Transient absorption spectroscopy of a monofullerene C<Subscript>60</Subscript>-bis-(pyropheophorbide <Emphasis Type="Italic">a</Emphasis>) molecular system in polar and nonpolar environments

The population dynamics of the excited and ground states of the monofullerene-bis (pyropheophorbide a) complex (FP1) were studied in polar (DMF) and nonpolar (toluene) solvents using picosecond transient absorption techniques. A strong quenching of the fluorescence signal of FP1 was observed in both solvents, in comparison to the fluorescence of bis (pyropheophorbide a) (P2). This quenching is due to an intramolecular photoinduced electron transfer from the pyropheophorbide a (pyroPheo) moiety to the fullerene C₆₀ monoadduct. In DMF the charge-separated (CS) state of FP1 has a lifetime of 0.32 ns and undergoes a direct transition to the ground state, resulting in a very low value of photosensitised singlet oxygen generation. In toluene, energy transfer from the first excited triplet state of pyroPheo, which has been populated via relaxation of the CS state, generates a considerable amount of singlet oxygen. The lifetime of the CS state in the nonpolar solvent was estimated to be 0.29 ns. It was also shown that in both DMF and toluene the first excited singlet state as well as the triplet state of the fullerene moiety in FP1 are not occupied. PACS 31.70.Dk; 31.70.Hq; 33.50.-j; 34.70.+e     

The structure of fullerite C<Subscript>60</Subscript> intercalated with molecular oxygen

A (O₂) _x C₆₀ sample with a high content of oxygen (x ≥ 0.4) and free of technological solvent impurities was obtained by precipitation from solution. For the first time, the results of the determination of the x coefficients using ¹³C NMR and elemental analysis were compared. It was shown by Raman spectroscopy, mass spectrometry, and NMR that the inclusion of oxygen into fullerite was accompanied by a decrease in the frequency of O=O stretching vibrations by no less than 12 cm⁻¹ compared with gaseous O₂. Nevertheless, oxygen exists in the molecular form in (O₂)_0.4C₆₀ and is released in the form of O₂ as the sample is heated to 373 K. The number of oxygen molecules occupying octahedral pores closets to the fullerene molecule takes on all the possible values, from 0 to 6. At room temperature, the (O₂) _x C₆₀ sample lost oxygen much more slowly than similar products prepared by diffusion saturation of pure fullerite with oxygen.     

光敏化反应生成单线态氧的电子耦合计算及其分子轨道重叠描述

三重态融合反应又称三重态-三重态湮灭反应,近年来被广泛应用于光催化、太阳能电池和生物成像等前沿领域. 在光敏化生成单线态氧的反应中,三重态激发的光敏剂分子通过三重态融合反应将激发态能量传递给基态氧分子³O₂,生成单重态的激发氧分子即单线态氧. 本文以6-aza-2-thiothymine为光敏剂,通过量子化学计算得到该反应的非绝热耦合强度,然后通过分子间运动下的积分转换,得到反应的透热电子耦合强度. 最后使用光敏剂分子和O₂的前线分子轨道计算轨道重叠强度,对量子化学计算得到的电子耦合值进行拟合,验证三重态融合反应的分子轨道重叠描述. 结果表明,分子轨道重叠可以较好地描述不同间距下光敏剂-O₂三线态融合反应的电子耦合强度分布,为预测三重态融合反应电子耦合提供了一种简便而有效的新方法.     

Specific features of the luminescence of singlet oxygen in solutions of fullerene in aerated organic liquids

The luminescence of singlet oxygen at wavelengths of 760 and 1270 nm in solutions of fullerene in aerated organic liquids irradiated by high-power short laser pulses and by xenon lamps is considered theoretically. The obtained analytical formulas allow one to determine the lifetimes of the ¹Σ O₂ and ¹Δ O₂ oxygen levels, as well as the rate constant of the reaction of generation of singlet oxygen by triplet fullerene in this solution.     

Statics and dynamics of excited states of oxygen-deficient centers in SiO<Subscript>2</Subscript>

The parameters of excited states of oxygen-deficient centers (ODCs) in high-energy-electron irradiated crystalline and glassy SiO₂ have been studied using optical absorption, luminescence, and photoelectron emission spectroscopy. Additional evidence has been gained in support of the model of a neutral oxygen vacancy in ODCs, the diagram of electronic transitions has been refined, and their characteristics have been quantified. The possibility of ionization of the singlet and triplet defect states at a transition to the anomalously relaxed configuration has been demonstrated using the particular example of α-ODCs. Nonradiative excitation transfer from nonbridging oxygen centers to the triplet ODC state has been observed.     

Glass and phase transitions in solid C<Subscript>60</Subscript> charged with Ar,Ne, He,and O<Subscript>2</Subscript>

C₆₀ pellets, charged respectively with He, Ne, Ar, and O₂ under high pressure, were studied with complex impedance spectroscopy. The latter two were found to depress the temperatures for both the phase change (T_c) and glass transition (T_g), although in time shifts, they stayed almost constant in the Ar, but decreased in the O₂, case. The effective barriers for the glass transition were determined as 218±15 meV in Ar_0.49C₆₀ and 182±20 meV in (O₂)_0.5C₆₀. In contrast, neither He nor Ne had a discernible influence on these material parameters. These observations could be explained as follows. (1) Interstitial Ar causes a reduction in the energy barrier and a weakening in the restorative force of the cage libration mode, thereby depressing T_c. (2) For (O₂)_0.5C₆₀, coupling between the cage libration and the tumbling of an O₂ diatomic molecule further weakens the restorative force, so that a larger temperature shift results. (3) Its tumbling motion makes O₂ more susceptible to the “paddle wheel” action of rotating C₆₀ and more easy to diffuse even under ambient conditions.     

Potential Energy Surface for Oxidation of Indenyl C<Subscript>9</Subscript>H<Subscript>7</Subscript>

Ab initio calculations were performed to obtain local energy extrema, including an effect of reagents, intermediates, and reaction products on the potential energy surface for the C₉H₇+O₂ reaction, playing a significant role in oxidation of polycyclic aromatic hydrocarbons at combustion conditions. The final products, determined as a result of the calculations are styrenyl radical C₈H₇+CO₂, ortho-vinyl phenyl radical C₈H₇+CO₂ and 1-H-inden-1-one C₉H₆O+OH, which is predicted to be the prevailing reaction product.     

A quantum-chemical study of intermediates of the 1O2 photogeneration sensitized by buckminsterfullerene and accompanying photochemical reactions

The intermediates of hypothetical photochemical reactions that accompany the quenching of the ³C ₆₀ ^* triplet state by triplet oxygen are studied by the (U)PBE0 quantum-chemical method. The diradical C₆₀-O-O formed from ³O₂ and photoexcited buckminsterfullerene ³C ₆₀ ^* is characterized by a negative binding energy ?1.11 eV (with respect to C₆₀ and ³O₂), the singlet-triplet splitting ΔE _ST of 0.07 eV, and the dipole moment of 3.2 D at the equilibrium internuclear separations 1.522 Å (CO) and 1.294 Å (OO). Its decay produces ¹O₂. The formation of a dioxetane circle lowers the energy by 0.8 eV. The ground-state energy of diketone C₅₈(C=O)₂ is 2.0 eV lower than the energy of C₆₀-O-O. The metastable centrosymmetric diradical C₆₀-C₆₀, formed upon ineffective light absorption by clusters (C₆₀)_N, has a single interpolyhedral C-C bond (1.657 Å). Its triplet state T ₁ lies 0.16 eV higher than the S ₁ singlet. The S ₁ → S ₀ relaxation leads to the formation of a stable C₆₀-C₆₀ dimer with a shorter (1.584 Å) bis-single exothermic (+0.24 eV) bond of polyhedra. The photoexcited C₆₀-C₆₀ dimer is able to form isomeric metastable diradicals C₆₀-C₆₀-O-O.     

Thermal stability of EuMnO<Subscript>3</Subscript> compound

We determine the low-oxygen border of the region of homogeneity for the compound showing the pressure of oxygen and temperrature at which it is possible to obtain materials based on EuMnO₃ with various useful properties. It is established that under conditions of low oxygen pressures, EuMnO₃ dissociates according to the reaction EuMnO₃ = 1/2Eu₂O₃ + MnO + 1/4O₂ in the temperature range of 973–1190 K. We determine temperature dependences of the equilibrium pressure of oxygen and the changes in free Gibbs energy for this reaction. The thermodynamic parameters for the formation of EuMnO₃ from its elements are calculated on the basis of our experimental data.     

Yield of singlet oxygen from optically pumped CCl<Subscript>4</Subscript> solution of fullerenes

Boiling occurs in a solution of oxygen and fullerenes in CCl₄ upon optical pumping of C₆₀ upon the fast appearance of incandescent fullerenes in cold solvent. Upon single-photon absorption, a spherical zone of the critical state of CCl₄ is formed within 5 ns (with a diameter of 22–25 nm, P _cr ∼ 45 atm, and T _cr ∼ 556 K). This spherical zone (gas-bubble nucleus) expands to a diameter of ∼100–400 nm for 2–5 ns. If the external pressure (natural or artificial) is rapidly released, the bubble accelerates and emerges into a vacuum chamber within 0.7–25 μs (the length of the passage is 0.1–5 cm depending on the construction of the singlet oxygen generator). We note that singlet oxygen appears 50 ns after the absorption of a photon by fullerene (i.e., inside of the almost formed gas bubble that only begins to emerge from the liquid to a low-pressure gas region).     

HgO-added YB<Subscript>a2</Subscript>Cu<Subscript>3</Subscript>O<Subscript>7</Subscript>−δ superconductors

The HgO-added YB_a2Cu₃O_7−δ (YBCO) superconductor has been studied for its structural and superconducting properties. Polycrystalline YBCO samples were synthesized through solid-state reaction method by adding HgO in different concentrations without using oxygen annealing. All the samples showed a sharp superconducting transition temperature around 90 K. The X-ray diffraction patterns of all the samples revealed monophasic Y-123 nature. The structural studies were carried out by neutron scattering and Rietveld analysis. The neutron scattering revealed that Hg is not incorporated in the Y-123 system and has shown optimum oxygen concentration. The significant role played by the HgO is to provide oxygen ambient through its decomposition, thus changing the oxygen balance in favour of high Cu-valence state.     

Electronic Structure of Oxygen Vacancies in the Orthorhombic Noncentrosymmetric Phase Hf<Subscript>0.5</Subscript>Zr<Subscript>0.5</Subscript>O<Subscript>2</Subscript>

The electronic structure of stoichiometric and oxygen-depleted Hf_0.5Zr_0.5O₂ in the orthorhombic noncentrosymmetric phase has been studied by X-ray photoelectron spectroscopy and quantum-chemical simulation based on the density functional theory. It has been established that the ion-etching-induced peak in the photoelectron emission spectrum with the energy above the top of the o-Hf_0.5Zr_0.5O₂ valence band is due to oxygen vacancies. A method of estimating the density of oxygen vacancies from the comparison of the experimental and theoretical photoelectron spectra of the valence band has been proposed. It has been established that oxygen polyvacancies in o-Hf_0.5Zr_0.5O₂ are not formed: the energetically favorable spatial arrangement of oxygen vacancies in a crystal corresponds to noninteracting oxygen vacancies distant from each other.     

Synthesis and application of nanostructured MCo<Subscript>2</Subscript>O<Subscript>4</Subscript>(M=Co,Ni) for hybrid Li-air batteries

We report the synthesis of MCo₂O₄ (M=Co, Ni) on Ni-mesh by a simple metal acetate decomposition method. Stability tests of the samples in aqueous acidified LiCl, LiOH and LiTFSI in H₂O/DME showed that Co₃O₄/Ni and Co₃O₄-PVP/Ni are relatively stable in alkaline and neutral environments, with Co₃O₄/Ni being relatively more stable. For NiCo₂O₄/Ni and NiCo₂O₄-PVP/Ni, the low weight percentage change of cobalt in LiTFSI in H₂O/DME suggests that they are mostly stable in this electrolyte. The electrochemical performance of the Li-air cell was evaluated using Li anode and a LAGP ceramic separator with above mentioned electrolytes. Co₃O₄ showed slightly higher catalytic activity for oxygen reduction reaction (ORR) than for oxygen evolution reaction (OER) for the first three cycles. The cell with LiTFSI in H₂O/DME as aqueous catholyte showed that NiCo₂O₄ is a better catalyst for the OER than for the ORR, while the reverse was observed when LiOH was used as the electrolyte.     

Magnetic and structural anomalies of Na<Subscript><Emphasis Type="Italic">n</Emphasis></Subscript>C<Subscript>60</Subscript> (n = 2, 3)

Sodium fullerides Na _n C60 (n = 2, 3) have been synthesized by a liquid phase reaction and investigated with X-ray diffraction (XRD), nuclear magnetic resonance (NMR), electron paramagnetic resonance, and differential thermal analysis. XRD data indicate that the crystal structure of Na₂C₆₀ at 300 K is face centered cubic (FCC). A phase transition from primitive cubic to FCC crystal structure has been observed in this work in Na₂C₆₀ fulleride at 290 K. The transition is accompanied by the step-like change of paramagnetic susceptibility. The crystal structure of Na₃C₆₀ is more complicated than, and different from, what has been reported in the literature. A nearly seven-fold increase of paramagnetic susceptibility with increasing temperature has been observed in the Na₃C₆₀ fulleride at 240–260 K. In the same temperature range, a new line at about 255 ppm appears in the ²³Na NMR spectrum, indicating a significant increase of electron density near the Na nucleus. The observed effect can be explained by a metal-insulator transition caused by a structural transition.     

Effect of oxygen and iodine on the optical and magnetic properties of fullerite C<Subscript>60</Subscript>

The effect of oxygen and iodine on the optical and magnetic properties of fullerite C₆₀ is studied by luminescence and EPR spectroscopy within widely varied experimental conditions (temperature of the medium, oxygen or buffer gas pressure, concentration of iodine vapor). It is demonstrated that the efficiency of the singlet oxygen formation when a fullerene sample is irradiated by a neodymium laser at a wavelength of 532 nm and the amplitude of the EPR signal emitted from the unirradiated sample are strongly affected by the concentrations of both oxygen and iodine vapor sorbed by the fullerene sample, as well as by its surface temperature. The spin-spin and spin-lattice relaxation times of paramagnetic centers in fullerite samples studied in the presence of molecular oxygen are determined by the method of microwave radiation absorption saturation.     

Dynamics and efficiency of the photosensitized singlet oxygen formation by chlorin <Emphasis Type="Italic">e</Emphasis><Subscript>6</Subscript>: The effects of the solution pH and polyvinylpyrrolidone

The effects of the solution pH and polyvinylpyrrolidone on the dynamics and efficiency of the formation of singlet oxygen ¹O₂ in buffer media (pH 6.3–8.5) photosensitized by chlorin e ₆ are studied. It is demonstrated that the quantum yield of the ¹O₂ formation photosensitized by chlorin e ₆ decreases with decreasing solution pH due to the aggregation of photosensitizer molecules. Polyvinylpyrrolidone facilitates the disaggregation of chlorin e ₆, thus increasing its photosensitizing ability. For a complex of chlorin e ₆ with this polymer, the luminescence kinetics of singlet oxygen is inverted, which should be taken into account in the determination of the lifetime of ¹O₂ in real biological systems.     

Asymmetric Anderson model and spin excitations in the Kondo insulator YbB<Subscript>12</Subscript>

A cluster problem is analyzed as an example demonstrating that the observed three-mode behavior of spin-triplet excitations in YbB₁₂ can be described by the asymmetric Anderson model with insulating singlet ground state. In the case of an infinite system, it is argued that the behavior of the f subsystem can be analyzed by using an effective Hamiltonian ? _J with direct antiferromagnetic f-f exchange interaction. The spin excitation spectrum is shown to have a minimum at the antiferromagnetic vector, as observed experimentally. A distinctive feature of the analysis is the use of singlet and triplet basis operators.     

Evolution of MgAl<Subscript>2</Subscript>O<Subscript>4</Subscript> crystals in Al-Mg-SiO<Subscript>2</Subscript> composites

The present study analyzes the morphological transformations of reaction products i.e., MgO, MgAl₂O₄ occurring during the reaction between SiO₂ and Al-Mg alloy in Al-Mg-SiO₂ composite processed by the liquid metallurgy technique. Different phases of platelet and hexagonal morphologies are detected and their composition analysis by EDS has confirmed them as being transition phases existing between MgO, MgAl₂O₄ and Al₂O₃. This study has also revealed the gradual transformation of (i) MgO needles to octahedral MgAl₂O₄ through Mg-Al-Si-O and Mg-Al-O transition phases having platelet morphologies and (ii) MgAl₂O₄ to Al₂O₃ through hexagonal transition phases on holding of Al-5Mg-SiO₂ and Al-1Mg-SiO₂ composites respectively at 1023K. Fully developed α-Al₂O₃ crystals are not observed under the present experimental conditions, wherein the Mg content is well above the equilibrium Mg content required for the formation of stable Al₂O₃ (<0.05 wt. %). PACS 05.70.Np     

Atomic and Electronic Structures of Intrinsic Defects in Ta<Subscript>2</Subscript>O<Subscript>5</Subscript>: Ab Initio Simulation

The atomic and electronic structure of intrinsic point defects in orthorhombic tantalum oxide has been studied by numerical simulation within the density functional theory. It has been shown that all defects responsible for metal enrichment of Ta₂O₅ serve as electron and hole traps. Under conditions of strong oxygen depletion and at a metal–insulator interface, which are characteristic of resistive memory elements, interstitial tantalum atoms compete with an oxygen vacancy in the formation of a conducting filament. Interstitial oxygen atoms are not involved in charge transport. Tantalum substituting oxygen can be considered as a combination of the oxygen vacancy and interstitial tantalum. The analysis of the calculated thermal and optical energies of trap ionization shows that the oxygen vacancy is a key defect for charge transport in Ta₂O₅.     

CaCuMn<Subscript>6</Subscript>O<Subscript>12</Subscript> vs. CaCu<Subscript>2</Subscript>Mn<Subscript>5</Subscript>O<Subscript>12</Subscript>: A comparative study

The ferrimagnetic compounds Ca(Cu_xMn_3?x)Mn₄O₁₂ of the double distorted perovskites AC₃B₄O₁₂ family exhibit a rapid increase of the ferromagnetic component in magnetization at partial substitution of square coordinated (Mn³⁺)_C for (Cu²⁺)_C. In the transport properties, this is seen as a change of the semiconducting type of resistivity for the metallic one. The evolution of magnetic properties of Ca(Cu_xMn_3?x)Mn₄O₁₂ is driven by strong antiferromagnetic exchange interaction of (Cu²⁺)_C with (Mn³⁺/Mn⁴⁺)_B coordinated octahedra. The competing interactions of (Mn³⁺)_C with (Mn³⁺/Mn⁴⁺)_B lead to the formation of noncollinear magnetic structures that can be aligned by magnetic fields.