Macroscopic Magnetic Susceptibility Research Articles

Strewn field, mineralogy, and petrology of Al Haggounia 001: A unique enstatite chondrite

AbstractIn this work, we investigate macroscopic characteristics, magnetic susceptibility, mineralogy, and mineral composition of Al Haggounia 001. The samples were collected during eight field missions in the period between 2015 and 2019. In the strewn field of about 65 km in length, the specimens are found either on the surface or shallowly buried in loose sediments, which rules out the previous suggestions that this meteorite is a fossil meteorite. Macroscopically, the samples exhibit three major lithologies with various colors, porosities, and distributions of oxidized veins. The data obtained using transmitted and reflected light microscopy, scanning electron microscopy, and electron microprobe analysis confirm the macroscopic observations and show a heterogenous distribution of silicates and metal sulfides. Al Haggounia 001 is composed of enstatite, plagioclase, kamacite, taenite, schreibersite, daubreelite, troilite, graphite, sinoite, and silica polymorphs. We identified a new type of chondrules that are flattened and composed of rods of albite and enstatite, as well as elongated nodules of metal and sulfides, in addition to compression fractures in the form of subparallel veinlets. These features presumably reflect the deformation caused by shock. The magnetic susceptibility of Al Haggounia 001 (4.39 ± 0.20) is much lower than that of usual EH (5.48 ± 0.16) and EL (5.46 ± 0.04) chondrites but is in the range of E finds (5.05 ± 0.43). The thermomagnetic and hysteresis measurements are controlled by type, size, distribution of metal‐sulfide nodules, arrangement of oxyhydroxide veins, and weathering. Al Haggounia 001 is an anomalous meteorite with a polymict nature. It records multiple events revealing its unique origin which expends the groups of enstatite chondrites and provides insights into the complex formation and evolution history of their parent body.

Structural Setting, Paleomagnetism, and Magnetic Fabric of Miocene Plutons in a Transpressional Sinistral Shear Zone, Tonalá, Chiapas, Mexico: Evidence of Shortening During Magma Emplacement

AbstractWe studied the structure, paleomagnetism, and magnetic fabric of Miocene granitoids intruded along the left‐lateral, transpressional, Tonalá shear zone in Chiapas, southern Mexico. Magmatic fabrics delineate patterns of regional folding striking parallel to the shear zone, suggesting syn‐magmatic shortening. Magnetic susceptibility fabrics are well developed, and mean magnetic susceptibility averages 18.6 × 10−3 SI. The magnetic fabric of the plutons is controlled primarily by MD and finer PSD magnetite, which also carries the magnetic remanence. The orientations of macroscopic mineral fabrics and magnetic susceptibility fabrics are consistently parallel in protomylonites, but their coincidence is good to poor in granitoids that preserve magmatic fabrics. Most site mean directions are NW‐NE directed of moderate positive inclination (or antipodal), but on a local scale site, mean directions are very discordant. The overall mean direction, omitting highly discordant sites, is of Decl. = 359.6° and Incl. = +41.9° (k = 14.4, α95 = 8.1°, N = 24 sites); it is nearly concordant with the North America reference direction, and the slight difference may indicate a gentle, north‐side down regional tilt. High directional dispersion is interpreted to reflect relative rotation about local vertical to sub‐vertical axes of plutons, or parts of plutons, along the shear zone, with some rotations interpreted to be caused by progressive deformation within the shear zone. Paleomagnetic and AMS data from the protomylonite rocks are interpreted to have been affected by the distortional strain, which accommodated shape and volume change in the rock. We suggest that the introduction of granitic magma into middle crustal levels critically enhanced the crustal response to shortening within the shear zone, possibly due to melt compressibility.

Spin rotation induced by applied pressure in the Cd-doped Ce2RhIn8 intermetallic compound

The pressure evolution of the magnetic properties of the Ce2RhIn7.79Cd0.21 heavy fermion compound was investigated by single crystal neutron magnetic diffraction and electrical resistivity experiments under applied pressure. From the neutron magnetic diffraction data, up to P = 0.6 GPa, we found no changes in the magnetic structure or in the ordering temperature T N = 4.8 K. However, the increase of pressure induces an interesting spin rotation of the ordered antiferromagnetic moment of Ce2RhIn7.79Cd0.21 into the ab tetragonal plane. From the electrical resistivity measurements under pressure, we have mapped the evolution of T N and the maximum of the temperature dependent electrical resistivity (T MAX) as a function of the pressure (P ≲ 3.6 GPa). To gain some insight into the microscopic origin of the observed spin rotation as a function of pressure, we have also analyzed some macroscopic magnetic susceptibility data at ambient pressure for pure and Cd-doped Ce2RhIn8 using a mean-field model including tetragonal crystalline electric field (CEF). The analysis indicates that these compounds have a Kramers doublet -type ground state, followed by a first excited state at Δ1 ∼ 80 K and a Γ6 second excited state at Δ2 ∼ 270 K for Ce2RhIn8 and Δ2 ∼ 250 K for Ce2RhIn7.79Cd0.21. The evolution of the magnetic properties of Ce2RhIn8 as a function of Cd doping and the rotation of the direction of the ordered moment for the Ce2RhIn7.79Cd0.21 compound under pressure suggest important changes of the single ion anisotropy of Ce3+ induced by applying pressure and Cd doping in these systems. These changes are reflected in modifications in the CEF scheme that will ultimately affect the actual ground state of these compounds.

Single-Scan High-Resolution 2-D $J$ -Resolved Spectroscopy in Inhomogeneous Magnetic Fields.

A method is proposed to obtain high-resolution 2-D -resolved nuclear magnetic resonance (NMR) spectra in inhomogeneous magnetic fields. The proposed experiment enables the acquisition of an entire 2-D spectrum in a single scan by utilizing intermolecular double-quantum coherences and the spatial encoding of NMR observables. Chemical shifts, coupling constants, and multiplet patterns are recovered even when field inhomogeneities are severe enough to completely obscure conventional NMR spectra. After intentional deshimming to yield inhomogeneous magnetic fields, the method was demonstrated on ethyl 3-bromoproprionate in acetone and on a complex mixture of organic compounds. To illustrate the technique's applicability to biological samples with intrinsic magnetic field inhomogeneities arising from macroscopic magnetic susceptibility variations, we performed the experiment on a pig bone marrow sample. Our results show that the new method is a fast and effective tool for studying complex chemical mixtures and biological tissues. The method could potentially be useful for real-time in vivo NMR studies.

Spatially Localized Two-Dimensional J-Resolved NMR Spectroscopy via Intermolecular Double-Quantum Coherences for Biological Samples at 7 T.

Background and PurposeMagnetic resonance spectroscopy (MRS) constitutes a mainstream technique for characterizing biological samples. Benefiting from the separation of chemical shifts and J couplings, spatially localized two-dimensional (2D) J-resolved spectroscopy (JPRESS) shows better identification of complex metabolite resonances than one-dimensional MRS does and facilitates the extraction of J coupling information. However, due to variations of macroscopic magnetic susceptibility in biological samples, conventional JPRESS spectra generally suffer from the influence of field inhomogeneity. In this paper, we investigated the implementation of the localized 2D J-resolved spectroscopy based on intermolecular double-quantum coherences (iDQCs) on a 7 T MRI scanner.Materials and MethodsA γ-aminobutyric acid (GABA) aqueous solution, an intact pig brain tissue, and a whole fish (Harpadon nehereus) were explored by using the localized iDQC J-resolved spectroscopy (iDQCJRES) method, and the results were compared to those obtained by using the conventional 2D JPRESS method.ResultsInhomogeneous line broadening, caused by the variations of macroscopic magnetic susceptibility in the detected biological samples (the intact pig brain tissue and the whole fish), degrades the quality of 2D JPRESS spectra, particularly when a large voxel is selected and some strongly structured components are included (such as the fish spinal cord). By contrast, high-resolution 2D J-resolved information satisfactory for metabolite analyses can be obtained from localized 2D iDQCJRES spectra without voxel size limitation and field shimming. From the contrastive experiments, it is obvious that the spectral information observed in the localized iDQCJRES spectra acquired from large voxels without field shimming procedure (i.e. in inhomogeneous fields) is similar to that provided by the JPRESS spectra acquired from small voxels after field shimming procedure (i.e. in relatively homogeneous fields).ConclusionThe localized iDQCJRES method holds advantage for recovering high-resolution 2D J-resolved information from inhomogeneous fields caused by external non-ideal field condition or internal macroscopic magnetic susceptibility variations in biological samples, and it is free of voxel size limitation and time-consuming field shimming procedure. This method presents a complementary way to the conventional JPRESS method for MRS measurements on MRI systems equipped with broad inner bores, and may provide a promising tool for in vivo MRS applications.

Magnetic single-domain state of the monochiral helimagnet MnSi in the zero-field limit: Magnetic properties study

Attention is drawn to a possibility to obtain the monochiral helimagnet MnSi in a magnetic single domain state (SDS) in zero magnetic field limit. It is shown that this metastable zero field magnetic SDS can be achieved by gradual decrease of the field down to zero after initial transformation of MnSi to a spin-polarized state in high fields $H$. This can be achieved only for $\bf{H}\parallel$ [111]. Investigations of MnSi in magnetic SDS give us a possibility to determine the two components of low field magnetic susceptibility of this compound, $\chi_{\perp}(T)$ and $\chi_{\parallel}(T)$ [$\chi_{\perp}$ and $\chi_{\parallel}$ correspond to $\bf{H}\perp$, and $\bf{H}\parallel$ (111)-plane containing magnetic moments in helically ordered state]. These results are compared with macroscopic magnetic susceptibility of MnSi earlier determined for this compound only in magnetic multi domain state (MDS). In addition our results are compared with the data reported for some non-monochiral helimagnets. Characteristic features of monochiral helimagnets are elucidated.

A high-resolution 2D J-resolved NMR detection technique for metabolite analyses of biological samples.

NMR spectroscopy is a commonly used technique for metabolite analyses. Due to the observed macroscopic magnetic susceptibility in biological tissues, current NMR acquisitions in measurements of biological tissues are generally performed on tissue extracts using liquid NMR or on tissues using magic-angle spinning techniques. In this study, we propose an NMR method to achieve high-resolution J-resolved information for metabolite analyses directly from intact biological samples. A dramatic improvement in spectral resolution is evident in our contrastive demonstrations on a sample of pig brain tissue. Metabolite analyses for a postmortem fish from fresh to decayed statuses are presented to further reveal the capability of the proposed method. This method is a previously-unreported high-resolution 2D J-resolved spectroscopy for biological applications without specialised hardware requirements or complicated sample pretreatments. It provides a significant contribution to metabolite analyses of biological samples, and may be potentially applicable to in vivo samples. Furthermore, this method also can be applied to measurements of semisolid and viscous samples.

Macrocharcoal analysis of a 4200 year old lake sediment profile from Northern Romania - fire regimes and climate implications

Macroscopic charcoal particles, magnetic susceptibility and AMS C14 dates were performed on a sediment sequence from a small subalpine lake (Buhaescu Mare), Rodnei Mts. in order to reconstruct fire regimes in the area. Specifically we aim to distinguish between natural fire activity and human driven fires. Buhaescu Mare lake, also known as Rebra lake (0.4 ha; 1920 m a.s.l.,) is today surrounded by mire vegetation, Ericaceae, Carex and Pinus mugo patches further away, being situated just above the current tree line. The sedimentary profile, with a total length of 98 cm is composed of clayey silt (98-80 cm) and gyttja (80-0 cm). Magnetic susceptibility was used to support the charcoal results, this parameter being expected to rise during episodes of intense fire and subsequent erosive events. The results from the charcoal record indicate periods of high charcoal activity at about 4200 cal. BP, 3000 cal. BP, 2700 cal BP, 2000 cal BP and 1350 cal BP. and point to a succession of warm/dry and cold/wet periods. The increase in charcoal particles over the last 2000 years was probably related to human impact, but this remains to be documented through the analysis of pollen and coprophilous fungi record.

Hadamard-encoded high-resolution NMR spectroscopy via intermolecular single-quantum coherences

NMR spectroscopy plays an important role in metabolite studies because it can provide atomic level information critical for understanding biological systems. Nevertheless, NMR investigations on biological tissues are hampered by the magnetic field inhomogeneities originating from variations in macroscopic magnetic susceptibility, which lead to broad spectral lines and subsequently obscure metabolite signals. A new pulse sequence based on intermolecular single-quantum coherences was proposed to obtain one-dimensional high-resolution NMR spectra in inhomogeneous magnetic fields via Hadamard encoding. The new method can provide resolution-improved spectra directly through one-dimensional acquisition within a relatively short acquisition time. Theoretical derivation was performed and the conclusion was tested by solution samples in purposely de-shimmed magnetic fields and pig brain tissue sample. The experimental results show that this sequence can yield useful structural information, even when the field inhomogeneity is sufficiently severe to erase almost all spectral information with conventional one-dimensional single-quantum coherence techniques. Moreover, good solvent suppression efficiency can be achieved by this sequence. This sequence may provide a promising way for high-resolution NMR spectroscopy of biological tissue.

High-Resolution Two-Dimensional J-Resolved NMR Spectroscopy for Biological Systems

NMR spectroscopy is a principal tool in metabolomic studies and can, in theory, yield atom-level information critical for understanding biological systems. Nevertheless, NMR investigations on biological tissues generally have to contend with field inhomogeneities originating from variations in macroscopic magnetic susceptibility; these field inhomogeneities broaden spectral lines and thereby obscure metabolite signals. The congestion in one-dimensional NMR spectra of biological tissues often leads to ambiguities in metabolite identification and quantification. We propose an NMR approach based on intermolecular double-quantum coherences to recover high-resolution two-dimensional (2D) J-resolved spectra from inhomogeneous magnetic fields, such as those created by susceptibility variations in intact biological tissues. The proposed method makes it possible to acquire high-resolution 2D J-resolved spectra on intact biological samples without recourse to time-consuming shimming procedures or the use of specialized hardware, such as magic-angle-spinning probes. Separation of chemical shifts and J couplings along two distinct dimensions is achieved, which reduces spectral crowding and increases metabolite specificity. Moreover, the apparent J coupling constants observed are magnified by a factor of 3, facilitating the accurate measurement of small J couplings, which is useful in metabolic analyses. Dramatically improved spectral resolution is demonstrated in our applications of the technique on pig brain tissues. The resulting spectra contain a wealth of chemical shift and J-coupling information that is invaluable for metabolite analyses. A spatially localized experiment applied on an intact fish (Crossocheilus siamensis) reveals the promise of the proposed method in in vivo metabolite studies. Moreover, the proposed method makes few demands on spectrometer hardware and therefore constitutes a convenient and effective manner for metabonomics study of biological systems.

Magnetic susceptibility anisotropy: Cylindrical symmetry from macroscopically ordered anisotropic molecules and accuracy of MRI measurements using few orientations

White matter is an essential component of the central nervous system and is of major concern in neurodegenerative diseases such as multiple sclerosis (MS). Recent MRI studies have explored the unique anisotropic magnetic properties of white matter using susceptibility tensor imaging. However, these measurements are inhibited in practice by the large number of different head orientations needed to accurately reconstruct the susceptibility tensor. Adding reasonable constraints reduces the number of model parameters and can help condition the tensor reconstruction from a small number of orientations. The macroscopic magnetic susceptibility is decomposed as a sum of molecular magnetic polarizabilities, demonstrating that macroscopic order in molecular arrangement is essential to the existence of and symmetry in susceptibility anisotropy and cylindrical symmetry is a natural outcome of an ordered molecular arrangement. Noise propagation in the susceptibility tensor reconstruction is analyzed through its condition number, showing that the tensor reconstruction is highly susceptible to the distribution of acquired subject orientations and to the tensor symmetry properties, with a substantial over- or under-estimation of susceptibility anisotropy in fiber directions not favorably oriented with respect to the acquired orientations. It was found that a careful acquisition of three non-coplanar orientations and the use of cylindrical symmetry guided by diffusion tensor imaging allowed reasonable estimation of magnetic susceptibility anisotropy in certain major white matter tracts in the human brain.

Magnetic susceptibility anisotropy of human brain in vivo and its molecular underpinnings

Frequency shift of gradient-echo MRI provides valuable information for assessing brain tissues. Recent studies suggest that the frequency and susceptibility contrast depend on white matter fiber orientation. However, the molecular underpinning of the orientation dependence is unclear. In this study, we investigated the orientation dependence of susceptibility of human brain in vivo and mouse brains ex vivo. The source of susceptibility anisotropy in white matter is likely to be myelin as evidenced by the loss of anisotropy in the dysmyelinating shiverer mouse brain. A biophysical model is developed to investigate the effect of the molecular susceptibility anisotropy of myelin components, especially myelin lipids, on the bulk anisotropy observed by MRI. This model provides a consistent interpretation of the orientation dependence of macroscopic magnetic susceptibility in normal mouse brain ex vivo and human brain in vivo and the microscopic origin of anisotropic susceptibility. It is predicted by the theoretical model and illustrated by the experimental data that the magnetic susceptibility of the white matter is least diamagnetic along the fiber direction. This relationship allows an efficient extraction of fiber orientation using susceptibility tensor imaging. These results suggest that anisotropy on the molecular level can be observed on the macroscopic level when the molecules are aligned in a highly ordered manner. Similar to the utilization of magnetic susceptibility anisotropy in elucidating molecular structures, imaging magnetic susceptibility anisotropy may also provide a useful tool for elucidating the microstructure of ordered biological tissues.

Density-operator theory of orbital magnetic susceptibility in periodic insulators

The theoretical treatment of homogeneous static magnetic fields in periodic systems is challenging, as the corresponding vector potential breaks the translational invariance of the Hamiltonian. Based on density operators and perturbation theory, we propose, for insulators, a periodic framework for the treatment of magnetic fields up to arbitrary order of perturbation, similar to widely used schemes for electric fields. The second-order term delivers a new, remarkably simple, formulation of the macroscopic orbital magnetic susceptibility for periodic insulators. We validate the latter expression using a tight-binding model, analytically from the present theory and numerically from the large-size limit of a finite cluster, with excellent numerical agreement.

Estimation of single-ion anisotropies, crystal-field and exchange interactions in Gd-based frustrated pyrochlore anti-ferromagnets Gd2M2O7 (M=Ti, Sn, Hf, Zr)

The temperature dependence of the experimental results of dc (macroscopic) magnetic susceptibility and nuclear hyperfine properties of frustrated magnetic Gd-based pyrochlore compounds, Gd2Ti2O7, Gd2Sn2O7, Gd2Hf2O7 and Gd2Zr2O7, are analyzed within the frame work of appropriate crystal-field theory and a mean field approximation by introducing effective anisotropic molecular field tensors, and formulating an exact relation between single-ion susceptibility tensors and site susceptibility tensors. Components of the calculated susceptibility along and perpendicular to the local 〈111〉 axis of the tetrahedral sublattice of pyrochlore structure show that these pyrochlores are easy-planar anisotropic magnetic systems. The crystal-field parameters and anisotropic exchange coupling have been determined and their systematic variations over the Gd-based pyrochlores studied here are discussed.

Chalcogen-Height Dependent Magnetic Interactions and Magnetic Order Switching inFeSexTe1−x

Magnetic properties of iron chalcogenide superconducting materials are investigated using density-functional calculations. We find that the stability of magnetic phases is very sensitive to the height of chalcogen species from the Fe plane: while FeTe with optimized Te height has the double-stripe (pi, 0) magnetic ordering, the single-stripe (pi, pi) ordering becomes the ground state when Te is lowered below a critical height by, e.g., Se doping. This behavior is understood by opposite Te-height dependences of the superexchange interaction and a longer range magnetic interaction mediated by itinerant electrons. We also demonstrate a linear temperature dependence of the macroscopic magnetic susceptibility in the single-stripe phase in contrast with the constant behavior in the double-stripe phase. Our findings provide a comprehensive and unified view on the magnetism in FeSexTe1-x and iron pnictide superconductors.

On the existence of temperature induced changes in the magnetic topology of crystals that show no first-order crystallographic phase transitions

The First-Principles Bottom– Up study of the 88 K and 273 K X-ray diffraction structures of the bis-2,3-dimethylpyridinium tetrabromocuprate molecular magnet shows that the analysis of the magnetic properties of a molecule-based magnet, that does not present any first order polymorphic transition in the range of temperature studied, depends on the X-ray structure employed. The reason is the thermal expansion anisotropy when the crystal goes from the low temperature phase to 273 K, which induces changes in the radical–radical J AB interactions. As a consequence, the magnetic topology of the low temperature and 273 K structures change, a fact that induces a change in the macroscopic magnetic susceptibility curve (only the 88 K structure of bis-2,3-dimethylpyridinium tetrabromocuprate reproduces well the two-leg spin ladder experimental properties of this magnet). When anisotropic thermal effects are suspected one should use low temperature structures to study the magnetic properties at low temperature, and high temperature structures for the study of the magnetic properties in that range of temperatures.

Vegetation and fire history during the last 18,000 cal yr B.P. in Southern Patagonia: Mallín Pollux, Coyhaique, Province Aisén (45°41′30″ S, 71°50′30″ W, 640 m elevation)

To better understand the climate, vegetation and fire history of southern South America since the last deglaciation, sediment characteristics, diatoms, pollen, microscopic and macroscopic charcoal and magnetic susceptibility were analyzed in a 14-m long sediment core from a closed basin fen at Lago Pollux, Aisén Province, southern Chile (45°41′30″ S lat, 71°50′30″ W long, 640 m elev.). Sediment characteristics, absence of diatoms and scarce pollen suggest that before 18,000 cal yr BP, glacier meltwaters were feeding the small basin when local glaciers were at their maximum position. From 18,000 to ca. 14,000 cal yr BP, the site was a shallow productive pond surrounded by a sparse scrub–steppe and accompanied some fire activity. This period was markedly drier, but warmer than before. By 14,000 cal yr BP, the fen developed and a species-rich steppe expanded suggesting a moderate increase in effective moisture and temperature. High fluctuations of terrestrial and aquatic pollen taxa occur between 14,000 and 11,000 cal yr BP, attesting to climate variability at this time. Between 11,000 and 7500 cal yr BP, Nothofagus steppe–woodland developed and fire activity was very high, with several large local events. Precipitation must have increased, but most likely summers were drier than today with high frequency of convective storms. After 7500 cal yr BP present-day closed Nothofagus forest became established, and fire activity decreased, suggesting establishment of present-day equable precipitation regime. The forest was more open between 4000 and 1500 cal yr BP than before and shrubs or trees grew on the fen. Forest clearance and grazing only began in the mid-20th century. Both in terms of timing and character of past changes in vegetation and fire activity, the record from M. Pollux takes an intermediate position between records from high southern latitudes, versus those from mid-latitudes, indicating the different latitudinal expression of the southern westerly storm tracks during the last 18,000 cal yr BP.

1H NMR spectra and echoes in Pd–H and Pd–Ag–H alloys

The paper presents the experimental results of rigid-lattice proton magnetic resonance spectra and second moments in Pd–H, Pd 0.90Ag 0.10–H, Pd 0.80Ag 0.20–H, Pd 0.75Ag 0.25–H, and Pd 0.65Ag 0.35–H alloys at T = 2.4 K in a wide hydrogen concentration range. Free induction decay (FID), solid and inhomogeneous echoes were detected and interpreted. The interpretation based on dipole–dipole interaction of homogeneously distributed proton spin system is satisfactory at high hydrogen concentration, but an inhomogeneous field of paramagnetic origin (most probably coming from Fe impurities) plays the dominant role at small hydrogen content. An unexpected correlation was found between the macroscopic magnetic susceptibility and the second moment coming from the inhomogeneous internal field.

Magnetic state of f electrons in δ-phase of Pu–Ga alloys studied by Ga NMR

69Ga nuclear magnetic resonance (NMR) line shift ( 69 K) and nuclear spin–lattice relaxation rate ( 69 T 1 −1) are measured for Pu 0.95Ga 0.05 alloy, stabilized in δ-phase, in the temperature range 10 and 650 K at magnetic field of 9.4 T. The shift and 69 T 1 −1 are determined correspondingly by the static and fluctuating-in-time parts of the local magnetic fields arisen at Ga due to transferred hyperfine coupling with the nearest f electron environment of more magnetic Pu. At T > 200 K, the temperature dependent part of the shift 69 K( T) scales macroscopic magnetic susceptibility χ( T), following the Curie–Weiss law, and the product ( 69 T 1 T) increases with temperature proportionally ( T + 255) 1.5(1). Both of the NMR observations are typical of the incoherent spin fluctuation regime of f electrons in nonmagnetic 3D Kondo lattice. An estimate of the effective magnetic moment μ eff,5f( g e = 2) = 0.15(5) μ B per Pu atom points out a strong suppression of the spin magnetism in the alloy.

Direct versus Mediated Through‐Space Magnetic Interactions: A First Principles, Bottom‐Up Reinvestigation of the Magnetism of the Pyridyl‐Verdazyl:Hydroquinone Molecular Co‐Crystal

The mechanism of the magnetic interaction in the pyridyl-verdazyl radical:hydroquinone (pyvd:hq) molecular co-crystal is important as it has been suggested to originate by a unique "mediated through-space" magnetic interaction. This interaction was proposed to magnetically connect two nonadjacent pyridyl-verdazyl radicals within a pi stack, where adjacent radicals pile up in a head-over-tail orientation. The connection is made through a third radical sitting between the previous two mediated radicals. Given the relevance of this proposal, we decided to reinvestigate the magnetic properties of this co-crystal by using our recently proposed first-principles "bottom-up" procedure. Based on B3LYP/6-31+G(d) and CASSCF(6,6)/6-31+G(d) calculations (the results of which are identical to those provided by CASSCF(10,10)/6-31+G(d) calculations), we have computed the microscopic J(AB) values for all direct through-space magnetic interactions between nearby pyridyl-verdazyl radicals. The magnetic interactions give rise to two dominant values of similar strength: -56 and -54 cm(-1) at the B3LYP level, which are calculated as -38 and -31 cm(-1) at the CASSCF(6,6) and CAS(10,10) levels (all other interactions being smaller than |1| cm(-1)). The dominant interactions correspond to the direct through-space interaction between two adjacent radicals of a pi stack. The crystal also exhibits a radical-mediated through-space interaction of -0.31 cm(-1) between two nonadjacent radicals of a pi stack. The direct through-space magnetic interactions are two orders of magnitude larger than the mediated through-space interaction. Thus, first-principles calculations do not support a mediated through-space mechanism to explain the magnetism of the pyvd:hq co-crystal. The magnetic topology generated by the two dominant antiferromagnetic interactions in the pyvd:hq co-crystal consists of one-dimensional (1D) alternating chains (interacting very weakly along the b and c axes). By using this topology, the computed macroscopic magnetic susceptibility curve reproduces the experimental one properly. This first-principles bottom-up description of the magnetism in the pyvd:hq co-crystal differs in some fundamental aspects from that previously proposed in the literature.