Superexchange-like interaction of encaged molecular oxygen in nitrogen-doped water cages of clathrate hydrates

Clathrate hydrates are a highly prospective material in energy and environmental fields, but the inherent nature of inclusion phenomena occurring in the stacked water cages has not been completely resolved yet. Investigating the magnetism of guest molecules is a new experimental approach in clathrate hydrate research to open the possibility of icy magnetic applications as a novel material as well as to understand the unrevealed host-guest interactions in icy inclusion compounds. In this study, we observed an indirect spin coupling between encaged dioxygen molecules via a nonmagnetic water framework through the measurement of guest magnetization. This spin coupling is reminiscent of superexchange coupling between magnetic ions through intervening oxygens in antiferromagnetic oxides, such as MnO and CoO. Theoretical calculations revealed that OH(-) incorporated in the framework induced the mixing of perpendicular π* orbitals of two distant dioxygens and that ammonia doping into the hydrate cage leads to a longer lifetime of that orientation.     

Electrically Switchable Magnetic Molecules: Inducing a Magnetic Coupling by Means of an External Electric Field in a Mixed‐Valence Polyoxovanadate Cluster

Herein we evaluate the influence of an electric field on the coupling of two delocalized electrons in the mixed‐valence polyoxometalate (POM) [GeV₁₄O₄₀]^8? (in short V₁₄) by using both a t‐J model Hamiltonian and DFT calculations. In absence of an electric field the compound is paramagnetic, because the two electrons are localized on different parts of the POM. When an electric field is applied, an abrupt change of the magnetic coupling between the two delocalized electrons can be induced. Indeed, the field forces the two electrons to localize on nearest‐neighbors metal centers, leading to a very strong antiferromagnetic coupling. Both theoretical approaches have led to similar results, emphasizing that the sharp spin transition induced by the electric field in the V₁₄ system is a robust phenomenon, intramolecular in nature, and barely influenced by small changes on the external structure.     

Finding all‐nonmetal transition‐metal‐like superatom and its magnetic building block

In novel superatom chemistry, it is very attractive that all‐metal clusters can mimic the behaviors of nonmetal atoms and simple nonmetal molecules. Wizardly all‐metal halogen‐like superatom Al₁₃ with 2P⁵ sub shell (corresponding to the 3p⁵ of chlorine) is the most typical example. In contrast, how to mimic the behaviors of magnetic transition‐metal atom using all‐nonmetal cluster is an intriguing challenge for superatom chemistry. In response to this based on human intuition, using quantum chemistry methods and extending jellium model from metal cluster to all‐nonmetal cluster, we have found out that all‐nonmetal octahedral B₆ cluster with characteristic jellium electron configuration 1S²1P⁶2S²1D⁸ in the triplet ground state can mimic the behaviors of transition‐metal Ni atom with electron configuration 3s²3p⁶4s²3d⁸ in electronic configuration, physics and chemistry. Interestingly, the characteristic order of 1S1P2S1D for the B₆ nonmetal cluster with short B‐B lengths is different from that of the traditional jellium model—1S1P1D2S for metal clusters with long M‐M lengths, which exhibits a novel size effect of nonmetal cluster on jellium orbital ordering. Based on the jellium electron configuration, the B₆ with the spin moment value of 2μ_B is a new all‐nonmetal transition‐metal nickel‐like superatom exhibiting a new kind of all‐nonmetal magnetic superatom. Finding the application of the all‐nonmetal magnetic superatom, we encapsulate the magnetic superatom B₆ inside fully hydrogenated fullerene forming a clathrate B₆@C₆₀H₆₀ with the spin moment value of 2μ_B. As the C₆₀H₆₀ cage as a polymerization unit can conserve the spin moment of endohedral B₆, the clathrate B₆@C₆₀H₆₀ is a new all‐nonmetal magnetic superatom building block. Naturally, magnetic superatom structures of the B₆ and B₆@C₆₀H₆₀ may be metastable.     

Measurement of Spatial Distributions of Electron Density and Electron Temperature in Direct Current Glow Discharge by Double Langmuir Probes

The spatial distributions of electron temperature and density in a dc glow discharge that is created by a pair of planar electrodes were obtained by using double Langmuir probes. The contribution of double Langmuir probes measurement is to provide a relatively quantitative tool to identify the electron distribution behavior. Electrons gain energy from the imposed electric field, and electron temperature (T_e) rises very sharply from the cathode to the leading edge of the negative glow where T_e reaches the maximum. In this region, the number of electrons (N_e) is relatively small and does not increase much. The accelerated electrons lose energy by ionizing gas atoms, and T_e decreases rapidly from the trailing edge of the negative glow and extends to the anode. N_e was observed to increase from the cathode to the anode, which is due to the electron impact ionization and electron movement. The electron density was observed to increase with increasing discharge voltage while the electron temperature remained approximately. At 800 V and 50 mTorr argon glow discharge, Te ranged from 15 to 52 eV and Ne ranged from 6.3×10⁶/cm³ to 3.1×10⁸/cm³ in the DC glow discharge, and T_e and N_e were dependent on the axial position.     

Maximum Spin Polarization in Chromium Dimer Cations as Demonstrated by X‐ray Magnetic Circular Dichroism Spectroscopy

X‐ray magnetic circular dichroism spectroscopy has been used to characterize the electronic structure and magnetic moment of Cr₂⁺. Our results indicate that the removal of a single electron from the 4sσ_g bonding orbital of Cr₂ drastically changes the preferred coupling of the 3d electronic spins. While the neutral molecule has a zero‐spin ground state with a very short bond length, the molecular cation exhibits a ferromagnetically coupled ground state with the highest possible spin of S=11/2, and almost twice the bond length of the neutral molecule. This spin configuration can be interpreted as a result of indirect exchange coupling between the 3d electrons of the two atoms that is mediated by the single 4s electron through a strong intraatomic 3d‐4s exchange interaction. Our finding allows an estimate of the relative energies of two states that are often discussed as ground‐state candidates, the ferromagnetically coupled ¹²Σ and the low‐spin ²Σ state.     

Half metallic properties of LaSrVMoO6

The recent synthesized LaSrVMoO₆ was speculated to be compensated half metal, i.e., half metal with zero magnetic moment. Based on the experimental structure, our first principles study indicates that it is ferrimagnetic and half metallic with the magnetic moment 2.0 μ_B when the electron correlation of Mo 4d electrons is larger than 2.72 eV. This indicates the strong electron correlation effect of Mo 4d electrons. Nonetheless, the obtained large magnetic moment (2.0 μ_B) contradicts with the experimental observed nearly zero magnetic moment. Although the large antisite defects of the experimental sample might be the reason to reduce the saturated magnetic moment, further physical insights need to be investigated. The spin‐orbit coupling effect has minor effect on the studied properties. © 2010 Wiley Periodicals, Inc. J Comput Chem, 2010     

Theoretical study of a novel organic electride with large nonlinear optical responses

The design of stable organic electrides with high nonlinear optical (NLO) properties is a challenge in organic and materials chemistry. Here we theoretically design of a novel organic molecular electride model, Li⁺(C₂₀H₁₅Li₅)e⁻, by modifying the lithiation and Li-doping based on dodecahedrane (C₂₀H₂₀). Its electride characteristic is verified by the quantum theory of atoms in molecules and electron localization function analyses. For the first time, the strategy of steric protection is applied to improve the stability of the organic electride Li⁺@(C₂₀H₁₅Li₅)e⁻, in which the closed C₂₀ cage serves not only as the ligand with a negative inner electric field to stabilize the Li cation but also as a barrier to prevent the Li cation from escaping. Meanwhile, the released excess electron is firmly captured in the cavity of Li₅. Moreover, Li⁺(C₂₀H₁₅Li₅)e⁻ displays a remarkably large first hyperpolarizability of 1.4 × 10⁴ au with potential application in organic second-order NLO materials.     

Intramolecular Spin Alignment within Mono‐Oxidized and Photoexcited Anthracene‐Based π Radicals as Prototypical Photomagnetic Molecular Devices: Relationships Between Electrochemical,Photophysical, and Photochemical Control Pathways

AnOV is a π‐conjugated radical built from an anthracene (An) unit linked by a p‐phenylene to an oxoverdazyl (OV) moiety. The mono‐oxidized (cationic) form of AnOV was generated both electrochemically and photochemically (in the presence of an electron acceptor). The triplet nature (S=1) of the electronic ground state of AnOV ⁺ was demonstrated by combining spectroelectrochemistry, electron‐spin resonance (ESR) experiments, and ab initio molecular orbital (MO) calculations. The intramolecular spin alignment (ISA) within AnOV ⁺ results from the ferromagnetic coupling (J_electrochem>0) of the two unpaired electrons located on the oxidized electron donor (An⁺) and on the pendant OV radical. The spin‐density distribution pattern of AnOV ⁺ is akin to that of AnOV when photopromoted ( AnOV *) to its high‐spin (HS) lowest excited quartet (S=3/2) state. This high‐spin state results from the ferromagnetic coupling (J_photophys>0) of the triplet locally excited state of An (³An*) with the doublet ground state of OV. As a shared salient feature, AnOV ⁺ and AnOV * (HS) show a spin delocalization within the domain of activated An in either An⁺ or ³An* (nexus states) forms. The present study essentially contributes to establish and clarify relationships between electrochemical, photophysical, and photochemical pathways to achieve ISA processes within AnOV . In particular, we discuss the impact of the spin polarization of the unpaired electron of OV on electronic features of the An electron‐donating subunit. Close analysis of this polarizing interplay allows one to derive a novel functional paradigm to manipulate electron spins at the intramolecular level with light and under an external magnetic field. Indeed, two original functional elements are identified: light‐triggered donors of spin‐polarized electrons and spin‐selective electron acceptors, which are of potential interest for molecular spintronics.     

Electric Double‐Layer Capacitor Based on an Ionic Clathrate Hydrate

Herein, we suggest a new approach to an electric double‐layer capacitor (EDLC) that is based on a proton‐conducting ionic clathrate hydrate (ICH). The ice‐like structures of clathrate hydrates, which are comprised of host water molecules and guest ions, make them suitable for applications in EDLC electrolytes, owing to their high proton conductivities and thermal stabilities. The carbon materials in the ICH Me₄NOH ? 5 H₂O show a high specific capacitance, reversible charge–discharge behavior, and a long cycle life. The ionic‐hydrate complex provides the following advantages in comparison with conventional aqueous and polymer electrolytes: 1) The ICH does not cause leakage problems under normal EDLC operating conditions. 2) The hydrate material can be utilized itself, without requiring any pre‐treatments or activation for proton conduction, thus shortening the preparation procedure of the EDLC. 3) The crystallization of the ICH makes it possible to tailor practical EDLC dimensions because of its fluidity as a liquid hydrate. 4) The hydrate solid electrolyte exhibits more‐favorable electrochemical stability than aqueous and polymer electrolytes. Therefore, ICH materials are expected to find practical applications in versatile energy devices that incorporate electrochemical systems.     

Calorimetric study on pure and KOH-doped argon clathrate hydrates

Pure and KOH (x=1.3×10^?3)-doped argon clathrate hydrates were synthesized in an adiabatic high-pressure calorimetric cell from one mole of water and 200 MPa of Ar gas. The heat capacities of the hydrates were measured from 12 to 130 K. No anomaly was found in the pure sample but a glass transition considered to be related to a proton-configurational mode of the host hydrogen-bonded lattice was observed for the first time at 55 K in the doped sample. Comparison with the results on pure and KOH-doped tetrahydrofuran clathrate hydrates indicated that the thermodynamic properties of a hydrogen-bonded system depend on the kind of guest molecule. The heat capacity of argon in the hydrate cages was adequately analyzed with the one-dimensional Pöschl-Teller potential as used in the Ar-β-quinol clathrate and the addivity of heat capacities of the guest and host was shown to be valid in the temperature range 12–130 K.     

电场对金属串配合物M3(dpa)4Cl2 (M=Co,Rh, Ir; dpa=dipyridylamide)结构的影响

应用密度泛函理论PBE0 方法研究具有分子导线潜在应用的金属串配合物M₃(dpa)₄Cl₂ (1: M=Co, 2: M=Rh, 3: M=Ir; dpa=dipyridylamide)在电场作用下的几何和电子结构. 结果表明: 配合物基态均是二重态. 1和2的M₃⁶⁺金属链形成三中心三电子σ键, 3 中M₃⁶⁺形成三中心四电子σ键且存在弱的δ键. 随金属原子周期数增大其M―M键增强、LUMO与HOMO能隙减小、金属原子的反铁磁耦合减弱以至消失且自旋密度向配体的离域增强. 在Cl4→Cl5 电场作用下, 低电势端的M3－Cl5 键缩短, 高电势端的M2―Cl4 键增长, M―M平均键长略为缩短, M―M键增强, 有利于分子线的电子传递; 分子能量降低, 偶极矩线性增大. 低电势端Cl5的负电荷向高电势端Cl4 转移, 且3 中金属原子的正电荷由高电势端向低电势端的转移较明显, 自旋电子由低电势端向高电势端金属原子移动, 但桥联配体dpa^-与M和Cl 所在的分子轴间没有电荷转移. 电场使LUMO与HOMO能隙减小, 有利于分子的电子输运. 随金属原子周期数增大, 电场作用下M―M平均键长变化减小, LUMO、HOMO的能级交错现象减少.     

Heat capacity and transition phenomena of structure I and II trimethylene oxide clathrate hydrates

Heat capacities of structure I and II trimethylene oxide (TMO) clathrate hydrates doped with small amount of potassium hydroxide (x=1.8×10^–4 to water) were measured by an adiabatic calorimeter in the temperature range 11–300 K. In the str. I hydrate (TMO·7.67H₂O), a glass transition and a higher order phase transition were observed at 60 K and 107.9 K, respectively. The glass transition was considered to be due to the freezing of the reorientation of the host water molecules, which occurred around 85 K in the pure sample and was lowered owing to the acceleration effect of KOH. The relaxation time of the water reorientation and its distribution were estimated and compared with those of other clathrate hydrates. The phase transition was due to the orientational ordering of the guest TMO molecules accommodated in the cages formed by water molecules. The transition was of the higher order and the transition entropy was 1.88 J·K^–1(TMO-mol)^–1, which indicated that at least 75% of orientational disorder was remaining in the low temperature phase. In the str. II hydrates (TMO·17H₂O), only one first-order phase transition appeared at 34.5 K. This transition was considered to be related to the orientational ordering of the water molecules as in the case of the KOH-doped acetone and tetrahydrofuran (THF) hydrates. The transition entropy was 2.36 JK^–1(H₂O-mol)^–1, which is similar to those observed in the acetone and THF hydrates. The relations of the transition temperature and entropy to the guest properties (size and dipole moment) were discussed.Contribution No 57 from the Microcalorimetry Research CenterThe authors would like to express their sincere thanks to the Nissan Science Foundation for their financial support.     

Electronic Structure Modulation in an Exceptionally Stable Non‐Heme Nitrosyl Iron(II) Spin‐Crossover Complex

The highly stable nitrosyl iron(II) mononuclear complex [Fe(bztpen)(NO)](PF₆)₂ (bztpen=N‐benzyl‐N,N′,N′‐tris(2‐pyridylmethyl)ethylenediamine) displays an S=1/2?S=3/2 spin crossover (SCO) behavior (T_1/2=370 K, ΔH=12.48 kJ mol^?1, ΔS=33 J K^?1 mol^?1) stemming from strong magnetic coupling between the NO radical (S=1/2) and thermally interconverted (S=0?S=2) ferrous spin states. The crystal structure of this robust complex has been investigated in the temperature range 120–420 K affording a detailed picture of how the electronic distribution of the t_2g–e_g orbitals modulates the structure of the {FeNO}⁷ bond, providing valuable magneto–structural and spectroscopic correlations and DFT analysis.     

Giant Magnetoresistance in the Half‐Metallic Double‐Perovskite Ferrimagnet Mn2FeReO6

The first transition‐metal‐only double perovskite compound, Mn²⁺₂Fe³⁺Re⁵⁺O₆, with 17 unpaired d electrons displays ferrimagnetic ordering up to 520 K and a giant positive magnetoresistance of up to 220 % at 5 K and 8 T. These properties result from the ferrimagnetically coupled Fe and Re sublattice and are affected by a two‐to‐one magnetic‐structure transition of the Mn sublattice when a magnetic field is applied. Theoretical calculations indicate that the half‐metallic state can be mainly attributed to the spin polarization of the Fe and Re sites.     

Magnetic Resonance of Paramagnetic Complexes

The line width of the ESR and NMR signals of paramagnetic transition metal complexes is determined mainly by the electron spin-lattice relaxation time τ_e. Values of τ_e greater than 10^?9 lead to ESR spectra that are readily resolved, while values smaller than 10^?11 give NMR spectra having small line widths. Since fast relaxation processes are effective in nearly all transition metal complexes with several unpaired electrons and in all complexes having an orbitally degenerate ground state, the NMR method has a wider scope. The sign and magnitude of the electron-nucleus coupling can be determined with great sensitivity from the NMR spectra, whereas only the magnitude of this interaction can be determined from the ESR spectra. Free spin densities can be found very accurately from the NMR shifts, and the method can therefore be advantageously applied to kinetic measurements, e.g. on short-lived contact complexes.     

Low energye ± — Li2 scattering using LFCC method

The scattering of slow electrons and positrons by lithium metal dimer has been studied in the laboratory frame close coupling method. The effect of polarization is included through the parameter free model correlation potential given by Perdew and Zunger. In the case of electron, the exchange kernel is replaced by a local model exchange potential as used by Sur and Ghosh. To have a convergent result seven rotational states (j=0, 2, 4, 6, 8, 10, 12) are retained in the coupling scheme. The results for elastic, rotational and total cross sections fore ^? — Li₂ ande ⁺ — Li₂ are reported. The electron results are in fair agreement with measured values and existing theoretical predictions.     

A Molecular Perspective on Lithium–Ammonia Solutions

A detailed molecular orbital (MO) analysis of the structure and electronic properties of the great variety of species in lithium–ammonia solutions is provided. In the odd‐electron, doublet states we have considered: e^?@(NH₃)_n (the solvated electron, likely to be a dynamic ensemble of molecules), the Li(NH₃)₄ monomer, and the [Li(NH₃)₄⁺ ? e^?@(NH₃)_n] ion‐pairs, the Li 2s electron enters a diffuse orbital built up largely from the lowest unoccupied MOs of the ammonia molecules. The singly occupied MOs are bonding between the hydrogen atoms; we call this stabilizing interaction H

     

Low temperature thermodynamic properties of Gd<Subscript>2</Subscript>SrCo<Subscript>2</Subscript>O<Subscript>7</Subscript>

Summary Thermodynamic properties of a layered perovskite oxide Gd₂SrCo₂O₇ have been studied. Powder X-ray diffraction, electric resistivity, magnetic susceptibility and heat capacity measurements were carried out. The crystal structure was determined as I4/mmm. The temperature dependence of the magnetic susceptibility was fitted to the Curie-Weiss behavior with antiferromagnetic interaction. Spin state of Co³⁺ ion was derived to be intermediate spin state configuration (t_2g⁵e_g¹). The spin ordering was observed as a broad anomaly in the heat capacity curve with a peak at 2 K. The measured entropy was 35.47 J K^-1mol^-1, which was 65% of expected value. Thus the spin ordering should not be completed at the lowest temperature 0.2 K covered in the present experiments and/or some short range ordering remains at higher temperatures.     

Ab initio surface hopping excited-state molecular dynamics approach on the basis of spin–orbit coupled states: An application to the A-band photodissociation of CH3I

Ab initio molecular dynamics approach has been extended to multi-state dynamics on the basis of the spin–orbit coupled electronic states that are obtained through diagonalization of the spin–orbit coupling matrix with the multi-state second-order multireference perturbation theory energies in diagonal elements and the spin–orbit coupling terms at the state-averaged complete active space self-consistent field level in off-diagonal elements. Nonadiabatic transitions over the spin–orbit coupled states were taken into account explicitly by a surface hopping scheme with utilizing the nonadiabatic coupling terms calculated by numerical differentiation of the spin–orbit coupled wavefunctions and analytical nonadiabatic coupling terms. The present method was applied to the A-band photodissociation of methyl iodide, CH₃I + hv → CH₃ + I (²P_3/2)/I* (²P_1/2), for which a pioneering theoretical work was reported by Amatatsu, Yabushita, and Morokuma. The present results reproduced well the experimental branching ratio and energy distributions in the dissociative products. © 2018 Wiley Periodicals, Inc.