Polyvalent s-block elements: A missing link challenges the periodic law of chemistry for the heavy elements.

The Periodic Law of Chemistry is one of the great discoveries in cultural history. Elements behaving chemically similar are empirically merged in groups G of a Periodic Table, each element with G valence electrons per neutral atom, and with upper limit G for the oxidation and valence numbers. Here, we report that among the usually mono- or di-valent s-block elements (G = 1 or 2), the heaviest members (87Fr, 88Ra, 119E, and 120E) with atomic numbers Z = 87, 88, 119, 120 form unusual 5- or 6-valent compounds at ambient conditions. Together with well-reported basic changes of valence at the end of the 6d-series, in the whole 7p-series, and for 5g6f-elements, it indicates that at the bottom of common Periodic Tables, the classic Periodic Law is not as straightforward as commonly expected. Specifically, we predict the feasible experimental synthesis of polyvalent [RaL-n] (n = 4, 6) compounds.

Generalized Foldy-Wouthuysen transformation for relativistic two-component methods: Systematic analysis of two-component Hamiltonians.

The generalized Foldy-Wouthuysen (GFW) transformation was proposed as a generic form that unifies four types of transformations in relativistic two-component methods: unnormalized GFW(UN), and normalized form 1, form 2, and form 3 (GFW(N1), GFW(N2), and GFW(N3)). The GFW transformation covers a wide range of transformations beyond the simple unitary transformation of the Dirac Hamiltonian, allowing for the systematic classification of all existing two-component methods. New two-component methods were also systematically derived based on the GFW transformation. These various two-component methods were applied to hydrogen-like and helium-like ions. Numerical errors in energy were evaluated and classified into four types: the one-electron Hamiltonian approximation, the two-electron operator approximation, the newly defined "picture difference error (PDE)," and the error in determining the transformation, and errors in multi-electron systems were discussed based on this classification.

Beyond Electrons: Correlation and Self-Energy in Multicomponent Density Functional Theory.

Post-Kohn-Sham methods are used to evaluate the ground-state correlation energy and the orbital self-energy of systems consisting of multiple flavors of different fermions. Starting from multicomponent density functional theory, suitable ways to arrive at the corresponding multicomponent random-phase approximation and the multicomponent Green's function G W ${GW}$ approximation, including relativistic effects, are outlined. Given the importance of both of this methods in the development of modern Kohn-Sham density functional approximations, this work will provide a foundation to design advanced multicomponent density functional approximations. Additionally, the G W ${GW}$ quasiparticle energies are needed to study light-matter interactions with the Bethe-Salpeter equation.

Chirality in electromagnetic radiation from relativistic electrons.

Electrons in circular motion emit electromagnetic radiation and lose their energy and angular momentum, both of which are carried away by the radiation field. Electromagnetic radiation from such electrons is not only circularly polarized but also, in general, possessing helical phase structure, the former of which corresponds to spin angular momentum and the latter orbital angular momentum. Based on the classical electrodynamics, we show that the chiral topological property related to the orbital angular momentum arises from deformation of the electromagnetic field due to the relativistic effect.

On the geometry dependence of the nuclear magnetic resonance chemical shift of mercury in thiolate complexes: A relativistic density functional theory study.

Thiolate containing mercury(II) complexes of the general formula [Hg(SR) n $$ {}_n $$ ] 2 - n $$ {}^{2-n} $$ have been of great interest since the toxicity of mercury was recognized. 199Hg nuclear magnetic resonance spectroscopy (NMR) is a powerful tool for characterization of mercury complexes. In this work, the Hg shielding constants in a series of [Hg(SR) n $$ {}_n $$ ] 2 - n $$ {}^{2-n} $$ complexes are therefore investigated computationally with particular emphasis on their geometry dependence. Geometry optimizations and NMR chemical shift calculations are performed at the density functional theory (DFT) level with both the zeroth-order regular approximation (ZORA) and four-component relativistic methods. The four exchange-correlation (XC) functionals PBE0, PBE, B3LYP, and BLYP are used in combination with either Dyall's Gaussian-type (GTO) or Slater-type orbitals (STOs) basis sets. Comparing ZORA and four-component calculations, one observes that the calculated shielding constants for a given molecular geometry have a constant difference of ∼ $$ \sim $$ 1070 ppm. This confirms that ZORA is an acceptable relativistic method to compute NMR chemical shifts. The combinations of four-component/PBE0/v3z and ZORA/PBE0/QZ4P are applied to explore the geometry dependence of the isotropic shielding. For a given coordination number, the distance between mercury and sulfur is the key factor affecting the shielding constant, while changes in bond and dihedral angles and even different side groups have relatively little impact.

Chemical characterization of heavy actinides and light transactinides - Experimental achievements at JAEA.

The chemical characterization of the heaviest elements at the farthest reach of the periodic table (PT) and the classification of these elements in the PT are undoubtedly crucial and challenging subjects in chemical and physical sciences. The elucidation of the influence of relativistic effects on their outermost electronic configuration is also a critical and fascinating aspect. However, the heaviest elements with atomic numbers Z ≳ 100 must be produced at accelerators using nuclear reactions of heavy ions and target materials. Therefore, production rates for these elements are low, and their half-lives are as short as a few seconds to a few minutes; they are usually available in a quantity of only a few atoms at a time. Here, we review some highlighted studies on heavy actinide and light transactinide chemical characterization performed at the Japan Atomic Energy Agency tandem accelerator facility. We discuss briefly the prospects for future studies of the heaviest elements.

Does the Differential Structure of Space-Time Follow from Physical Principles?

This article examines Wigner's view on the unreasonable effectiveness of mathematics in the natural sciences, which was based on Cantor's claim that 'mathematics is a free creation of the human mind'. It is contended that Cantor's claim is not relevant to physics because it was based on his power set construction, which does not preserve neighborhoods of geometrical points. It is pointed out that the physical notion of Einstein causality can be defined on a countably infinite point set M with no predefined mathematical structure on it, and this definition endows M with a Tychonoff topology. Under Shirota's theorem, M can therefore be embedded as a closed subspace of RJ for some J. While this suggests that the differentiable structure of RJ may follow from the principle of causality, the argument is constrained by the fact that the completion processes (analyzed here in some detail) required for the passage from QJ to RJ remain empirically untestable.

Theories of Relativistic Dissipative Fluid Dynamics.

Relativistic dissipative fluid dynamics finds widespread applications in high-energy nuclear physics and astrophysics. However, formulating a causal and stable theory of relativistic dissipative fluid dynamics is far from trivial; efforts to accomplish this reach back more than 50 years. In this review, we give an overview of the field and attempt a comparative assessment of (at least most of) the theories for relativistic dissipative fluid dynamics proposed until today and used in applications.

Effect of Longitudinal Fluctuations of 3D Weizsäcker-Williams Field on Pressure Isotropization of Glasma.

We investigate the effects of boost invariance breaking on the isotropization of pressure in the glasma, using a 3+1D glasma simulation. The breaking is attributed to spatial fluctuations in the classical color charge density along the collision axis. We present numerical results for pressure and energy density at mid-rapidity and across a wider rapidity region. It is found that, despite varying longitudinal correlation lengths, the behaviors of the pressure isotropizations are qualitatively similar. The numerical results suggest that, in the initial stage, longitudinal color electromagnetic fields develop, similar to those in the boost invariant glasma. Subsequently, these fields evolve into a dilute glasma, expanding longitudinally in a manner akin to a dilute gas. We also show that the energy density at mid-rapidity exhibits a 1/τ decay in the dilute glasma stage.

Relativistic Roots of κ-Entropy.

The axiomatic structure of the κ-statistcal theory is proven. In addition to the first three standard Khinchin-Shannon axioms of continuity, maximality, and expansibility, two further axioms are identified, namely the self-duality axiom and the scaling axiom. It is shown that both the κ-entropy and its special limiting case, the classical Boltzmann-Gibbs-Shannon entropy, follow unambiguously from the above new set of five axioms. It has been emphasized that the statistical theory that can be built from κ-entropy has a validity that goes beyond physics and can be used to treat physical, natural, or artificial complex systems. The physical origin of the self-duality and scaling axioms has been investigated and traced back to the first principles of relativistic physics, i.e., the Galileo relativity principle and the Einstein principle of the constancy of the speed of light. It has been shown that the κ-formalism, which emerges from the κ-entropy, can treat both simple (few-body) and complex (statistical) systems in a unified way. Relativistic statistical mechanics based on κ-entropy is shown that preserves the main features of classical statistical mechanics (kinetic theory, molecular chaos hypothesis, maximum entropy principle, thermodynamic stability, H-theorem, and Lesche stability). The answers that the κ-statistical theory gives to the more-than-a-century-old open problems of relativistic physics, such as how thermodynamic quantities like temperature and entropy vary with the speed of the reference frame, have been emphasized.

Relativistic Heat Conduction in the Large-Flux Regime.

We propose a general procedure for evaluating, directly from microphysics, the constitutive relations of heat-conducting fluids in regimes of large fluxes of heat. Our choice of hydrodynamic formalism is Carter's two-fluid theory, which happens to coincide with Öttinger's GENERIC theory for relativistic heat conduction. This is a natural framework, as it should correctly describe the relativistic "inertia of heat" as well as the subtle interplay between reversible and irreversible couplings. We provide two concrete applications of our procedure, where the constitutive relations are evaluated, respectively, from maximum entropy hydrodynamics and Chapman-Enskog theory.

The causal axioms of algebraic quantum field theory: A diagnostic.

Algebraic quantum field theory (AQFT) puts forward three "causal axioms" that aim to characterize the theory as one that implements relativistic causation: the spectrum condition, microcausality, and primitive causality. In this paper, I aim to show, in a minimally technical way, that none of them fully explains the notion of causation appropriate for AQFT because they only capture some of the desiderata for relativistic causation I state or because it is often unclear how each axiom implements its respective desideratum. After this diagnostic, I will show that a fourth condition, local primitive causality (LPC), fully characterizes relativistic causation in the sense of fulfilling all the relevant desiderata. However, it only encompasses the virtues of the other axioms because it is implied by them, as I will show from a construction by Haag and Schroer (1962). Since the conjunction of the three causal axioms implies LPC and other important results in QFT that LPC does not imply, and since LPC helps clarify some of the shortcomings of the three axioms, I advocate for a holistic interpretation of how the axioms characterize the causal structure of AQFT against the strategy in the literature to rivalize the axioms and privilege one among them.

Tipping the Balance Between the bcc and fcc Phase Within the Alkali and Coinage Metal Groups.

Why the Group 1 elements crystallize in the body-centered cubic (bcc) structure, and the iso-electronic Group 11 elements in the face-centered cubic (fcc) structure, remains a mystery. Here we show that a delicate interplay between many-body effects, vibrational contributions and dispersion interactions obtained from relativistic density functional theory offers an answer to this long-standing controversy. It also sheds light on the Periodic Table of Crystal Structures. A smooth diffusionless transition through cuboidal lattices gives a detailed insight into the bcc→fcc phase transition for the Groups 1 and 11 elements.

Bismuth as a Z-Type Ligand: an Unsupported Pt-Bi Donor-Acceptor Interaction and its Umpolung by Reaction with H2.

Establishing unprecedented types of bonding interactions is one of the fundamental challenges in synthetic chemistry, paving the way to new (electronic) structures, physicochemical properties, and reactivity. In this context, unsupported element-element interactions are particularly noteworthy since they offer pristine scientific information about the newly identified structural motif. Here we report the synthesis, isolation, and full characterization of the heterobimetallic Bi / Pt compound [Pt(PCy3)2(BiMe2)(SbF6)] (1), bearing the first unsupported transition metal→bismuth donor/acceptor interaction as its key structural motif. 1 is surprisingly robust, its electronic spectra are interpreted in a fully relativistic approach, and it reveals an unprecedented reactivity towards H2.

Computational NMR spectroscopy of 205 Tl.

We have investigated the NMR chemical shift of 205 Tl in several thallium compounds, ranging from small covalent Tl(I) and Tl(III) molecules to supramolecular complexes with large organic ligands and some thallium halides. NMR calculations were run at the ZORA relativistic level, with and without spin-orbit coupling using few selected GGA and hybrid functionals, namely BP86, PBE, B3LYP, and PBE0. We also tested solvent effects both at the optimization level and at the NMR calculation step. At the ZORA-SO-PBE0 (COSMO) level of theory we find a very good performance of the computational protocol that allows to discard or retain possible structures/conformations based on the agreement between the calculated chemical shift and the experimental value.

Relativistic adapted Gaussian basis sets free of variational prolapse of small and medium size for cesium through radon.

Relativistic adapted Gaussian basis sets of small and medium sizes are presented in this study for all elements from cesium to radon, including some alternative electron configurations. Both basis sets are made free of variational prolapse, being developed by means of a polynomial version of the generator coordinate Dirac-Fock method. In addition, these sets were designed to be promptly used with two popular finite nuclear models, uniform sphere and Gaussian nuclei. The largest basis set errors found with the uniform sphere nucleus are 27.3 and 10.6 mHartree, respectively, for the small- and medium-size sets. The largest basis set errors obtained with the Gaussian nuclear model are smaller, reaching 23.2 and 7.1 mHartree for the small- and medium-size sets, respectively. Soon, these basis sets will be augmented with polarization functions to be properly used in molecular calculations.

Solvent effects in four-component relativistic electronic structure theory based on the reference interaction-site model.

A combined method of the Dirac-Hartree-Fock (DHF) method and the reference interaction-site model (RISM) theory is reported; this is the initial implementation of the coupling of the four-component relativistic electronic structure theory and an integral equation theory of molecular liquids. In the method, the DHF and RISM equations are solved self-consistently, and therefore the electronic structure of the solute, including relativistic effects, and the solvation structure are determined simultaneously. The formulation is constructed based on the variational principle with respect to the Helmholtz energy, and analytic free energy gradients are also derived using the variational property. The method is applied to the iodine ion (I- ), methyl iodide (CH3 I), and hydrogen chalcogenide (H2 X, where X = O-Po) in aqueous solutions, and the electronic structures of the solutes, as well as the solvation free energies and their component analysis, solvent distributions, and solute-solvent interactions, are discussed.

Toward a correct treatment of core properties with local hybrid functionals.

In local hybrid functionals (LHs), a local mixing function (LMF) determines the position-dependent exact-exchange admixture. We report new LHs that focus on an improvement of the LMF in the core region while retaining or partly improving upon the high accuracy in the valence region exhibited by the LH20t functional. The suggested new pt-LMFs are based on a Padé form and modify the previously used ratio between von Weizsäcker and Kohn-Sham local kinetic energies by different powers of the density to enable flexibly improved approximations to the correct high-density and iso-orbital limits relevant for the innermost core region. Using TDDFT calculations for a set of K-shell core excitations of second- and third-period systems including accurate state-of-the-art relativistic orbital corrections, the core part of the LMF is optimized, while the valence part is optimized as previously reported for test sets of atomization energies and reaction barriers (Haasler et al., J Chem Theory Comput 2020, 16, 5645). The LHs are completed by a calibration function that minimizes spurious nondynamical correlation effects caused by the gauge ambiguities of exchange-energy densities, as well as by B95c meta-GGA correlation. The resulting LH23pt functional relates to the previous LH20t functional but specifically improves upon the core region.

Realistic nuclear charge distribution model function for analytic nuclear attraction integrals in Gaussian basis functions.

In electronic structure theory, the charge distribution of a nucleus is usually approximated by point charge, Gaussian function, or homogeneously charged sphere, because they have an analytical nuclear attraction integral (NAI) formula. However, these functions do not always provide good approximations for nuclei with large mass number. The two-parameter Fermi (2pF) distribution and more realistic distributions describe well even nuclei with large mass number but do not have analytical NAI formulas. We propose a new function model called augmented Gaussian 12 (AG12), which has sufficient number of parameters and analytical NAI formulas. With the proposed fitting scheme, the AG12 charge distribution model optimally reproduces 2pF and the more realistic charge distributions. Moreover, AG12 fitted to 2pF model reproduces the energy difference of hydrogen-like ions well between the Gaussian distribution and 2pF models. Calculations using AG12 also suggested necessity to use more realistic nuclear charge distributions than 2pF.

Toward ICP-SIFT mass spectrometry and atomic cation ligation as a probe of relativistic effects-A personal journey.

The ICP-SIFT mass spectrometer at York University, a derivative of flowing afterglow (FA) and selected-ion flow tube (SIFT) mass spectrometers, has provided a powerful technique to measure the chemistry and kinetics of atomic cation-molecule reactions. Here, I focus on periodic trends in the kinetics of ligation reactions of atomic ions with small molecules. I examine trends in ammonia ligation kinetics across the first two rows of the atomic transition metal cations and their correlation with ligand bond enthalpies and ligand field stabilization energies. Also explored are trends down Groups 1 and 2 in the kinetics of noncovalent electrostatic ligand bonding and the tendency for s electron solvation of the atomic alkaline-earth cations with ammonia. Finally, I briefly review trends observed with 12 different ligands in the ligation rate down the periodic table with Group 9-12 transition atomic metal cations. These trends provide a compelling probe for the presence of relativistic effects that influence the strengths of the metal-ion ligand bonds that are formed. There is a clear third-row rate enhancement with Ir+ , Pt+ , Au+ , and Hg+ , the extent of which depends on the nature of the ligand. This large set of kinetic data provides an unprecedented broad perspective of relativistic effects in ligand bonding. With CS2 as a ligand, the third-row relativistic effect is apparent in the formation of both the first and the second ligand bond with the Groups 10 and 11 atomic cations as predicted by our quantum chemical calculations of ligation energies.