structures using the hybrid functional B3LYP-D3 and the 6-31+G(d,p) basis set. To determine the formation thermochemistry of the ions, electronic energy corrections was performed using the DLPNO-CCSD(T)/aug-cc-pVTZ/C method. Starting from the optimised forms, shielding, nuclear magnetic resonance (NMR) spectra employing gauge-independent atomic orbital (GIAO), and NBO calculations were performed for these monomers, using the PBE0 functional and the pCSseg-2 atomic basis set. The magnetochemical analysis of ring currents was performed using the GIMIC formalism. For the topological analysis, it was applied the combination DLPNO-CCSD(T)/aug-cc-pVTZ/C, previously used for correcting the electronic energy.

Quantum theory only makes sense in Lazare Carnot's participatory engineering thermodynamics, a development of Leibniz's dynamics.

Feynman insisted 'no one understands quantum theory'. Yet, experimentalists tell us quantum theory is the most successful theory in history. Quantum theory cannot be understood as a classical mechanical theory since it arose through the 'interpolation' of two highly successful but complementary classical mechanics: Newtonian particle mechanics and Maxwellian wave mechanics. The two-slit experiment illustrates that what is experienced depends on choice of experimental set-up. Quantum theory is properly understood within the more general framework of engineering thermodynamics. In Part One, I point to four essential characteristics of quantum theory that cannot be understood in any framework defined by the classical mechanical presuppositions of symmetry and conservation. These four characteristics are the participatory, the complementary, the indeterminate and the new non-commutative geometry. In Part Two, articulating engineering thermodynamics, I note there are two histories and two formulations of thermodynamics: Carnot's engineering thermodynamics and the 'rational mechanical' tradition of Clausius-Boltzmann. These four essential characteristics of quantum theory are also characteristics of engineering thermodynamics. In Part Three, I trace the precursors of Lazare Carnot's engineering thermodynamics to earlier insights of Huygens, d'Alembert, Leibniz and the Bernoullis. Leibniz brought these forth in his meta-paradigm shift from Statics to Dynamics. This article is part of the theme issue 'Thermodynamics 2.0: Bridging the natural and social sciences (Part 2)'.

Ga···C Triel Bonds-Why They Are Not Strong Enough to Change Trigonal Configuration into Tetrahedral One: DFT Calculations on Dimers That Occur in Crystal Structures.

Structures characterized by the trigonal coordination of the gallium center that interacts with electron rich carbon sites are described. These interactions may be classified as Ga···C triel bonds. Their properties are analyzed in this study since these interactions may be important in numerous chemical processes including catalytical activities; additionally, geometrical parameters of corresponding species are described. The Ga···C triel bonds discussed here, categorized also as the π-hole bonds, do not change the trigonal configuration of the gallium center into the tetrahedral one despite total interactions in dimers being strong; however, the main contribution to the stabilization of corresponding structures comes from the electrostatic forces. The systems analyzed theoretically here come from crystal structures since the Cambridge Structural Database, CSD, search was performed to find structures where the gallium center linked to CC bonds of Lewis base units occurs. The majority structures found in CSD are characterized by parallel, stacking-like arrangements of species containing the Ga-centers. The theoretical results show that interactions within dimers are not classified as the three-centers links as in a case of typical hydrogen bonds and numerous other interactions. The total interactions in dimers analyzed here consist of several local intermolecular atom-atom interactions; these are mainly the Ga···C links. The DFT results are supported in this study by calculations with the use of the quantum theory of atoms in molecules, QTAIM, the natural bond orbital, NBO, and the energy decomposition analysis, EDA, approaches.

The quantum foundations of utility and value.

This work presents a generalization of game theory and new perspectives on utility and value. Using quantum formalism, we prove that classical game theory is a special case of quantum game theory. We show that the von Neumann entropy and von Neumann-Morgenstern utility are equivalent and that the Hamiltonian operator represents value. This article is part of the theme issue 'Thermodynamics 2.0: Bridging the natural and social sciences (Part 1)'.

On Geometry of p-Adic Coherent States and Mutually Unbiased Bases.

This paper considers coherent states for the representation of Weyl commutation relations over a field of p-adic numbers. A geometric object, a lattice in vector space over a field of p-adic numbers, corresponds to the family of coherent states. It is proven that the bases of coherent states corresponding to different lattices are mutually unbiased, and that the operators defining the quantization of symplectic dynamics are Hadamard operators.

Electronic and dynamical properties of non-covalent diatomic aggregates formed by He with neutral and ionic Li and Be.

CONTEXT AND RESULTS: This work aims to study the influence of the absence and presence of permanent charges on the electronic and dynamical properties of the non-covalent bound diatomic systems involving He and Li, Be as neutral and ionic partners. The charge displacement results suggest that in the formation of HeLi[Formula: see text], HeBe[Formula: see text], and HeBe[Formula: see text], the neutral He atom undergoes, in the electric field of the ion, a pronounced electronic polarization, and the natural bond order theoretical approach indicates that in the formation of the molecular orbital He acts as a weak electron donor. The energy decomposition analysis provides the dispersion and induction components as the attractive leading terms controlling the stability of all systems, confirming that the formed bond substantially maintains a non-covalent nature which is also supported by the Quantum Theory of Atoms in Molecules (QTAIM) analysis. Finally, it was found that the HeLi and HeBe neutral systems are unstable under any condition, HeLi[Formula: see text] and HeBe[Formula: see text] ionic systems are stable below 317K and 138K, respectively, while the HeBe[Formula: see text] system becomes unstable only after 3045K. COMPUTATIONAL AND THEORETICAL TECHNIQUES: The potential energy curves and interactions in all systems were studied theoretically based on coupled-cluster singles and doubles method with perturbative inclusion of triples CCSD(T) method with an aug-cc-pV5Z basis set. More precisely, it was determined the potential energy curves describing the stability of the HeLi, HeLi[Formula: see text], HeBe, HeBe[Formula: see text], and HeBe[Formula: see text] systems, the charge displacement within the formed adducts, the decomposition of their total interaction energy, the topological analysis of their bonds, their rovibrational energies, their spectroscopic constants and lifetimes.