Compressed sensing magnetic resonance imaging (CS-MRI) diagnosis of rotator cuff tears.

OBJECTIVE: The present prospective study was performed to evaluate the diagnostic efficiency of compressed sensing magnetic resonance imaging (CS-MRI) for rotator cuff tears. METHODS: Between December 1, 2021 and April 1, 2022, 62 patients with suspected rotator cuff tears were admitted to Affiliated Hospital of Jinggangshan University and received CS-MRI and arthroscopy to determine the diagnosis and the disease type of tears. Their medical data were obtained and analyzed to evaluate the clinical feasibility of CS-MRI in diagnosing rotator cuff tears. RESULTS: Of the 62 cases of suspected rotator cuff tears, 45 were confirmed by arthroscopy, including 31 cases of total tears and 14 partial tears. Using arthroscopic findings as the gold standard for the diagnosis of rotator cuff tears, the sensitivity of clinical signs to diagnose rotator cuff tears was 66.67%, the specificity was 70.59%, and the accuracy was 67.74%, while the sensitivity of CS-MRI in diagnosing rotator cuff tears was 84.44%, the specificity was 88.24%, and the accuracy was 81.54%. The accuracy of CS-MRI was significantly higher than that of clinical signs as determined by chi-square test within groups (P=0.019). CONCLUSION: CS-MRI provides high resolution for muscles, tendons, and soft tissues, significantly contributing to the diagnosis of soft tissue injuries. Although there were no significant differences in the sensitivity and specificity of CS-MRI for the clinical diagnosis of rotator cuff tears compared to the clinical signs, CS-MRI significantly improved the diagnostic accuracy.

Iron Kß X-ray Emission Spectroscopy: The Origin of Spectral Features from Atomic to Molecular Systems Using Multi-configurational Calculations.

Kß X-ray emission spectroscopy (XES) is widely used to fingerprint the local spin of transition-metal ions, including in pump-probe experiments, to identify excited states or in chemical and biological reactions to characterize short-lived intermediates. In this study, the spectra of ferrous and ferric complexes for various spin states were measured experimentally and described theoretically through restricted active space (RAS) calculations including dynamic correlations. Through the RAS calculations from simple atomic models to complex molecular systems, spectral effects such as the exchange interactions, crystal-field strength, and covalent orbital mixing were evaluated and discussed. The calculations find that only the spectral features of low-spin cases show a dependence on the crystal-field strength, particularly for ferrous low spin. The effect of the covalent orbital mixing strength on the first moment of the Kß1,3 main line and the Kß1,3-Kß' energy splitting is quantitatively described. Clear relationships are found within a given nominal spin but less between different spin states, which calls for careful selection of reference spectra in future experiments. This study further advances our understanding of the correlation between changes in experimental spectral features and their corresponding electronic structure information.

Interpreting the Cu-O2 Antibonding Nature in Two Cu-O2 Complexes from Cu L-Edge X-ray Absorption Spectra.

Cu-O2 structures play important roles in bioinorganic chemistry and enzyme catalysis, where the bonding between the Cu and O2 parts serves as a fundamental research concern. Here, we performed a multiconfigurational study on the copper L2,3-edge X-ray absorption spectra (XAS) of two copper enzyme model complexes to gain a better understanding of the antibonding nature from the clearly interpreted structure-spectroscopy relation. We obtained spectra in good agreement with the experiments by using the restricted active space second-order perturbation theory (RASPT2) method, which facilitated reliable chemical analysis. Spectral feature interpretations were supported by computing the spin-orbit natural transition orbitals. All major features were assigned to be mainly from Cu 2p to antibonding orbitals between Cu 3d and O2 π*, Cu 3d-πO-O* (type A), and a few also to mixed antibonding/bonding orbitals between Cu 3d and O2 π, Cu 3d ± πO-O (type M). Our calculations provided a clear illustration of the interactions between Cu 3d and O2 π*/π orbitals that are carried in the metal L-edge XAS.

Electronic Structure of the Complete Series of Gas-Phase Manganese Acetylacetonates by X-ray Absorption Spectroscopy.

Metal centers in transition metal-ligand complexes occur in a variety of oxidation states causing their redox activity and therefore making them relevant for applications in physics and chemistry. The electronic state of these complexes can be studied by X-ray absorption spectroscopy, which is, however, due to the complex spectral signature not always straightforward. Here, we study the electronic structure of gas-phase cationic manganese acetylacetonate complexes Mn(acac)1-3+ using X-ray absorption spectroscopy at the metal center and ligand constituents. The spectra are well reproduced by multiconfigurational wave function theory, time-dependent density functional theory as well as parameterized crystal field and charge transfer multiplet simulations. This enables us to get detailed insights into the electronic structure of ground-state Mn(acac)1-3+ and extract empirical parameters such as crystal field strength and exchange coupling from X-ray excitation at both the metal and ligand sites. By comparison to X-ray absorption spectra of neutral, solvated Mn(acac)2,3 complexes, we also show that the effect of coordination on the L3 excitation energy, routinely used to identify oxidation states, can contribute about 40-50% to the observed shift, which for the current study is 1.9 eV per oxidation state.

Ferricyanide photo-aquation pathway revealed by combined femtosecond Kß main line and valence-to-core x-ray emission spectroscopy.

Reliably identifying short-lived chemical reaction intermediates is crucial to elucidate reaction mechanisms but becomes particularly challenging when multiple transient species occur simultaneously. Here, we report a femtosecond x-ray emission spectroscopy and scattering study of the aqueous ferricyanide photochemistry, utilizing the combined Fe Kß main and valence-to-core emission lines. Following UV-excitation, we observe a ligand-to-metal charge transfer excited state that decays within 0.5 ps. On this timescale, we also detect a hitherto unobserved short-lived species that we assign to a ferric penta-coordinate intermediate of the photo-aquation reaction. We provide evidence that bond photolysis occurs from reactive metal-centered excited states that are populated through relaxation of the charge transfer excited state. Beyond illuminating the elusive ferricyanide photochemistry, these results show how current limitations of Kß main line analysis in assigning ultrafast reaction intermediates can be circumvented by simultaneously using the valence-to-core spectral range.

The OpenMolcas Web: A Community-Driven Approach to Advancing Computational Chemistry.

The developments of the open-source OpenMolcas chemistry software environment since spring 2020 are described, with a focus on novel functionalities accessible in the stable branch of the package or via interfaces with other packages. These developments span a wide range of topics in computational chemistry and are presented in thematic sections: electronic structure theory, electronic spectroscopy simulations, analytic gradients and molecular structure optimizations, ab initio molecular dynamics, and other new features. This report offers an overview of the chemical phenomena and processes OpenMolcas can address, while showing that OpenMolcas is an attractive platform for state-of-the-art atomistic computer simulations.

Quantifying the Steric Effect on Metal-Ligand Bonding in Fe Carbene Photosensitizers with Fe 2p3d Resonant Inelastic X-ray Scattering.

Understanding the electronic structure and chemical bonding of transition metal complexes is important for improving the function of molecular photosensitizers and catalysts. We have utilized X-ray absorption spectroscopy (XAS) and resonant inelastic X-ray scattering (RIXS) at the Fe L3 edge to investigate the electronic structure of two Fe N-heterocyclic carbene complexes with similar chemical structures but different steric effects and contrasting excited-state dynamics: [Fe(bmip)2]2+ and [Fe(btbip)2]2+, bmip = 2,6-bis(3-methyl-imidazole-1-ylidine)pyridine and btbip = 2,6-bis(3-tert-butyl-imidazole-1-ylidene)pyridine. In combination with charge transfer multiplet and ab initio calculations, we quantified how changes in Fe-carbene bond length due to steric effects modify the metal-ligand bonding, including σ/π donation and π back-donation. We find that σ donation is significantly stronger in [Fe(bmip)2]2+, whereas the π back-donation is similar in both complexes. The resulting stronger ligand field and nephelauxetic effect in [Fe(bmip)2]2+ lead to approximately 1 eV destabilization of the quintet metal-centered 5T2g excited state compared to [Fe(btbip)2]2+, providing an explanation for the absence of a photoinduced 5T2g population and a longer metal-to-ligand charge-transfer excited-state lifetime in [Fe(bmip)2]2+. This work demonstrates how combined modeling of XAS and RIXS spectra can be utilized to understand the electronic structure of transition metal complexes governed by correlated electrons and donation/back-donation interactions.

Resonant X-ray photo-oxidation of light-harvesting iron (II/III) N-heterocyclic carbene complexes.

Two photoactive iron N-heterocyclic carbene complexes [Formula: see text] and [Formula: see text], where btz is 3,3'-dimethyl-1,1'-bis(p-tolyl)-4,4'-bis(1,2,3-triazol-5-ylidene) and bpy is 2,2'-bipyridine, have been investigated by Resonant Photoelectron Spectroscopy (RPES). Tuning the incident X-ray photon energy to match core-valence excitations provides a site specific probe of the electronic structure properties and ligand-field interactions, as well as information about the resonantly photo-oxidised final states. Comparing measurements of the Fe centre and the surrounding ligands demonstrate strong mixing of the Fe [Formula: see text] levels with occupied ligand [Formula: see text] orbitals but weak mixing with the corresponding unoccupied ligand orbitals. This highlights the importance of [Formula: see text]-accepting and -donating considerations in ligand design strategies for photofunctional iron carbene complexes. Spin-propensity is also observed as a final-state effect in the RPES measurements of the open-shell [Formula: see text] complex. Vibronic coupling is evident in both complexes, where the energy dispersion hints at a vibrationally hot final state. The results demonstrate the significant impact of the iron oxidation state on the frontier electronic structure and highlights the differences between the emerging class of [Formula: see text] photosensitizers from those of more traditional [Formula: see text] complexes.

The electronic structure and deexcitation pathways of an isolated metalloporphyrin ion resolved by metal L-edge spectroscopy.

The local electronic structure of the metal-active site and the deexcitation pathways of metalloporphyrins are crucial for numerous applications but difficult to access by commonly employed techniques. Here, we applied near-edge X-ray absorption mass spectrometry and quantum-mechanical restricted active space calculations to investigate the electronic structure of the metal-active site of the isolated cobalt(iii) protoporphyrin IX cation (CoPPIX+) and its deexcitation pathways upon resonant absorption at the cobalt L-edge. The experiments were carried out in the gas phase, thus allowing for control over the chemical state and molecular environment of the metalloporphyrin. The obtained mass spectra reveal that resonant excitations of CoPPIX+ at the cobalt L3-edge lead predominantly to the formation of the intact radical dication and doubly charged fragments through losses of charged and neutral side chains from the macrocycle. The comparison between experiment and theory shows that CoPPIX+ is in a 3A2g triplet ground state and that competing excitations to metal-centred non-bonding and antibonding σ* molecular orbitals lead to distinct deexcitation pathways.

Exact semi-classical light-matter interaction operator applied to two-photon processes with strong relativistic effects.

X-ray processes involve interactions with high-energy photons. For these short wavelengths, the perturbing field cannot be treated as constant, and there is a need to go beyond the electric-dipole approximation. The exact semi-classical light-matter interaction operator offers several advantages compared to the multipole expansion such as improved stability and ease of implementation. Here, the exact operator is used to model x-ray scattering in metal K pre-edges. This is a relativistic two-photon process where absorption is dominated by electric-dipole forbidden transitions. With the restricted active space state-interaction approach, spectra can be calculated even for the multiconfigurational wavefunctions including second-order perturbation. However, as the operator itself depends on the transition energy, the cost for evaluating integrals for hundreds of thousands unique transitions becomes a bottleneck. Here, this is solved by calculating the integrals in a molecular-orbital basis that only runs over the active space, combined with a grouping scheme where the operator is the same for close-lying transitions. This speeds up the calculations of single-photon processes and is critical for the modeling of two-photon scattering processes. The new scheme is used to model Kα resonant inelastic x-ray scattering of iron-porphyrin complexes with relevance to studies of heme enzymes, for which the total computational time is reduced by several orders of magnitude with an effect on transition intensities of 0.1% or less.

HERFD-XANES probes of electronic structures of ironII/III carbene complexes.

Iron centered N-heterocyclic carbene (Fe-NHC) complexes have shown long-lived excited states with charge transfer character useful for light harvesting applications. Understanding the nature of the metal-ligand bond is of fundamental importance to rationally tailor the properties of transition metal complexes. The high-energy-resolution fluorescence detected X-ray absorption near edge structure (HERFD-XANES) has been used to probe the valence orbitals of three carbene complexes, [FeII(bpy)(btz)2](PF6)2 (bpy = 2,2'-bipyridine, btz = 3,3'-dimethyl-1,1'-bis(p-tolyl)-4,4'-bis(1,2,3-triazol-5-ylidene)), [FeIII(btz)3](PF6)3, and [FeIII(phtmeimb)2]PF6 (phtmeimb = [phenyl(tris(3-methylimidazol-2-ylidene))borate]-). The multiconfigurational restrict active space (RAS) approach has been used to simulate the metal K pre-edge X-ray absorption spectroscopy of these carbene complexes, and have reproduced the metal K pre-edge spectral features in terms of relative intensity and peak positions. The evident intensity difference between the FeII and the other two FeIII complexes has been elucidated with different intensity mechanisms in the transition. The smaller splitting between the t2g and eg character peak for [FeIII(btz)3](PF6)3 has been observed in the experimental measurements and been reproduced in the RAS calculations. The results show how the combination of experimental HERFD-XANES measurements and ab initio RAS simulations can give quantitative evaluation of the orbital interactions between metal and ligands for such large and strongly interacting systems and thus allow to understand and predict properties of novel complexes.

Simulations of valence excited states in coordination complexes reached through hard X-ray scattering.

Hard X-ray spectroscopy selectively probes metal sites in complex environments. Resonant inelastic X-ray scattering (RIXS) makes it is possible to directly study metal-ligand interactions through local valence excitations. Here multiconfigurational wavefunction simulations are used to model valence K pre-edge RIXS for three metal-hexacyanide complexes by coupling the electric dipole-forbidden excitations with dipole-allowed valence-to-core emission. Comparisons between experimental and simulated spectra makes it possible to evaluate the simulation accuracy and establish a best-modeling practice. The calculations give correct descriptions of all LMCT excitations in the spectra, although energies and intensities are sensitive to the description of dynamical electron correlation. The consistent treatment of all complexes shows that simulations can rationalize spectral features. The dispersion in the manganese(iii) spectrum comes from unresolved multiple resonances rather than fluorescence, and the splitting is mainly caused by differences in spatial orientation between holes and electrons. The simulations predict spectral features that cannot be resolved in current experimental data sets and the potential for observing d-d excitations is also explored. The latter can be of relevance for non-centrosymmetric systems with more intense K pre-edges. These ab initio simulations can be used to both design and interpret high-resolution X-ray scattering experiments.

Electron Transfer Mediated by Iron Carbonyl Clusters Enhance Light-Driven Hydrogen Evolution in Water by Quantum Dots.

Photocatalytic water splitting has become a promising strategy for converting solar energy into clean and carbon-neutral solar fuels in a low-cost and environmentally benign way. Hydrogen gas is such a potential solar fuel/energy carrier. In a classical artificial photosynthetic system, a photosensitizer is generally associated with a co-catalyst to convert photogenerated charge into (a) chemical bond(s). In the present study, assemblies consisting of CdSe quantum dots that are coupled with one of two molecular complexes/catalysts, that is, [Fe2 S2 (CO)6 ] or [Fe3 Te2 (CO)9 ], using an interface-directed approach, have been tested as catalytic systems for hydrogen production in aqueous solution/organic solution. In the presence of ascorbic acid as a sacrificial electron donor and proton source, these assemblies exhibit enhanced activities for the rate of hydrogen production under visible light irradiation for 8 h in aqueous solution at pH 4.0 with up to 110 µmol of H2 per mg of assembly, almost 8.5 times that of pure CdSe quantum dots under the same conditions. Transient absorption and time-resolved photoluminescence spectroscopies have been used to investigate the charge carrier transfer dynamics in the quantum dot/iron carbonyl cluster assemblies. The spectroscopic results indicate that effective electron transfer from the molecular iron complex to the valence band of the excited CdSe quantum dots significantly inhibits the recombination of photogenerated charge carriers, boosting the photocatalytic activity for hydrogen generation; that is, the iron clusters function as effective intermediaries for electron transfer from the sacrificial electron donor to the valence band of the quantum dots.

Site-Selective Orbital Interactions in an Ultrathin Iron-Carbene Photosensitizer Film.

We present the first experimental study of the frontier orbitals in an ultrathin film of the novel hexa-carbene photosensitizer [Fe(btz)3]3+, where btz is 3,3'-dimethyl-1,1'-bis(p-tolyl)-4,4'-bis(1,2,3-triazol-5-ylidene). Resonant photoelectron spectroscopy (RPES) was used to probe the electronic structure of films where the molecular and oxidative integrities had been confirmed with optical and X-ray spectroscopies. In combination with density functional theory calculations, RPES measurements provided direct and site-selective information about localization and interactions of occupied and unoccupied molecular orbitals. Fe 2p, N 1s, and C 1s measurements selectively probed the metal, carbene, and side-group contributions revealing strong metal-ligand orbital mixing of the frontier orbitals. This helps explain the remarkable photophysical properties of iron-carbenes in terms of unconventional electronic structure properties and favorable metal-ligand bonding interactions-important for the continued development of these type of complexes toward light-harvesting and light-emitting applications.

Hot Branching Dynamics in a Light-Harvesting Iron Carbene Complex Revealed by Ultrafast X-ray Emission Spectroscopy.

Iron N-heterocyclic carbene (NHC) complexes have received a great deal of attention recently because of their growing potential as light sensitizers or photocatalysts. We present a sub-ps X-ray spectroscopy study of an FeII NHC complex that identifies and quantifies the states involved in the deactivation cascade after light absorption. Excited molecules relax back to the ground state along two pathways: After population of a hot 3 MLCT state, from the initially excited 1 MLCT state, 30 % of the molecules undergo ultrafast (150 fs) relaxation to the 3 MC state, in competition with vibrational relaxation and cooling to the relaxed 3 MLCT state. The relaxed 3 MLCT state then decays much more slowly (7.6 ps) to the 3 MC state. The 3 MC state is rapidly (2.2 ps) deactivated to the ground state. The 5 MC state is not involved in the deactivation pathway. The ultrafast partial deactivation of the 3 MLCT state constitutes a loss channel from the point of view of photochemical efficiency and highlights the necessity to screen transition-metal complexes for similar ultrafast decays to optimize photochemical performance.

OpenMolcas: From Source Code to Insight.

In this Article we describe the OpenMolcas environment and invite the computational chemistry community to collaborate. The open-source project already includes a large number of new developments realized during the transition from the commercial MOLCAS product to the open-source platform. The paper initially describes the technical details of the new software development platform. This is followed by brief presentations of many new methods, implementations, and features of the OpenMolcas program suite. These developments include novel wave function methods such as stochastic complete active space self-consistent field, density matrix renormalization group (DMRG) methods, and hybrid multiconfigurational wave function and density functional theory models. Some of these implementations include an array of additional options and functionalities. The paper proceeds and describes developments related to explorations of potential energy surfaces. Here we present methods for the optimization of conical intersections, the simulation of adiabatic and nonadiabatic molecular dynamics, and interfaces to tools for semiclassical and quantum mechanical nuclear dynamics. Furthermore, the Article describes features unique to simulations of spectroscopic and magnetic phenomena such as the exact semiclassical description of the interaction between light and matter, various X-ray processes, magnetic circular dichroism, and properties. Finally, the paper describes a number of built-in and add-on features to support the OpenMolcas platform with postcalculation analysis and visualization, a multiscale simulation option using frozen-density embedding theory, and new electronic and muonic basis sets.

Synthesis of a miniaturized [FeFe] hydrogenase model system.

The reaction occurring during artificial maturation of [FeFe] hydrogenase has been recreated using molecular systems. The formation of a miniaturized [FeFe] hydrogenase model system, generated through the combination of a [4Fe4S] cluster binding oligopeptide and an organometallic Fe complex, has been monitored by a range of spectroscopic techniques. A structure of the final assembly is suggested based on EPR and FTIR spectroscopy in combination with DFT calculations. The capacity of this novel H-cluster model to catalyze H2 production in aqueous media at mild potentials is verified in chemical assays.

Fingerprinting Electronic Structure of Heme Iron by Ab Initio Modeling of Metal L-Edge X-ray Absorption Spectra.

The capability of the multiconfigurational restricted active space approach to identify electronic structure from spectral fingerprints is explored by applying it to iron L-edge X-ray absorption spectroscopy (XAS) of three heme systems that represent the limiting descriptions of iron in the Fe-O2 bond, ferrous and ferric [Fe(P)(ImH)2]0/1+ (P = porphine, ImH = imidazole), and FeII(P). The level of agreement between experimental and simulated spectral shapes is calculated using the cosine similarity, which gives a quantitative and unbiased assignment. Further dimensions in fingerprinting are obtained from the L-edge branching ratio, the integrated absorption intensity, and the edge position. The results show how accurate ab initio simulations of metal L-edge XAS can complement calculations of relative energies to identify unknown species in chemical reactions.

Probing the oxidation state of transition metal complexes: a case study on how charge and spin densities determine Mn L-edge X-ray absorption energies.

Transition metals in inorganic systems and metalloproteins can occur in different oxidation states, which makes them ideal redox-active catalysts. To gain a mechanistic understanding of the catalytic reactions, knowledge of the oxidation state of the active metals, ideally in operando, is therefore critical. L-edge X-ray absorption spectroscopy (XAS) is a powerful technique that is frequently used to infer the oxidation state via a distinct blue shift of L-edge absorption energies with increasing oxidation state. A unified description accounting for quantum-chemical notions whereupon oxidation does not occur locally on the metal but on the whole molecule and the basic understanding that L-edge XAS probes the electronic structure locally at the metal has been missing to date. Here we quantify how charge and spin densities change at the metal and throughout the molecule for both redox and core-excitation processes. We explain the origin of the L-edge XAS shift between the high-spin complexes MnII(acac)2 and MnIII(acac)3 as representative model systems and use ab initio theory to uncouple effects of oxidation-state changes from geometric effects. The shift reflects an increased electron affinity of MnIII in the core-excited states compared to the ground state due to a contraction of the Mn 3d shell upon core-excitation with accompanied changes in the classical Coulomb interactions. This new picture quantifies how the metal-centered core hole probes changes in formal oxidation state and encloses and substantiates earlier explanations. The approach is broadly applicable to mechanistic studies of redox-catalytic reactions in molecular systems where charge and spin localization/delocalization determine reaction pathways.