Open Shell Research Articles

Gas-phase preparation of silylacetylene (SiH3CCH) through a counterintuitive ethynyl radical (C2H) insertion.

Elementary reaction mechanisms constitute a fundamental infrastructure for chemical processes as a whole. However, while these mechanisms are well understood for second-period elements, involving those of the third period and beyond can introduce unorthodox reactivity. Combining crossed molecular beam experiments with electronic structure calculations and molecular dynamics simulations, we provide compelling evidence on an exotic insertion of an unsaturated sigma doublet radical into a silicon-hydrogen bond as observed in the barrierless gas-phase reaction of the D1-ethynyl radical (C2D) with silane (SiH4). This pathway, which leads to the D1-silylacetylene (SiH3CCD) product via atomic hydrogen loss, challenges the prerequisite and fundamental concept that two reactive electrons and an empty orbital are required for the open shell, unsaturated radical reactant to insert into a single bond.

Ring Currents in the Clar Goblet Calculated Using Configurational State Averaging.

The closed-shell Hückel-London-Pople-McWeeny formalism for ring currents is extended to Aufbau configurations with open shells calculated as configurational averages. The method is applied to the non-Kekulean benzenoid known as the Clar goblet, recently synthesized on the Au(111) surface. Multiplicity of the ground state is a complication: for the Clar goblet, Hund's rule of maximum multiplicity implies a triplet whereas Ovchinnikov's rule implies a singlet. This disagreement has little effect on the predicted ring currents. Ring-current maps are calculated for the 36π dication, 40π dianion, and low-lying states of the 38π neutral, using Hückel-London and Hubbard-London models. All show twin diatropic perimeter currents on separate halves of the molecule. These are compared with ipsocentric pseudo-π and ab initio maps of induced π-current for closed-shell singlet configurations of dianion, dication, and neutral. Configurationally averaged Hückel-London calculations give a good account of the consistent diatropic ring currents in the Clar goblet for the three charge states.

Accurate Thermochemistry with Multireference Methods: A Stress Test for Internally Contracted Multireference Coupled-Cluster Theory.

The internally contracted multireference coupled-cluster method with single, double and perturbative triple excitations, icMRCCSD(T), was tested for its performance in the context of computational high-accuracy thermochemistry. The results were gauged against the standard single-reference coupled-cluster hierarchy with up to 5-fold excitations. The test set comprised of a selection of first-row dinuclear compounds and the three 3d-transition metal compounds MnH, FeH, and CoH. The results revealed two problems with the current formulation of icMRCCSD(T). First, the choice of the Dyall Hamiltonian as the zeroth-order Hamiltonian, which leads to a biased description of the different orbital subspaces and particularly poor results for the atomic correlation energies, and second, the tendency to overestimate the perturbative correction for triply excited clusters, in particular in the presence of open shells and correspondingly low orbital-energy gaps. The two problems could be solved by resorting to the effective Fock operator as zeroth-order Hamiltonian and by adopting a modified amplitude equation that includes terms quadratic in the pair clusters. A similar modification was recently proposed by Masios et al. (Phys. Rev. Lett. 2023, 131, 186401) in the context of applying single-reference coupled-cluster theory to systems with small or vanishing band gaps and we chose the acronym '(cT*) correction' in analogy to that work. In contrast to the work of Masios et al., additional terms including single excitation clusters were omitted, as these again lead to an overestimation of correlation effects in more difficult cases. We also tested another alternative for the zeroth-order Hamiltonian and additional higher-order corrections for the correlation energy. These extensions did not significantly improve the results and were also computationally more demanding. The improved icMRCCSD(cT*)F method yields very accurate results with errors, relative to accurate benchmarks, better than 2 kJ/mol for total energies and atomization energies for the entire set of examples considered in this work.

Photokatalytische PPh3‐vermittelte Synthese von C3‐funktionalisierten Indolen über radikalische Anellierung von Nitroaromaten und Alkenen

AbstractOxidativ erzeugte Phosphin‐Radikalkationen sind reaktive Intermediate, die über Deoxygenierungsprozesse zur Erzeugung von kohlenstoff‐ und heteroatomzentrierten Radikalen verwendet werden können. Solche P‐Radikalkationen lassen sich leicht durch Ein‐Elektronentransfer‐Oxidation mit einem Redoxkatalysator erzeugen. Günstige und kommerziell erhältliche Nitroaromaten sind ideale Stickstoffquellen zum Aufbau organischer Amine und stickstoffhaltiger Heterozyklen. Die Aktivierung von Nitroaromaten mit Phosphinen wurde bereits in ionischen Prozessen erreicht, die jedoch spezielle Phosphor‐Nukleophile und hohe Temperaturen erfordern. In dieser Arbeit wird über einen alternativen Weg der Nitroaktivierung berichtet, der über einen radikalischen Prozess verläuft. Diese Strategie führt zu offenschaligen Zwischenprodukten, die eine interessante, unerforschte Reaktivität zeigen. Dies wird durch die Entwicklung einer wirtschaftlichen und hoch effizienten Synthese wertvoller Indolderivate durch photokatalytische PPh3‐vermittelte Anellierung von Nitroaromaten mit Alkenen dokumentiert. Die Sequenz weist eine große Toleranz gegenüber funktionellen Gruppen auf. Das Verfahren ermöglicht die Aktivierung von Nitroaromaten bei Raumtemperatur, wobei eine doppelte C−H‐Bindungsfunktionalisierung von Alkenen erreicht wird, um einen schnellen Zugang zu C3‐funktionalisierten Indolen zu bieten, die Schlüsselstrukturkomponenten verschiedener Naturstoffe und Arzneimittel darstellen. Mechanistische Studien, die durch DFT‐Berechnungen weiter unterstützt werden, deuten darauf hin, dass ein Nitrosoaryl‐Radikalkation eine Schlüsselrolle im Anellierungsprozess spielt.

Photocatalytic PPh3-Mediated Synthesis of C3-Functionalized Indoles via Radical Annulation of Nitroarenes and Alkenes.

Oxidatively generated phosphine radical cations are reactive intermediates that can be used for the generation of carbon and heteroatom centered radicals via deoxygenation processes. Such P-radical cations can readily be generated via single electron transfer oxidation using a redox catalyst. Cheap and commercially available nitroarenes are ideal nitrogen sources for the construction of organic amines and N-containing heterocycles. Activation of nitroarenes with phosphines has been achieved in the ionic mode, which requires specially designed P-nucleophiles and high temperatures. Herein, we report an alternative mode of nitro activation that proceeds via a radical process. The radical strategy leads to open shell intermediates that show interesting unexplored reactivity. This is documented by the development of an economic and highly efficient synthesis of valuable indole derivatives through photocatalytic PPh3-mediated annulation of nitroarenes with alkenes showing large functional group tolerance. The method allows room-temperature activation of nitroarenes and a double C-H bond functionalization of alkenes is achieved to provide rapid access to C3-functionalized indoles, which are key structural components of diverse natural and drug molecules. Experimental mechanistic studies that are further supported by DFT calculations indicate that a nitrosoarene radical cation plays a key role in the annulation process.

Expanding the Landscape of Phosphorous-Based Open Shell Species: Stable Mono-, Di-, and Trianionic Radicals Based on a Contorted Triphosphaalkene.

The stepwise reduction of the highly contorted truxene-based triphosphaalkene 1 using KC8 led to the isolation of mono-, di-and tri-anionic species. The solid-state molecular structures of mono- and diradical anionic species were elucidated by single crystal X-ray diffractions, revealing elongated P-C bonds and a pronounced "indene" aromatization compared to the parent system. All three radical species displayed distinct Electron Paramagnetic Resonance (EPR) spectra, providing compelling evidence for the open-shell electronic configuration of both the diradical and triradical species-an observation unprecedented in any previously reported phosphorous-based anionic polyradicals. Mulliken spin density calculations revealed a dominant localization of radical spin on a single phosphorous atom in the monoanion. In the dianion, spin localization is observed on two phosphorous atoms (~34% each), with a minor contribution from the third phosphorous (0.13%), while the trianion demonstrates a uniform distribution of spin density (~30%) across each phosphorous atom.

Expanding the Landscape of Phosphorous‐Based Open Shell Species: Stable Mono‐, Di‐, and Trianionic Radicals Based on a Contorted Triphosphaalkene

AbstractThe stepwise reduction of the highly contorted truxene‐based triphosphaalkene 1 using KC8 led to the isolation of mono‐, di‐, and tri‐anionic species. The solid‐state molecular structures of mono‐ and diradical anionic species were elucidated by single crystal X‐ray diffractions, revealing elongated P−C bonds and a pronounced “indene” aromatization compared to the parent system. All three radical species displayed distinct Electron Paramagnetic Resonance (EPR) spectra, providing compelling evidence for the open‐shell electronic configuration of both the diradical and triradical species—an observation unprecedented in any previously reported phosphorous‐based anionic polyradicals. Mulliken spin density calculations revealed a dominant localization of radical spin on a single phosphorous atom in the monoanion. In the dianion, spin localization is observed on two phosphorous atoms (~34 % each), with a minor contribution from the third phosphorous (0.13 %), while the trianion demonstrates a uniform distribution of spin density (~30 %) across each phosphorous atom.

Isonitrile Photochemistry: A Functional Group Class Coming in from the Cold.

Starting from a historical background that acknowledges isonitriles as a neglected class of compounds due to their unpleasant smell and hardly controlled reaction conditions with open shell species, the present concept article aims at highlighting the seeds of the modern isonitrile photochemistry. Representative essential transformations achieved via either UV light irradiation or radical initiators at high temperatures are brought into play to draw a parallel with the current literature relying on the exploitation of visible light photochemical methods. Such a comparison points out the potential of this enabling technology to further expand the scope of isonitrile chemistry and the unmet challenges which makes it a very stimulating field.

Putting the squeeze on valence tautomerism in cobalt-dioxolene complexes

Molecules that can reversibly switch between electronic states under an external stimulus are of interest to numerous applications. Complexes of open shell metal ions with redox active ligands undergo valence tautomerism, resulting in magnetic, colour and structural switching, relevant to data storage and actuators. However, the precise structural changes occurring during valence tautomerism in the solid state are unclear due to the lack of atomic-resolution characterization. Here, variable temperature and high-pressure single crystal X-ray diffraction is used to characterize valence tautomerism in two isostructural cobalt complexes, [Co(bis(6-methyl-2-pyridylmethyl) amine)(3,5-di-tert-butyl-1,2-dioxolene)]+ and [Co(tris(6-methyl-2-pyridylmethyl)amine)(3,5-di-tert-butyl-1,2-dioxolene)]+ to atomic resolution. The less sterically hindered dimethylated complex exhibits two-step thermally-induced interconversion between the high-spin CoII-seminquinonate and low-spin CoIII-catecholate forms (valence tautomerism) at 155 and 95 K due to the presence of two symmetry-independent complexes. In contrast, the more sterically hindered trimethylated complex does not display thermal valence tautomerism. Both complexes exhibit unique behaviour under high pressure. The dimethylated species undergoes gradual, one-step valence tautomerism in both symmetry-independent complexes concurrently between 0.43 GPa and 1.30 GPa. In the trimethylated species, pressure is sufficient to overcome steric hindrance, leading to one-step valence tautomerism between 2.60 GPa and 3.10 GPa, demonstrating pressure-triggered valence tautomerism in a thermally inactive complex. This study is among the few investigations using in situ high-pressure single crystal X-ray diffraction to achieve atomic-level structural characterization of valence tautomerism, aiding the development of robust structure-property relationships in these types of complexes.

Prediction by DFT and Docking Calculations of a Series of Hypothetical 3d Transition Element Isostructural Complexes [M(hfac)2(TTF)2]: A Comparative Study

AbstractThe study aims to predict and compare the structural, electronic, conductivity, and biological properties of a series of 3d transition element complexes with those of the previously studied isostructural copper complex [Cu(hfac)2(TTF)2][PF6]2 (TTF: tetrathiafulvalene, hfac: hexafluoroacetylacetonate). Because transition metals hold open electronic shells, all possible spin states for all divalent compounds have to be considered in order to determine the most stable configurations. These configurations are those corresponding to the highest spin state (5 for Mn, 4 for Fe, 3 for Co, 2 for Ni, 1 for Cu, and 0 for Zn). However, the configurations with the smallest gap are Mn(3) and Co(1), suggesting that these are the most conductive complexes. A significant metal–ligand charge transfer is observed for both Mn and Co complexes. Antifungal (CYP121 (PDB: 2IJ7) and CYP51 (PDB: 1EA1)) and antibacterial (Escherichia coli (PDB: 1KZN)) properties of the compounds studied were evaluated by molecular docking; the results obtained reveal that the following complexes show significant activity: Zn(hfac)2(TTF)2] [PF6]2 (−8.9 kcal/mol), Ni(hfac)2(TTF)2] [PF6]2 (−7.8 kcal/mol), and Cu(hfac)2(TTF)2] [PF6]2 (−8.2 kcal/mol).

Bonding and Interactions in UO22+ for Ground and Core Excited States: Extracting Chemistry from Molecular Orbital Calculations.

Theoretical analyses of actinyls are necessary in order to understand and correctly interpret the chemical and physical properties of these molecules. Here, wave functions of Uranyl, UO22+, are considered for the ground state and for the core excited states where an electron is promoted from the U 3d5/2 shell into a low-lying unoccupied orbital that is U 5f antibonding with the ligand, O, orbitals. A focus is on the application of novel theoretical methods to the analysis of these wave functions so that measurements, especially with X-ray absorption, can be related to the UO22+ chemical bonding. The bond covalency is examined with these theoretical methods. The study includes how the covalent character is different for the ground and excited configurations and how this character changes as the U-O distance is changed. Furthermore, analyses are mode of how many-body effects may modify excitation energies and X-ray adsorption intensities. This includes determining the extent to which a single configuration provides a satisfactory model for the UO22+ wave functions. Two distinct types of many-body effects are considered. One involves the angular momentum coupling of the open shell electrons in the excited states to yield correct multiplets. The second adds excitations from shells that are bonding into the antibonding open shell space. These excitations are essential to properly describe the X-ray adsorption. While these many-body effects must be taken into account, their importance and their role can be explained and understood using orbitals and orbital occupations.

Free Vibration of Carbon Nanotube Reinforced Functionally Graded Shells

The main objective of this research is to investigate the vibration patterns of cylindrical panels composed of epoxy composites containing functionally graded Multiwall Carbon Nanotube (FG MWCNT). The research specifically addresses the issue of resonance failure, which is common in lightweight polymer composite structures that are subjected to dynamic forces. Curved components used in aircraft, automobiles, and marine vehicles, i.e. curved panels, conical shells, open shells and circular cylindrical shells, are particularly susceptible to this type of failure. The ANSYS software was used to consider three different types of uniaxial reinforcement distribution for modelling cylindrical panels made of FG-MWCNT epoxy composites. The extended rule of mixture of a micromechanical model is employed to determine the distribution of carbon nanotubes transversely the thickness of the structure, utilizing effective parameters. The research examines the impact of various geometrical considerations, such as the volume fraction of carbon nanotubes (CNTs),length to thickness ratio and boundary conditions on the analysis of vibration of the shell structure. The outcomes obtained from the suggested Finite Element Method (FEM) are obtainable to validate the performance and usefulness of the model.

Classification of Open and Closed Pistachio Shells Using Machine Vision Approach

Pistachio nuts are a type of nut that is widely consumed around the world due to their high nutritional value and pleasant taste. Pistachios are usually sold in their shells, either open or closed. However, closed-shell pistachios are not well received by consumers, resulting in a lower commercial value. It is essential to be able to distinguish between open and closed pistachio shells in order to ensure quality control during production processes and processing. This can be done manually or by using mechanical devices. Manual inspection and categorization of pistachio nuts have traditionally been done by workers, but this process is inefficient in terms of time and money. Mechanical separation of open and closed-shell pistachio can damage the kernels of open-shell nuts due to the needle mechanism used in the sorting process. This study aims to classify pistachio nuts using a machine vision-based system and evaluate its applicability in terms of classification accuracy. The system is evaluated on the Antep pistachio species, which can be distinguished from other pistachio varieties, such as Siirt and Urfa pistachios, based on their shape, size, and taste properties. The machine vision system in this study classifies pistachio nuts into closed and open shell classes in a completely automated manner. In this study, 1,000 Antep pistachio nuts images were obtained and examined, including 500 open and 500 closed nuts. The images were pre-processed and prepared for feature extraction. From the images, a total of 14 color features were extracted. Although the single feature was used, promising classification accuracy rates of 95.6%, 94.8%, and 93.6% from the Random Forest, Support Vector Machine (SVM), and Logistic Regression were achieved, respectively. The performances of classifiers were compared to each other. Almost similar performances were detected. These results demonstrate that the Random Forest classifier is the most effective algorithm for classifying open and closed Antep pistachio nuts.

Vibration of composite open shell of hydrogen-electric fuselage with rectangular cutout in hygrothermal circumstances: theoretical and experimental research

An effective formulation is performed to approximate calculate the vibration of the typical composite fuselage battery compartment structures of the hydrogen-electric aircraft, which are highly sensitive to hygrothermal circumstances. The strain energy, kinetic energy and hygrothermal potential energy of CLOCSRC are deduced in frame of Donnell's shell assumption and a series of hypothetical elastic springs operating on the edges of divided components are introduced to simulate coupling connection and the elastic supports of the open shell, which contribute to total system energy in the form of elastic spring potential energy. The equations of motion for CLOCSRC subjected to distinct hygrothermal circumstances and arbitrary boundaries are eventually obtained in frame of the Rayleigh-Ritz method by means of the modified orthogonal polynomial as the displacement admissible function. After confirming the convergence and accuracy of the presented formulation by experiment and finite element method, several numerical examples are presented to investigative the effects of geometric parameters, elastic boundaries and hygrothermal circumstances on the vibration of CLOCSRC. Differ from traditional investigation, the present paper offers an effective approach to insight the hygrothermal mechanism of open shell with rectangular cutouts creatively. The relevant investigation demonstrated that the current strategy is beneficial for further research on the vibration characteristics of CLOCSRC.

Vibration analysis of functionally graded carbon nanotube‐reinforced composite open cylindrical shells with damping film embedded

AbstractIn the present study, a discrete layer model was established to explore the vibration performance of Functionally Graded Carbon Nanotube‐Reinforced Composite (FG‐CNTRC) open cylindrical shells with damping film embedded based on the first‐order shell theory. There are four configurations of stacking arrangements considered for FG‐CNTRC open cylindrical shells with damping film embedded. The equivalent structural parameters of the top and bottom FG‐CNTRC panels are generated by implementing the extended mixing rule. Governing equations are derived based on the Hamilton principle and solved with the Naiver solution. Subsequently, after verifying the validity of this paper's solution by comparing it with the published literature, a parametric elaborated investigation discloses the variation patterns of vibration performance of four FG‐CNTRC open cylindrical shells with damping film embedded. The conclusions of the study can be used as a useful guide about open cylindrical composite shell structures with the design of high strength and damping.Highlights Discrete layer vibration model was bulit based on first‐order shell theory. Vbration performance of FG‐CNTRC open sandwich shells was studied. Variation patterns of frequency and loss factor was disclosed.

Analytical seismic model for a tunnel with segmental liner buried in the half-space soil

In this paper, by using the wave function expansion (WFE) and the expansion of the cylindrical wave into plane wave (ECPW) methods, an analytical method for the dynamic response of a circular tunnel with segmental liner buried in the half-space soil to harmonic elastic waves is developed. The liner of the tunnel is supposed to consist of several segments and joints. Both the segments and joints are treated as open cylindrical shells, and the segment and joint shells together thus form an equivalent continuous shell (ECS) liner, and the thin shell theory is utilized to describe its vibration. The scattered wave field due to the presence of the tunnel and boundary of the half-space soil is divided into two parts, namely, the direct scattered wave field and secondary scattered wave field. The expressions for the direct scattered cylindrical waves in the soil is determined via the WFE method, while the secondary scattered waves form the boundary of the half-space soil are obtained by the ECPW method together with the application of the boundary condition along the soil surface. Applying the cylindrical shell theory on the ECS liner and using the Fourier series expansions for the variables and parameters of the ECS liner along the azimuthal direction together with introducing the Fourier component constitutive relation for the ECS liner, a system of equations for the Fourier component ECS displacements are derived with the differential equations for the ECS liner displacements. By using the system of equations, the expressions for the free and scattered wave fields and the continuity conditions at the interface between the liner and soil, the system of equations for the ECS liner coupled with the soil are derived. By using the developed analytical method for the tunnel, some results of the ECS tunnel under different incident waves are given.

Quantum Tunneling of the Magnetization in Systems with Anisotropic 4f Ion Pairs: Rates from Low-Temperature Zero-Field Relaxation.

Anisotropic open shell 4f ions have magnetic moments that can be read and written as atomic bits. If it comes to quantum applications where the phase of the wave function has to be written, controlled, and read, it is advantageous to rely on more than one atom that carries the quantum information on the system because states with different susceptibilities may be addressed. Such systems are realized for pairs of lanthanides in single-molecule magnets, where four pseudospin states are found and mixed in quantum tunneling processes. For the case of endohedral fullerenes like Dy2S@C82 or Tb2ScN@C80, the quantum tunneling of the magnetization is imprinted in the magnetization lifetimes at sub-Kelvin temperatures. A (4 × 4) Hamiltonian that includes quantum tunneling of the magnetization and the dipole and exchange interaction between the two lanthanide magnetic moments predicts the lifting of the zero-field ground state degeneracy and nonlinear coupling to magnetic fields in such systems.

Free vibration analysis of closed and open horizontal cylindrical shells utilizing coupled transfer function method and differential transform method

This article aims to analyze the free vibration of closed and open horizontal circular cylindrical shells based on the concept of state-space transformation in conjunction with the differential transform method (DTM). The governing equations of the cylinders were developed based upon Sanders’ thin shell theory. Then, the set of coupled governing differential equations transformed into nine first-order differential equations. Afterwards, the well-established semi-analytical scheme so-called DTM was employed to solve the differential equations. The numerical investigation of the present method was also comprehensively carried out by analyzing some closed and open cylindrical shells with different boundary and compatibility conditions. To ensure the correctness of the results, the outcomes were compared with experimental and other numerical results, especially with the well-known finite element method. Furthermore, some plots of two-dimensional and three-dimensional mode shapes for the first and second axial modes are depicted.

Mathematical modelling of stability problems for thin transversally graded cylindrical shells

The objects of consideration are thin linearly elastic Kirchhoff–Love-type open circular cylindrical shells having a functionally graded macrostructure and a tolerance-periodic microstructure in circumferential direction. The first aim of this contribution is to formulate and discuss a new mathematical averaged non-asymptotic model for the analysis of selected stability problems for such shells. As a tool of modelling we shall apply the tolerance averaging technique. The second aim is to derive and discuss a new mathematical averaged asymptotic model. This model will be formulated using the consistent asymptotic modelling procedure. The starting equations are the well-known governing equations of linear Kirchhoff–Love second-order theory of thin elastic cylindrical shells. For the functionally graded shells under consideration, the starting equations have highly oscillating, non-continuous and tolerance-periodic coefficients in circumferential direction, whereas equations of the proposed models have continuous and slowly-varying coefficients. Moreover, some of coefficients of the tolerance model equations depend on a microstructure size. It will be shown that in the framework of the tolerance model not only the fundamental cell-independent, but also the new additional cell-dependent critical forces can be derived and analysed.

Linear analytical model for the seismic response of a straight‐jointed shield tunnel

AbstractIn this study, the segment joint and ring joint of the lining of the straight‐jointed tunnel are simplified as an equivalent open cylindrical shell with a small central angle and an equivalent closed cylindrical shell with a small width, and the lining of the straight‐jointed tunnel is thus simplified as an equivalent continuous periodic shell (ECPS) described by the cylindrical shell theory. Since the ECPS lining is periodic along the longitudinal direction, the tunnel‐soil system can thus be treated as a periodic system, which is referred to as the periodic tunnel‐soil system (PTSS) in this study. Based on the proposed ECPS lining model, an analytical method for the tunnel with the ECPS lining (ECPS tunnel) under seismic waves is established in this study. By employing the periodicity condition for the PTSS as well as the wave function expansion method, the representation for the wave field in the soil is established. With the aforementioned cylindrical shell theory and Fourier series expansion method, the convolution type constitutive relation for the ECPS lining and the Fourier space equations of motion are derived. By using the soil‐lining continuity condition and aforementioned formulations for the ECPS lining and soil, the coupled Fourier space equations of motion for the PTSS are established, with which the response of the ECPS lining and scattered waves in the soil can be determined.