Optical Phenomena in Molecule-Based Magnetic Materials.

Since the last century, we have witnessed the development of molecular magnetism which deals with magnetic materials based on molecular species, i.e., organic radicals and metal complexes. Among them, the broadest attention was devoted to molecule-based ferro-/ferrimagnets, spin transition materials, including those exploring electron transfer, molecular nanomagnets, such as single-molecule magnets (SMMs), molecular qubits, and stimuli-responsive magnetic materials. Their physical properties open the application horizons in sensors, data storage, spintronics, and quantum computation. It was found that various optical phenomena, such as thermochromism, photoswitching of magnetic and optical characteristics, luminescence, nonlinear optical and chiroptical effects, as well as optical responsivity to external stimuli, can be implemented into molecule-based magnetic materials. Moreover, the fruitful interactions of these optical effects with magnetism in molecule-based materials can provide new physical cross-effects and multifunctionality, enriching the applications in optical, electronic, and magnetic devices. This Review aims to show the scope of optical phenomena generated in molecule-based magnetic materials, including the recent advances in such areas as high-temperature photomagnetism, optical thermometry utilizing SMMs, optical addressability of molecular qubits, magneto-chiral dichroism, and opto-magneto-electric multifunctionality. These findings are discussed in the context of the types of optical phenomena accessible for various classes of molecule-based magnetic materials.

Influence of O-H⋠⋠⋠Pt interactions on photoluminescent response in the (Et4N)2{[Pt(bph)(CN)2][phenylene-1,4-diresorcinol]} framework.

Tunable photoluminescence (PL) is one of the hot topics in current materials science, and research performed on the molecular phases is at the forefront of this field. We present the new (Et4N)2[PtII(bph)(CN)2]⋅rez3⋅1/3H2O (Pt2rez3) (bph=biphenyl-2,2'-diyl; rez3=3,3",5,5"-tetrahydroxy-1,1':4',1"-terphenyl, phenylene-1,4-diresorcinol coformer, a linear quaternary hydrogen bond donor) co-crystal salt based on the recently appointed promising [PtII(bph)(CN)2]2- luminophore. Within the extended hydrogen-bonded subnetwork [PtII(bph)(CN)2]2- complexes and rez3 coformer molecules form two types of contacts: the rez3O-H⋅⋅⋅Ncomplex ones in the equatorial plane of the complex and non-typical rez3O-H⋅⋅⋅Pt ones along its axial direction. The combined structural, PL, and DFT approach identified the rez3O-H⋅⋅⋅Pt synthons to be crucial in promoting the noticeable uniform redshift of bph ligand centered (LC) emission compared to the LC emission of the (Et4N)2[PtII(bph)(CN)2]⋅H2O (Pt2) precursor, owing to the direct interference of the phenol group with the PtII-bph orbital system via altering the CT processes within. The high-resolution emission spectra for Pt2 and Pt2rez3 were successfully reproduced at 77 K by using the Franck-Cordon expressions. The possibility to tune PL properties along the plausible continuum of rez3O-H⋅⋅⋅Pt synthons is indicated, considering various scenarios of molecular occupation of the space above and below the complex plane.

Tuning Crystal Packing and Magnetic Properties in a Series of [Dy12] Metallocubanes Based on Azobenzene Derivatives of Salicylic Acid.

A series of four new Dy12 dodecanuclear clusters based on azobenzene derivative ligands of salicylic acid (L1-L4) has been synthesized and characterized in the crystalline phase using X-ray diffraction on single crystal and powder, IR spectroscopy, elemental analysis, and DSC-TGA methods. It was revealed that all obtained clusters exhibit the formation of the similar metallic cluster nodes, as vertex-sharing heterocubanes, obtained from four Dy3+ cations, three bridging hydroxyl groups, and O atoms from the salicylic ligands. The coordination geometry around the Dy(III) centers has been carefully analyzed. Whereas Dy12-L1 and Dy12-L2 with L1 and L2 containing Me and OMe groups in para positions of the phenyl rings, respectively, form similar porous 3D diamond-like molecular networks due to CH-π interactions, for Dy12-L3 with L3 bearing NO2-electron-withdrawing group, the generation of 2D molecular grids assembled by π-π staking is observed, and for Dy12-L4 with L4 bearing phenyl substituent, 3D hexagonal channels have been generated. The complexes Dy12-L1, Dy12-L2, and Dy12-L3 exhibit a zero-field slow magnetic relaxation effect. After UV irradiation of Dy12-L1, a decrease of the magnetic anisotropy energy barrier displaying the possibility of control over magnetic properties by the external stimulus has been observed.

Quantum Chaos and Level Dynamics.

We review the application of level dynamics to spectra of quantally chaotic systems. We show that the statistical mechanics approach gives us predictions about level statistics intermediate between integrable and chaotic dynamics. Then we discuss in detail different statistical measures involving level dynamics, such as level avoided-crossing distributions, level slope distributions, or level curvature distributions. We show both the aspects of universality in these distributions and their limitations. We concentrate in some detail on measures imported from the quantum information approach such as the fidelity susceptibility, and more generally, geometric tensor matrix elements. The possible open problems are suggested.

Desolvation-Induced Highly Symmetrical Terbium(III) Single-Molecule Magnet Exhibiting Luminescent Self-Monitoring of Temperature.

A conjunction of Single-Molecule Magnet (SMM) behavior and luminescence thermometry is an emerging research line aiming at contactless read-out of temperature in future SMM-based devices. The shared working range between slow magnetic relaxation and the thermometric response is typically narrow or absent. We report TbIII -based emissive SMMs formed in a cyanido-bridged framework whose properties are governed by the reversible structural transformation from [TbIII (H2 O)2 ][CoIII (CN)6 ] ⋅ 2.7H2 O (1) to its dehydrated phase, TbIII [CoIII (CN)6 ] (2). The 8-coordinated complexes in 1 show the moderate SMM effect but it is enhanced for trigonal-prismatic TbIII complexes in 2, showing the SMM features up to 42 K. They are governed by the combination of QTM, Raman, and Orbach relaxation with the energy barrier of 594(18) cm-1 (854(26) K), one of the highest among the TbIII -based molecular nanomagnets. Both systems exhibit emission related to the f-f electronic transitions, with the temperature variations resulting in the optical thermometry below 100 K. The dehydration leads to a wide temperature overlap between the SMM behavior and thermometry, from 6 K to 42 K. These functionalities are further enriched after the magnetic dilution. The role of post-synthetic formation of high-symmetry TbIII complexes in achieving the SMM effect and hot-bands-based optical thermometry is discussed.

Phase Diagram of 1+1D Abelian-Higgs Model and Its Critical Point.

We determine the phase diagram of the Abelian-Higgs model in one spatial dimension and time (1+1D) on a lattice. We identify a line of first order phase transitions separating the Higgs region from the confined one. This line terminates in a quantum critical point above which the two regions are connected by a smooth crossover. We analyze the critical point and find compelling evidence for its description as the product of two noninteracting systems: a massless free fermion and a massless free boson. However, we find also some surprising results that cannot be explained by our simple picture, suggesting this newly discovered critical point is an unusual one.

Cold atoms meet lattice gauge theory.

The central idea of this review is to consider quantum field theory models relevant for particle physics and replace the fermionic matter in these models by a bosonic one. This is mostly motivated by the fact that bosons are more 'accessible' and easier to manipulate for experimentalists, but this 'substitution' also leads to new physics and novel phenomena. It allows us to gain new information about among other things confinement and the dynamics of the deconfinement transition. We will thus consider bosons in dynamical lattices corresponding to the bosonic Schwinger or [Formula: see text] Bose-Hubbard models. Another central idea of this review concerns atomic simulators of paradigmatic models of particle physics theory such as the Creutz-Hubbard ladder, or Gross-Neveu-Wilson and Wilson-Hubbard models. This article is not a general review of the rapidly growing field-it reviews activities related to quantum simulations for lattice field theories performed by the Quantum Optics Theory group at ICFO and their collaborators from 19 institutions all over the world. Finally, we will briefly describe our efforts to design experimentally friendly simulators of these and other models relevant for particle physics. This article is part of the theme issue 'Quantum technologies in particle physics'.

Shear wave elastography as a potential additional diagnostic tool in primary Sjögren's syndrome: an observational study.

The primary aim of this study was to verify if shear wave elastography can be used to evaluate salivary gland involvement in primary Sjögren's syndrome (pSS). The secondary objective was to establish an accurate cut-off value for parotid and submandibular salivary gland stiffness and to verify whether there are any distinctions among pSS patients with or without subjective mouth dryness. This prospective study included 45 patients with pSS (2016 ACR/EULAR classification criteria) and 108 healthy controls. All subjects underwent bilateral shear wave elastography of the parotid and submandibular salivary glands. Clinical data of pSS patients were collected and compared to elastography results. Patients with pSS had significantly higher shear wave elastography values for the parotid and submandibular salivary glands than the controls. There were no statistical differences in SWE values between patients with or without mouth dryness. The optimal cut-off value (mean value of 4 salivary glands shear wave elastography results) to distinguish patients with or without pSS was 13.19 kPa with sensitivity = 97.8% and specificity = 100.0%. It was, therefore, confirmed that shear wave elastography measurement of salivary glands has strong predictive ability in pSS detection (AUC 97.8%, 95% CI 93.4-100.0%). Shear wave elastography seems to be a promising, non-invasive and simple quantitative adjunct test to support the diagnosis of pSS with good sensitivity and specificity. More extensive prospective studies are needed to standardize a study protocol.

Supramolecular cis-"Bis(Chelation)" of [M(CN)6]3- (M = CrIII, FeIII, CoIII) by Phloroglucinol (H3PG).

Studies on molecular co-crystal type materials are important in the design and preparation of easy-to-absorb drugs, non-centrosymmetric, and chiral crystals for optical performance, liquid crystals, or plastic phases. From a fundamental point of view, such studies also provide useful information on various supramolecular synthons and molecular ordering, including metric parameters, molecular matching, energetical hierarchy, and combinatorial potential, appealing to the rational design of functional materials through structure-properties-application schemes. Co-crystal salts involving anionic d-metallate coordination complexes are moderately explored (compared to the generality of co-crystals), and in this context, we present a new series of isomorphous co-crystalline salts (PPh4)3[M(CN)6](H3PG)2·2MeCN (M = Cr, 1; Fe, 2; Co 3; H3PG = phloroglucinol, 1,3,5-trihydroxobenzene). In this study, 1-3 were characterized experimentally using SC XRD, Hirshfeld analysis, ESI-MS spectrometry, vibrational IR and Raman, 57Fe Mössbauer, electronic absorption UV-Vis-NIR, and photoluminescence spectroscopies, and theoretically with density functional theory calculations. The two-dimensional square grid-like hydrogen-bond {[M(CN)6]3-;(H3PG)2}∞ network features original {[M(CN)6]3-;(H3PG)4} supramolecular cis-bis(chelate) motifs involving: (i) two double cyclic hydrogen bond synthons M(-CN⋅⋅⋅HO-)2Ar, {[M(CN)6]3-;H2PGH}, between cis-oriented cyanido ligands of [M(CN)6]3- and resorcinol-like face of H3PG, and (ii) two single hydrogen bonds M-CN⋅⋅⋅HO-Ar, {[M(CN)6]3-;HPGH2}, involving the remaining two cyanide ligands. The occurrence of the above tectonic motif is discussed with regard to the relevant data existing in the CCDC database, including the multisite H-bond binding of [M(CN)6]3- by organic species, mononuclear coordination complexes, and polynuclear complexes. The physicochemical and computational characterization discloses notable spectral modifications under the regime of an extended hydrogen bond network.

Elastography as a possible useful method of assessment of skin involvement in systemic sclerosis.

Introduction: Scleroderma (Sc) is a connective tissue disorder associated with internal organ involvement, increased mortality, and unknown pathogenesis. It has been found that the more extensive the skin involvement the more severe internal organ manifestations and increased disability. The Rodnan skin score (RSS) is one of the established methods to examine skin thickness among patients with Sc. Due to RSS limitations, for instance, lack of detection of subclinical changes, a new tool is needed for the evaluation of Sc. In recent studies, shear wave elastography (SWE) has been examined as a potential tool to assess skin involvement through the evaluation of skin strain. Aim: To verify whether elastography is a reliable method to examine Sc progression and possibly provide one useful site to perform the examination - as an easy, cheap, and reliable examination tool. Material and methods: Forty Sc patients were examined, and 28 healthy individuals were recruited for the control group. Among the patients and control group, skin thickness was assessed using the RSS and skin strain measurements using elastography in 20 body locations. Results: SWE in the right-hand finger can be treated as an important diagnostic indicator of the severity of Sc. Conclusions: SWE is a reliable method for evaluating skin involvement among patients with systemic sclerosis (SSc). Right finger measurements correlate positively with Rodnan's results and can be a predictor of the severity of SSc. This study found SWE to be a reliable method for examining SSc progression and possibly one useful site for the examination.

Three-electron correlations in strong laser field ionization.

Strong field processes involving several active electrons reveal unambiguous dynamical signatures of the Pauli principle importance even in the nonrelativistic regime. We exemplify this statement studying three active electrons model atoms interacting with strong pulsed radiation, using an ab-initio time-dependent Schrödinger equation on a grid. In our restricted dimensionality model we are able to analyze momenta correlations of the three outgoing electrons using Dalitz plots. The different symmetries of the electronic wavefunctions, directly related to the initial state spin components, appear clearly visible.

Constraint-Induced Delocalization.

We study the impact of quenched disorder on the dynamics of locally constrained quantum spin chains, that describe 1D arrays of Rydberg atoms in both the frozen (Ising-type) and dressed (XY-type) regime. Performing large-scale numerical experiments, we observe no trace of many-body localization even at large disorder. Analyzing the role of quenched disorder terms in constrained systems we show that they act in two, distinct and competing ways: as an on-site disorder term for the basic excitations of the system, and as an interaction between excitations. The two contributions are of the same order, and as they compete (one towards localization, the other against it), one does never enter a truly strong disorder, weak interaction limit, where many-body localization occurs. Such a mechanism is further clarified in the case of XY-type constrained models: there, a term which would represent a bona fide local quenched disorder term acting on the excitations of the clean model must be written as a series of nonlocal terms in the unconstrained variables. Our observations provide a simple picture to interpret the role of quenched disorder that could be immediately extended to other constrained models or quenched gauge theories.

Solvent- and Temperature-Driven Photoluminescence Modulation in Porous Hofmann-Type SrII-ReV Metal-Organic Frameworks.

A unique family of three-dimensional (3D) luminescent SrII-ReV metal-organic frameworks (MOFs), {[SrII(MeOH)5][ReV(CN)4(N)(bpen)0.5]·MeOH}n [1·MeOH; N3- = nitrido ligand, bpen = 1,2-bis(4-pyridyl)ethane, and MeOH = methanol], {[SrII(MeOH)4][ReV(CN)4(N)(bpee)0.5]·2MeOH}n [2·MeOH; bpee = 1,2-bis(4-pyridyl)ethylene], and {[SrII(bpy)0.5(MeOH)2][ReV(CN)4(N)(bpy)0.5]}n (3·MeOH; bpy = 4,4'-bipyridine), is reported. They are obtained by the molecular self-assembly of Sr2+ ions with tetracyanidonitridorhenate(V) metalloligands, [ReV(CN)4(N)]2-, and pyridine-based organic spacers (L = bpen, bpee, bpy). Such a combination of molecular precursors results in bimetallic SrII-ReV cyanido-bridged layers further bonded by organic ligands into pillared Hofmann-type coordination skeletons. Because of the formation of {ReV-(L)-ReV} moieties providing emissive metal-to-ligand charge-transfer states, 1·MeOH-3·MeOH exhibit solid-state room-temperature photoluminescence tunable from green to orange by the applied organic ligand. The most stable MOF of 3·MeOH, based on the alternating {ReV-(bpy)-ReV} and {SrII-(bpy)-SrII} linkages, exhibits three interconvertible, variously solvated phases, methanol-solvated 3·MeOH, hydrated {[SrII(bpy)0.5(H2O)2][ReV(CN)4(N)(bpy)0.5]·0.6H2O}n (3·H2O), and desolvated {[SrII(bpy)0.5][ReV(CN)4(N)(bpy)0.5]}n (3). Their formation was correlated with water and methanol vapor sorption properties investigated for 3·H2O. The solvent content affects the luminescence mainly by tuning the emission energy within the series of 3·MeOH, 3·H2O, and 3. All of the obtained compounds exhibit temperature-driven modulation of luminescence, including the shift of the emission maximum and lifetime. The thermochromic luminescent response was found to be sensitive to the presence and type of solvent in the crystal lattice. This work shows that the construction of [ReV(CN)4(N)]2--based MOFs is an efficient route toward advanced solid luminophores tunable by external stimuli such as solvent or temperature.

A systematic construction of Gaussian basis sets for the description of laser field ionization and high-harmonic generation.

A precise understanding of mechanisms governing the dynamics of electrons in atoms and molecules subjected to intense laser fields has a key importance for the description of attosecond processes such as the high-harmonic generation and ionization. From the theoretical point of view, this is still a challenging task, as new approaches to solve the time-dependent Schrödinger equation with both good accuracy and efficiency are still emerging. Until recently, the purely numerical methods of real-time propagation of the wavefunction using finite grids have been frequently and successfully used to capture the electron dynamics in small one- or two-electron systems. However, as the main focus of attoscience shifts toward many-electron systems, such techniques are no longer effective and need to be replaced by more approximate but computationally efficient ones. In this paper, we explore the increasingly popular method of expanding the wavefunction of the examined system into a linear combination of atomic orbitals and present a novel systematic scheme for constructing an optimal Gaussian basis set suitable for the description of excited and continuum atomic or molecular states. We analyze the performance of the proposed basis sets by carrying out a series of time-dependent configuration interaction calculations for the hydrogen atom in fields of intensity varying from 5 × 1013 W/cm2 to 5 × 1014 W/cm2. We also compare the results with the data obtained using Gaussian basis sets proposed previously by other authors.

Octacyanidometallates for multifunctional molecule-based materials.

Octacyanidometallates have been successfully employed in the design of heterometallic coordination systems offering a spectacular range of desired physical properties with great potential for technological applications. The [M(CN)8]n- ions comprise a series of complexes of heavy transition metals in high oxidation states, including NbIV, MoIV/V, WIV/V, and ReV. Since the discovery of the pioneering bimetallic {MnII4[MIV(CN)8]2} and {MnII9[MV(CN)8]6} (M = Mo, W) molecules in 2000, octacyanidometallates were fruitfully explored as precursors for the construction of diverse d-d or d-f coordination clusters and frameworks which could be obtained in the crystalline form under mild synthetic conditions. The primary interest in [M(CN)8]n--based networks was focused on their application as molecule-based magnets exhibiting long-range magnetic ordering resulting from the efficient intermetallic exchange coupling mediated by cyanido bridges. However, in the last few years, octacyanidometallate-based materials proved to offer varied and remarkable functionalities, becoming efficient building blocks for the construction of molecular nanomagnets, magnetic coolers, spin transition materials, photomagnets, solvato-magnetic materials, including molecular magnetic sponges, luminescent magnets, chiral magnets and photomagnets, SHG-active magnetic materials, pyro- and ferroelectrics, ionic conductors as well as electrochemical containers. Some of these materials can be processed into the nanoscale opening the route towards the development of magnetic, optical and electronic devices. In this review, we summarise all important achievements in the field of octacyanidometallate-based functional materials, with the particular attention to the most recent advances, and present a thorough discussion on non-trivial structural and electronic features of [M(CN)8]n- ions, which are purposefully explored to introduce desired physical properties and their combinations towards advanced multifunctional materials.

Reversible Humidity-Driven Transformation of a Bimetallic {EuCo} Molecular Material: Structural, Sorption, and Photoluminescence Studies.

Functional molecule-based solids built of metal complexes can reveal a great impact of external stimuli upon their optical, magnetic, electric, and mechanical properties. We report a novel molecular material, {[EuIII(H2O)3(pyrone)4][CoIII(CN)6]}·nH2O (1, n = 2; 2, n = 1), which was obtained by the self-assembly of Eu3+ and [Co(CN)6]3- ions in the presence of a small 2-pyrrolidinone (pyrone) ligand in an aqueous medium. The as-synthesized material, 1, consists of dinuclear cyanido-bridged {EuCo} molecules accompanied by two H-bonded water molecules. By lowering the relative humidity (RH) below 30% at room temperature, 1 undergoes a single-crystal-to-single-crystal transformation related to the partial removal of crystallization water molecules which results in the new crystalline phase, 2. Both 1 and 2 solvates exhibit pronounced EuIII-centered visible photoluminescence. However, they differ in the energy splitting of the main emission band of a 5D0 → 7F2 origin, and the emission lifetime, which is longer in the partially dehydrated 2. As the 1 ↔ 2 structural transformation can be repeatedly reversed by changing the RH value, the reported material shows a room-temperature switching of detailed luminescent features including the ratio between emission components and the emission lifetime values.

Proton Conductive Luminescent Thermometer Based on Near-Infrared Emissive {YbCo2} Molecular Nanomagnets.

Lanthanide(III)-based coordination complexes have been explored as a source of bifunctional molecular materials combining Single-Molecule Magnet (SMM) behavior with visible-to-near-infrared photoluminescence. In pursuit of more advanced multifunctionality, the next target is to functionalize crystalline solids based on emissive molecular nanomagnets toward high proton conductivity and an efficient luminescent thermometric effect. Here, a unique multifunctional molecule-based material, (H5O2)2(H)[YbIII(hmpa)4][CoIII(CN)6]2·0.2H2O (1, hmpa = hexamethylphosphoramide), composed of molecular {YbCo2}3- anions noncovalently bonded to acidic H5O2+ and H+ ions, is reported. The resulting YbIII complexes present a slow magnetic relaxation below 6 K and room temperature NIR 4f-centered photoluminescence sensitized by [Co(CN)6]3- ions. The microporous framework, built on these emissive magnetic molecules, exhibits a high proton conductivity of the H-hopping mechanism reaching σ of 1.7 × 10-4 S·cm-1 at 97% relative humidity, which classifies 1 as a superionic conductor. Moreover, the emission pattern is strongly temperature-dependent which was utilized in achieving a highly sensitive single-center luminescent thermometer with a relative thermal sensitivity, Sr > 1% K-1 in the 50-175 K range. This work shows an unprecedented combination of magnetic, optical, and electrical functionalities in a single phase working as a proton conductive NIR-emissive thermometer based on Single-Molecule Magnets.

Polynomially Filtered Exact Diagonalization Approach to Many-Body Localization.

Polynomially filtered exact diagonalization method (POLFED) for large sparse matrices is introduced. The algorithm finds an optimal basis of a subspace spanned by eigenvectors with eigenvalues close to a specified energy target by a spectral transformation using a high order polynomial of the matrix. The memory requirements scale better with system size than in the state-of-the-art shift-invert approach. The potential of POLFED is demonstrated examining many-body localization transition in 1D interacting quantum spin-1/2 chains. We investigate the disorder strength and system size scaling of Thouless time. System size dependence of bipartite entanglement entropy and of the gap ratio highlights the importance of finite-size effects. We discuss possible scenarios regarding the many-body localization transition obtaining estimates for the critical disorder strength.

Thouless Time Analysis of Anderson and Many-Body Localization Transitions.

Spectral statistics of disordered systems encode Thouless and Heisenberg timescales, whose ratio determines whether the system is chaotic or localized. We show that the scaling of the Thouless time with the system size and disorder strength is very similar in one-body Anderson models and in disordered quantum many-body systems. We argue that the two parameter scaling breaks down in the vicinity of the transition to the localized phase, signaling a slowing-down of dynamics.

Confinement and Lack of Thermalization after Quenches in the Bosonic Schwinger Model.

We excite the vacuum of a relativistic theory of bosons coupled to a U(1) gauge field in 1+1 dimensions (bosonic Schwinger model) out of equilibrium by creating a spatially separated particle-antiparticle pair connected by a string of electric field. During the evolution, we observe a strong confinement of bosons witnessed by the bending of their light cone, reminiscent of what has been observed for the Ising model [Nat. Phys. 13, 246 (2017)NPAHAX1745-247310.1038/nphys3934]. As a consequence, for the timescales we are able to simulate, the system evades thermalization and generates exotic asymptotic states. These states are made of two disjoint regions, an external deconfined region that seems to thermalize, and an inner core that reveals an area-law saturation of the entanglement entropy.