Spin Inversion Research Articles

π‐Extended 4,5‐Fused Bis‐Fluorene: Highly Open‐Shell Compounds and their Cationic Tetrathiafulvalene Derivatives

AbstractThe synthesis of diradical organic compounds has garnered significant attention due to their thermally accessible spin inversion and optoelectronic properties. Yet, preparing such stable structures with high open‐shell behavior remains challenging. Herein, we report the synthesis and properties of four π‐extended, fused fluorene derivatives with high diradical character, taking advantage of a molecular design where the closed‐shell does not include any Clar sextet, comparatively to a maximum of 5 in the corresponding open‐shell state. This led to an unusual open‐shell triplet ground state with an outstanding singlet‐triplet energy difference (ΔEST) of ca. 19 kcal/mol, one of the highest values reported to date for an all‐carbon conjugated scaffold. Incorporation of dithiafulvene units at each end of the molecule (at the five‐membered rings) furnishes extended tetrathiafulvalenes (TTFs) undergoing reversible oxidations to the radical cation and diradical dication. The various pro‐aromatic structures presented herein show highly localized spin density and a limited conjugation due to the confined π‐electrons in the aromatic cycles, as supported by 1H NMR, UV/Visible, EPR spectroscopy and DFT calculations.

π-Extended 4,5-Fused Bis-Fluorene: Highly Open-Shell Compounds and their Cationic Tetrathiafulvalene Derivatives.

The synthesis of diradical organic compounds has garnered significant attention due to their thermally accessible spin inversion and optoelectronic properties. Yet, preparing such stable structures with high open-shell behavior remains challenging. Herein, we report the synthesis and properties of four π-extended, fused fluorene derivatives with high diradical character, taking advantage of a molecular design where the closed-shell does not include any Clar sextet, comparatively to a maximum of 5 in the corresponding open-shell state. This led to an unusual open-shell triplet ground state with an outstanding singlet-triplet energy difference (ΔEST) of ca. 19 kcal/mol, one of the highest values reported to date for an all-carbon conjugated scaffold. Incorporation of dithiafulvene units at each end of the molecule (at the five-membered rings) furnishes extended tetrathiafulvalenes (TTFs) undergoing reversible oxidations to the radical cation and diradical dication. The various pro-aromatic structures presented herein show highly localized spin density and a limited conjugation due to the confined π-electrons in the aromatic cycles, as supported by 1H NMR, UV/Visible, EPR spectroscopy and DFT calculations.

Vibrational squeezing via spin inversion pulses

Magnetic resonance force microscopy (MRFM) describes a range of approaches to detect nuclear spins with mechanical sensors. MRFM has the potential to enable magnetic resonance imaging with near-atomic spatial resolution, opening up exciting possibilities in solid state and biological research. In many cases, the spin-mechanics coupling in MRFM is engineered with the help of periodic radio frequency pulses. In this paper, we report that such pulses can result in unwanted parametric amplification of the mechanical vibrations, causing misinterpretation of the measured signal. We show how the parametric effect can be canceled by auxiliary radio frequency pulses or by appropriate post-correction after careful calibration. Future MRFM measurements may even make use of the parametric amplification to reduce the impact of amplifier noise.

Simultaneous Multiparameter Mapping of the Liver in a Single Breath-Hold or Respiratory-Triggered Acquisition Using Multi-Inversion Spin and Gradient Echo MRI.

Quantitative parametric mapping is an increasingly important tool for noninvasive assessment of chronic liver disease. Conventional parametric mapping techniques require multiple breath-held acquisitions and provide limited anatomic coverage. To investigate a multi-inversion spin and gradient echo (MI-SAGE) technique for simultaneous estimation of T1, T2, and T2* of the liver. Prospective. Sixteen research participants, both adult and pediatric (age 17.5 ± 4.6 years, eight male), with and without known liver disease (seven asymptomatic healthy controls, two fibrotic liver disease, five steatotic liver disease, and two fibrotic and steatotic liver disease). 1.5 T, single breath-hold and respiratory triggered MI-SAGE, breath-hold modified Look-Locker inversion recovery (MOLLI, T1 mapping), breath-hold gradient and spin echo (GRASE, T2 mapping), and multiple gradient echo (mGRE, T2* mapping) sequences. Agreement between hepatic T1, T2, and T2* estimated using MI-SAGE and conventional parametric mapping sequences was evaluated. Repeatability and reproducibility of MI-SAGE were evaluated using a same-session acquisition and second-session acquisition. Bland-Altman analysis with bias assessment and limits of agreement (LOA) and intraclass correlation coefficients (ICC). Hepatic T1, T2, and T2* estimates obtained using the MI-SAGE technique had mean biases of 72 (LOA: -22 to 166) msec, -3 (LOA: -10 to 5) msec, and 2 (LOA: -5 to 8) msec (single breath-hold) and 36 (LOA: -43 to 120) msec, -3 (LOA: -17 to 11) msec, and 4 (LOA: -3 to 11) msec (respiratory triggered), respectively, in comparison to conventional acquisitions using MOLLI, GRASE, and mGRE. All MI-SAGE estimates had strong repeatability and reproducibility (ICC > 0.72). Hepatic T1, T2, and T2* estimates obtained using an MI-SAGE technique were comparable to conventional methods, although there was a 12%/6% for breath-hold/respiratory triggered underestimation of T1 values compared to MOLLI. Both respiratory triggered and breath-hold MI-SAGE parameter maps demonstrated strong repeatability and reproducibility. 1 TECHNICAL EFFICACY: Stage 2.

Doping dependence of spin-momentum locking in bismuth-based high-temperature cuprate superconductors

Non-zero spin orbit coupling has been reported in several unconventional superconductors due to the absence of inversion symmetry breaking. This contrasts with cuprate superconductors, where such interaction has been neglected for a long time. The recent report of a non-trivial spin orbit coupling in overdoped Bi2212 cuprate superconductor, has re-opened an old debate on both the source and role of such interaction and its evolution throughout the superconducting dome. Using high-resolution spin- and angle-resolved photoemission spectroscopy, we reveal a momentum-dependent spin texture throughout the hole-doped side of the superconducting phase diagram for single- and double-layer bismuth-based cuprates. The universality of the reported effect among different dopings and the disappearance of spin polarization upon lead substitution, suggest a common source. We argue that local structural fluctuations of the CuO planes and the resulting charge imbalance may cause local inversion symmetry breaking and spin polarization, which might be crucial for understanding cuprates physics.

Evolution of nuclear shell structure in neutron-rich nuclei N=32 and N=34

This paper presents an overview of the experimental setup to study the structure of unstable nuclear isotopes in the region from 47Cl to 63V of the SEASTAR 3 project and the evolution of shell structure in neutron-rich nuclei N=32 and N=34. The first excited energies of Cl, Ar, and K isotopes around N=32, N=34 obtained from the SEASTAR 3 project were determined. The evolution of shell structure in neutron-rich nuclei N=32 và N=34 is explained by the contribution of tensor forces in addition to central and spin-orbit forces. The appearance of new magic neutron N=34 in 54Ca is explained due to proton-neutron tensor force that pulls neutron 0f5/2 lower than 1p1/2 level, leading to not only causes the spin inversion of neutrons at 1p1/2 and 0f5/2 levels and enlarges an energy gap between these levels. The change of proton and neutron energy levels in Cl, Ar, and K isotopes around N=32, N=34 driven by tensor force was also discussed in this article.

Pseudospin symmetry: Microscopic origin of the ground-state inversion in neutron-rich odd-A Cu isotopes

The role of the pseudospin symmetry in the inversion of the ground-state spin in Cu isotopes is investigated within the covariant density functional theory (CDFT). The density functional PC-PK1 gives a good agreement with the observed ground-state properties of the odd-A 69−79Cu. In particular, the inversion of the ground-state spin at A=75 is reproduced nicely, which can be explained by the level crossing between the proton pseudospin partners π2p3/2 and π1f5/2. It is found that the pseudospin symmetry plays a dominant role in the evolution of the energy splittings between the pseudospin partners. By comparing with the results of the nonrelativistic DFTs, our studies suggest that the pseudospin symmetry is essential to the shell evolution around this region.

In-phase and opposed-phase Dixon chemical shift imaging for the assessment of skeletal marrow lesions: comparison of measurements from longitudinal sequences to those from axial sequences.

In-phase and opposed-phase chemical shift imaging (CSI) is a useful technique for assessing skeletal lesions. This study determined the frequency of significant differences in measurements obtained from longitudinal (coronal or sagittal) sequences to those obtained from axial sequences. Chemical shift imaging was undertaken in 96 consecutive patients referred from the Musculoskeletal Sarcoma and Spinal Oncology services for assessment of possible bone tumours as part of a standard tumour protocol, which included turbo spin echo and inversion recovery sequences. For spinal lesions, CSI was obtained in the sagittal and axial planes, while for all other sites, it was obtained in the coronal and axial planes. The study included 49 (51.0%) males and 47 (49.0%) females with mean age 42.4 years (range 2-91 years). In 4 cases, 2 individual lesions were assessed, making a total of 100 lesions. Based on typical imaging features (n = 57) or histology (n = 43), 22 lesions (22%) were classified as non-neoplastic, 44 (44%) as benign neoplasms, 6 (6%) as intermediate-grade neoplasms, and 28 (28%) as malignant neoplasms. A significant discrepancy, wherein a lesion was classified as fat-containing (% SI drop >20%-25%) in the longitudinal plane, while in the axial plane it was classified as fat-replacing (% SI drop <20%-25%), or vice versa, occurred in 9%-14% of cases. However, this discrepancy had no appreciable effect on overall diagnostic accuracy, which was calculated at 79% for the longitudinal plane and 75%-80% for the axial plane. Significant differences in CSI measurements occur in 9%-14% of cases based on imaging plane, but with no significant effect on diagnostic accuracy. Radiologists should be aware that CSI measurements in different planes appear to have significant differences in up to 14% of lesions. However, diagnostic accuracy does not seem to be significantly affected.

Phase transitions and spectral shifts: a quantum mechanical exploration of vibrational frequency in magnesium ferrite.

Spinel ferrites represent an integral subset of magnetic materials, with their inherent properties largely influenced by cation occupancy and spin interaction. In this study, we present an in-depth theoretical exploration of the phase transition landscape of pure magnesium-ferrite, deploying hybrid functionals and a local Gaussian basis set to scrutinize the relaxed lattice structure, relative energy, magnetic properties, electronic characteristics, and vibrational frequencies. Our investigation reveals that the ground state of magnesium-ferrite is an open-shell system with an inverse structure. This is characterized by the complete occupancy of octahedral sites by magnesium atoms, with Iron atoms dispersed between both tetrahedral and octahedral sites. We found a relative energy difference of 0.41 eV between the antiferromagnetic ground configuration and the ferro arrangement within the inverse structure. Furthermore, our research also delved into the impact of spin rearrangement and inversion (X = 0.0, 0.5 and 1) on Raman and infrared spectra. Notably, the lattice distortion from the cubic form, apparent in the optimized structure, resonates in the IR and Raman spectra, resulting in significant splitting. The frequencies calculated in this study align well with experimental values, suggesting that the literature's current assignments warrant reevaluation in light of this new data. The results presented herein can be instrumental in detecting the phase of Mg ferrites from experimental spectra, thereby paving the way for a more profound comprehension of their properties and possible uses.

Chiral knife edge: A simplified rattleback to illustrate spin inversion.

We present the chiral knife edge rattleback, an alternative version of previously presented systems that exhibit spin inversion. We offer a full treatment of the model using qualitative arguments, analytical solutions as well as numerical results. We treat a reduced, one-mode problem which not only contains the essence of the physics of spin inversion, but that also exhibits an unexpected connection to the Chaplygin sleigh, providing insight into the nonholonomic structure of the problem. We also present exact results for the full problem together with estimates of the time between inversions that agree with previous results in the literature.

Simultaneous T1, T2 and T2⁎ mapping of the liver with multi-shot MI-SAGE

PurposeTo apply multi-shot high-resolution multi inversion spin and gradient echo (MI-SAGE) acquisition for simultaneous liver T1, T2 and T2* mapping. MethodsInversion prepared spin- and gradient-echo EPI was developed with ascending slice order across measurements for efficient acquisition with T1, T2, and T2⁎ weighting. Multi-shot EPI was also implemented to minimize distortion and blurring while enabling high in-plane resolution. A dictionary-matching approach was used to fit the images to quantitative parameter maps, which were compared to T1 measured by modified Look-Locker (MOLLI), T1 measured by variable flip angle (VFA), T2 measured by multiple echo time-based Half Fourier Single-shot Turbo spin-Echo (HASTE), T2 measured by radial turbo-spin-echo (rTSE) and T2⁎ measured by multiple gradient echo (MGRE) sequences. ResultsThe multi-shot variant of the sequence achieved higher in-plane resolution of 1.7 × 1.7 mm2 with good image quality in 28 s. Derived quantitative maps showed comparable values to conventional mapping methods. As measured in phantom and in vivo, MOLLI, MESE and MGRE give closest values to MISAGE. VFA, HASTE and rTSE show obvious overestimation. ConclusionsThe proposed multi-shot inversion prepared spin- and gradient-echo EPI sequence allows for high-resolution quantitative T1, T2 and T2 liver tissue characterization in a single breath-hold scan.

Simulation of oriented NMR spectra: Combining molecular dynamics and chemical shift tensor calculations.

Solid state NMR is widely used to study the orientation and other structural features of proteins and peptides in lipid bilayers. Using data obtained by PISEMA (Polarization Inversion Spin Exchange at Magic Angle) experiments, periodic spectral patterns arise from well-aligned α-helical molecules. Significant problems in the interpretation of PISEMA spectra may arise for systems that do not form perfectly defined secondary structures, like α-helices, or the signal pattern is disturbed by molecular motion. Here, we present a new method that combines molecular dynamics simulation with tensorial orientational constraints (MDOC) and chemical shift tensor calculations for the simulation and interpretation of PISEMA-like spectra. The calculations include the spectra arising from non α-helical molecules and molecules with non-uniform intrinsic mobility. In a first step, dipolar or quadrupolar interaction tensors drive molecular rotations and reorientations to obtain the proper mean values as observed in corresponding NMR experiments. In a second step, the coordinate snapshots of the MDOC simulations are geometry optimized with the isotropic 15 N chemical shifts as constraints using Bond Polarization Theory (BPT) to provide reliable 15 N CS tensor data. The averaged dipolar 1 H-15 N couplings and the δzz tensor components can then be combined to simulate PISEMA patterns. We apply this method to the ß-helical peptide gramicidin A (gA) and demonstrate that this method enables the assignment of most PISEMA resonances. In addition, MDOC simulations provide local order parameters for the calculated sites. These local order parameters reveal large differences in backbone mobility between L- and D-amino acids of gA.

VirtMRI: A Tool for Teaching MRI

Magnetic resonance image formation is not trivial and remains a difficult subject for teaching. Therefore, we saw an urgent need to facilitate teaching by developing a practical and easily accessible MR image generator. Due to the increasing interest in X-nuclei MRI, sodium image generation is also offered. The tool is implemented as a web application that is compatible with all standard desktop browsers and is open source. The user interface focuses on the parameters needed for the creation and display of the resulting images. Available MR sequences range from the standard Spin Echo and Inversion Recovery over steady-state to conventional sodium and more advanced single and triple quantum sequences. Additionally, the user interface has parameters to alter the resolution, the noise, and the k-space sampling. Our software is free to use and specifically suited for teaching purposes.

Ferroelectric phase transitions of nanoislands based on transverse ising model

Based on the transverse field Ising model, the phase transition properties of nanoislands with a spin-1/2 are studied by using the usual decoupling approximation of Fermi-type Green’s function. The phase diagram indicates that the phase transition curve (J S /J = t c , Ω S /J ∼ t c ) is highly sensitive to the interlayer exchange interaction (J R /J) and the ratio of surface to center transverse fields (Ω S /Ω). The polarization diagram reveals that the polarization curve exhibits steps attributed to spin inversion, and the temperature of the step point corresponds to the temperature at which spin configuration changes.

Unraveling the Complex Interplay of Phase Transitions in Spinel Ferrites: A Comprehensive Quantum Mechanical Vibrational Study of ZnFe2O4.

The rich phase transition landscape of spinel ferrites and its profound impact on their physical properties have garnered significant interest in recent years. The complex interplay of divalent and trivalent cations distributed across A- and B-sites gives rise to a captivating variety of interactions. In this study, we delve into the structural, electronic, magnetic, and vibrational properties of ZnFe2O4 as a function of the degree of inversion, employing first-principles density functional theory with global and range-separated hybrid functionals and a local basis set. The ground state of ZnFe2O4 is an open-shell system, characterized by Zn atoms occupying tetrahedral sites, Fe atoms residing in octahedral sites, and Fe atom spins exhibiting ligand parallel alignment. In the normal structure, the antiparallel arrangement is less stable than the ferro arrangement by 0.058 eV (673 K) for fully relaxed structures, decreasing to 0.034 eV (395 K) upon incorporating a zero-point vibrations contribution. For normal ferromagnetic ZnFe2O4, we calculated scattering for A1g, Eg, and 3T2g symmetry at 676.6, 367.1, and (189.7, 457.7, 602.3) cm-1, respectively. Additionally, four T1u vibrational frequencies predicted by group theory were obtained at 524.59, 358.48, 312.49, and 192.9 cm-1, demonstrating excellent agreement with the experimental studies. We also explored the influence of spin rearrangement and inversion (X = 0.5 and 1) on Raman and infrared spectra. By analyzing the infrared spectra of isotopic substitutions, we reevaluated the assignments of the four T1u modes in light of available experimental data. Notably, the sensitivity of peak positions and intensities for some Raman modes, particularly A1g and T2g(2), to spin arrangement could provide a convenient experimental tool for detecting phase transitions induced by changes in temperature or external electric fields. This investigation shines a light on the complex interplay of phase transitions in spinel ferrites, paving the way for a deeper understanding of their properties and potential applications.

Triggered Superradiance and Spin Inversion Storage in a Hybrid Quantum System.

We study the superradiant emission of an inverted spin ensemble strongly coupled to a superconducting cavity. After fast inversion, we detune the spins from the cavity and store the inversion for tens of milliseconds, during which the remaining transverse spin components disappear. Switching back on resonance enables us to study the onset of superradiance. A weak trigger pulse of a few hundred photons shifts the superradiant burst to earlier times and imprints its phase onto the emitted radiation. For long hold times, the inversion decreases below the threshold for spontaneous superradiance. There, the energy stored in the ensemble can be used to amplify microwave pulses passing through the cavity.

Exact solution of slow quench dynamics and nonadiabatic characterization of topological phases

Previous studies have shown that the bulk topology of single-particle systems can be captured by the band inversion surface or by the spin inversion surface emerging on the time-averaged spin polarization. Most of the studies, however, are based on the single-particle picture even though the systems are fermionic and multi-bands. Here, we study the slow quench dynamics of topological systems with all the valence bands fully occupied, and show that the concepts of band inversion surface and spin inversion surface are still valid. More importantly, the many-particle nonadiabatic quench dynamics is shown to be reduced to a new and nontrivial three-level Landau–Zener model. This nontrivial three-level Landau–Zener problem is then solved analytically by applying the integrability condition and symmetry considerations, and thus adds a new member to the few models that are exactly solvable. Based on the analytical results, the topological spin texture revealed by the time-averaged spin polarization can be applied to characterize the bulk topology and thus provides a direct comparison for future experiments.

Quantum-based solution of time-dependent complex Riccati equations

Using the Wei-Norman theory we obtain a time-dependent complex Riccati equation (TDCRE) as the solution of the time evolution operator (TEO) of quantum systems described by time-dependent (TD) Hamiltonians that are linear combinations of the generators of the $\mathfrak{su}(1,1)$, $\mathfrak{su}(2)$ and $\mathfrak{so}(2,1)$ Lie algebras. Using a recently developed solution for the time evolution of these quantum systems we solve the TDCRE recursively as generalized continued fractions, which are optimal for numerical implementations, and establish the necessary and sufficient conditions for the unitarity of the TEO in the factorized representation. The inherited symmetries of quantum systems can be recognized by a simple inspection of the TDCRE, allowing effective quantum Hamiltonians to be associated with it, as we show for the Bloch-Riccati equation whose Hamiltonian corresponds to that of a generic TD system of the Lie algebra $\mathfrak{su}(2)$. As an application, but also as a consistency test, we compare our solution with the analytic one for the Bloch-Riccati equation considering the Rabi frequency driven by a complex hyperbolic secant pulse generating spin inversion, showing an excellent agreement.

Prostate lesions characterization using diffusion-weighted spatiotemporal encoded MRI: Feasibility and initial assessment.

To assess the feasibility and reliability of a DWI protocol based on spatiotemporally encoding (SPEN), to target prostate lesions along guidelines normally used in EPI-based DWI clinical practice. Prostate Imaging-Reporting and Data System recommendations underlying clinical prostate scans were used to develop a SPEN-based DWI protocol, which included a novel, local, low-rank regularization algorithm. These DWI acquisitions were run at 3 T under similar nominal spatial resolutions and diffusion-weighting b-values as used in EPI-based clinical studies. Prostates of 11 patients suspected of clinically significant prostate cancer lesions were therefore scanned using the two methods, with the same number of slices, same slice thickness, and same interslice gaps. Of the 11 patients scanned, SPEN and EPI provided comparable information in 7 of the cases, whereas EPI was deemed superior in a case for which SPEN images had to be acquired with a shorter effective TR owing to scan-time constraints. SPEN provided reduced susceptibility to field-derived distortions in 3 of the cases. SPEN's ability to provide prostate lesion contrast was most clearly evidenced for DW images acquired with b ≥ 900 s/mm2 . SPEN also succeeded in decreasing occasional image distortions in regions close to the rectum, affected by field inhomogeneities. EPI advantages arose when using short effective TRs, a regime in which SPEN-based DWI was handicapped by its use of nonselective spin inversions, leading to the onset of an additional T1 weighting.

Two state reactivity (TSR) and hydrogen tunneling reaction kinetics measured in the Co+ mediated decomposition of CH3CHO.

The electronic structure of a transition metal atom allows it to act as a catalytic active site by providing lower energy alternative pathways in chemical transformations. We have identified and kinetically characterized three such pathways in the title reaction. One is an adiabatic pathway that occurs on a single potential energy surface described within the Born-Oppenheimer approximation. A second pathway opens microseconds into the reaction as a portion of the reacting population competitively transitions from triplet to singlet multiplicity to circumvent energetic barriers on the triplet surface. These pathways are single- and two-state reactive (SSR and TSR) where the Co+ cation mediates an oxidative addition/reductive elimination sequence of the CH3CHO molecule. The third observed reaction pathway is the aldehyde hydrogen tunneling through an Eyring barrier to form high-spin products. First-order rate constants for the adiabatic and nonadiabatic energy lowered pathways, and the hydrogen tunneling pathway, are each measured using the single photon initiated dissociative rearrangement reaction (SPIDRR) experimental technique. We believe that this is the first experimental study where such disparate dynamic features (SSR, TSR, and H-tunneling) are disentangled in a system's chemistry, attributing specific rate constant values to each effect and quantifying the various competitions. Moreover, multi-reference CASSCF/CASPT2 calculations indicate that structures with covalent Co-H bonds are present exclusively along the excited singlet surface. This phenomenon significantly reduces these structures' energy relative to their triplet counterparts, thus enabling the surface crossing and spin inversion that cause the observed two-state reactivity.