O2 diffusion in SiO2: triplet versus singlet

We address the diffusion of the oxygen molecule in SiO2, using first-principles spin-polarized total-energy calculations. We find that the potential energy surfaces for the singlet and triplet states are very different in certain regions, and that the O2 molecule preserves its spin-triplet ground state not only at its most stable interstitial position inside the solid but also throughout its diffusion pathway. Therefore, the singlet state is not a good approximation to describe the behavior of O2 inside SiO2, and spin-polarization effects are fundamental to understand the properties of this system.     

E' centers in alpha quartz in the absence of oxygen vacancies: a first-principles molecular-dynamics study

The displacement of an oxygen atom in pure alpha quartz is studied via first-principles molecular dynamics. The simulations show that when an O atom in a Si-O-Si bridge is moved away from its original equilibrium position, a new stable energy minimum can be reached. Depending on the spin state and charge Q of the system, this minimum can give rise to either a threefold oxygen (singlet ground state and Q=+1) or to an unsaturated Si atom carrying a dangling bond (triplet state). In the latter case, the hyperfine parameters associated with the 29Si dangling bond are in rather good agreement with electron paramagnetic resonance/electron nuclear double resonance experiments.     

Effect of halogen atom on electron spin polarization studied by CIDEP,using halogen substituted aromatic acyl compounds

The reaction and spin dynamics of the photocleavage reaction of 2-chloro-2′-acetylnaphthalene were studied by time-resolved FT-EPR and transient absorption (TA) spectroscopy. The photocleavage reaction from both singlet and triplet states was observed by TA and EPR experiments, although the radical cleavage reaction in the excited triplet state is energetically unfavourable. This feature has been explained by the ionic cleavage reaction due to the electro-negativity of the chlorine atoms. The time-resolved FT-EPR spectra were similar to those observed in the bromine substituted compound, 2-BAN, reported in a previous paper. The origin of the electron spin polarization was assigned to the radical triplet pair mechanism (RTPM) and free radical pair mechanism (F-pair RPM) from analysis of the time profiles of the spin polarization.     

Adsorption of triplet O(2) on Si(100): the crucial step in the initial oxidation of a silicon surface

It has long been understood that a precursor mediated chemisorption is a significant part of the dynamics for the adsorption of O(2) on Si(100), which is a much studied model system of surface reaction with considerable technological relevance. However, theoretical studies on the interaction between O(2) and Si(100) have been focused on the excited singlet state of O2 and unable to explain the observations in surface scattering experiments. We demonstrate by first principles calculations that such a focus is misplaced. In reality, triplet O(2) can also react with Si(100), after overcoming small barriers, and its reaction paths provide a full account for experiments. Our results highlight the important role played by triplet O(2) in surface oxidation.     

理论研究V2O6-的结构和电子性质

采用自旋非限制密度泛函(B3LYP)方法研究了V2O6-的结构和电子性质,得到的基态和前人的理论计算结果不同．V2O6-阴离子是具有C2v对称性的双重基态,而以前Vyboishchikov等人得到的结果为D2h对称性双重基态．V2O6中性分了是具有D2h对称性的开壳层单重基态,它的能量和三重态的非常接近,而Vyboishchikov等人和Calatayud等人分别得到D2h对称性的闭壳层单重基态和Cs对称性的三重基态．从该基态结果出发计算出的电子分离能和实验上的PES谱相符,相反前人得到的电子分离能和实验相差较大．     

Controlling and detecting spin correlations of ultracold atoms in optical lattices

We report on the controlled creation of a valence bond state of delocalized effective-spin singlet and triplet dimers by means of a bichromatic optical superlattice. We demonstrate a coherent coupling between the singlet and triplet states and show how the superlattice can be employed to measure the singlet-fraction employing a spin-blockade effect. Our method provides a reliable way to detect and control nearest-neighbor spin correlations in many-body systems of ultracold atoms. Being able to measure these correlations is an important ingredient in studying quantum magnetism in optical lattices. We furthermore employ a SWAP operation between atoms which are part of different triplets, thus effectively increasing their bond-length. Such a SWAP operation provides an important step towards the massively parallel creation of a multiparticle entangled state in the lattice.     

Douglas Henderson: a life in statistical mechanics

In a previous study (Wang, L. S., Nicholas, J. B., Dupuis, M., Wu, H., and Colson, S. D., 1997, Phys. Rev. Lett., 78, 4450) of small silicon oxide clusters with stochiometry Si3Oy(y = 1-6), it was found that the molecule Si3O2 and its anion required special theoretical attention. This is due to a particular electronic structure feature of the neutral cluster: the s,p hybrid atomic orbitals of the two bonded silicon atoms give rise to a low lying empty π molecular orbital. As a result the ground state of Si3O2 has a triplet spin, and a state of singlet spin is a low lying excited electronic state at about 0.5 eV above the triplet state. Ab initio molecular orbital calculations show that photoelectron detachment proceeds from the 2B1 state of the anion to the 3B1 ground state of the neutral cluster. Detachment via the 1A1 state of the neutral cluster lies in the shoulder of the detachment via the triplet state.     

强脉冲磁场冲击处理对铝基复合材料塑性的影响机制

铝基复合材料在加入颗粒相之后, 延伸率和塑性变形能力明显降低. 为改善其塑性变形能力, 通过对比强脉冲磁场冲击处理前后试样内部组织和残余应力的变化特征, 研究了磁致塑性效应对铝基复合材料塑性变形能力的影响机理. 结果表明: 当磁感应强度从2 T变化到4 T时, 铝基复合材料中位错密度显著增加, 4 T时的位错密度是未加磁场时的3.1倍; 3 T, 30个脉冲处理后的复合材料中残余应力值从未加磁场时的41 MPa减小为-1 MPa. 从原子尺度来看, 强磁场导致了磁致塑性效应, 从而引起了位错的运动, 并促进了位错的退钉扎和可移动位错数量的增加; 从材料内部整体结构变化来看, 磁场加速了材料内应力的释放速率, 降低了材料内部的残余应力, 从而改善了铝基复合材料的塑性变形能力.     

Final state interaction as the main mechanism of double hole creation in atomic K shells during electromagnetic nuclear decays

Large violations of the OZI-rule have been observed in pp-annihilation into ? mesons when the initial state is in triplet spin configuration. One possible explanation for this phenomenon is that this is due to a small negatively polarized ss?-component in the nucleon which has been found in polarized deep inelastic scattering of leptons. In the nonperturbative region there is little experimental information on the sign of Δs. We show by spin projection conservation arguments that if the ?-production enhancement in the p?p → ?π is due to the transfer of a ss? from the initial nucleon to the final ?, then Δs must be preferentially positive. We study polarization phenomena in the process N + N → + N+ V⁰ where V⁰ is a vector meson near threshold and we show that a comparison of the pp → pp? reaction (which is dominated by a spin triplet in the initial state, at threshold) and the np → np? (which is driven by non-interfering spin triplet and spin singlet amplitudes) would test quantitatively the ss?-driven spin triplet dominance. Finally we discuss the possibility of using the relationship between the Gerasimov-Drell-Hearn sum-rule and the integral of the spin structure function g_1p to measure the polarization of the ss?-component at low momentum transfer.     

铜配合物的光物理与电致发光性能

以中心原子为铜的磷光材料Cu4(C≡Cph)4L2[L=1，8-bis(diphenylphosphino)-3，6-dioxaoctane](简称Cu4)作为掺杂材料，选用空穴传输材料聚乙烯基咔唑(PVK)为母体材料，制作结构为ITO／Cu4PVK／TAZ／Mg：Ag／Ag的双层器件。其发光颜色随掺杂的变化而改变，在较高掺杂浓度的条件下，可观察到单纯Cu4的发光，即实现了单重态到三重态的能量转移。着重讨论了主客体材料间的能量转移过程，并研究了影响器件效率的外界因素如氧气的猝灭对Cu4发光强度的影响。     

EPR of photo-excited triplet states: A personal account

A sketch is presented of the path that has led from Zavoisky’s pioneering experiments to modern investigations by electron paramagnetic resonance (EPR) of the phosphorescent (S = 1) triplet state of polyatomic molecules or ions. The group-theoretical method first introduced by Wigner in his analysis of the multiplets of atomic spectroscopy, likewise provides a key for understanding the zero-field splitting and selection rules for radiative decay of the phosphorescent triplet state. Examples to illustrate the progress made through EPR experiments are selected from three fields. (i) Conformational instability on excitation. Both the zero-field splitting and the electron spin density distribution provide unique fingerprints of a triplet state’s geometry — structural information of a kind that is nonexistent for singlet states! Illustrations are provided by benzene C₆H₆ and fullerene C₆₀. (ii) The optical pumping cycle. The spin selectivity of singlet-to-triplet intersystem crossing and radiative decay of the individual spin components of the triplet state is discussed. In practice this selectivity is put to advantage by performing EPR on triplet states in zero-field by means of optical detection. In turn, such experiments have led to a detailed insight into the spin-orbit coupling mechanisms responsible for the spin selectivity of the above processes. The high sensitivity attainable with optical detection has recently culminated in EPR experiments on single molecules. (iii) Quantum interference. In a triplet state of low symmetry two of the spin sublevels may decay to the ground state by the emission of photons of a common polarization (i.e., out of plane for an aromatic hydrocarbon). In such a situation quantum interference between the two decay channels can be induced by an appropriate preparation of the excited state. An example is shown where flash-excitation in the singlet manifold followed by rapid intersystem crossing causes theS = 1 spin angular momentum to be created in a spin state which is not an eigenstate of the zero-field splitting tensor. This nonstationary character of the initial triplet state, which reflects the spin-orbit coupling pathway, is observed through the detection of a spontaneous microwave signal following the 25 ps laser flash.     

Oxidation of carbon nanotubes by singlet O2

Chemisorption of singlet (1)Delta(g) O2 on single-walled carbon nanotubes is reexamined by first principles calculations, and the reaction barrier is substantially lower than previously reported when the spin on O2 is correctly treated. The process is initiated by the cycloaddition of a singlet O2 on top of a C-C bond and ended with an epoxy structure with each of the two oxygen atoms occupying a bridge position. The overall process is exothermic, with an activation barrier as low as 0.61 eV for the (8, 0) tube. Our results raise the possibility that carbon nanotubes with small diameters could be degraded after exposure to air and sunlight, similar to the degradation of natural rubber and synthetic plastics.     

Josephson current versus potential strength of the interface in ferromagnetic superconductors

Based on the scattering theory, we calculate the Josephson current in a junction between two ferromagnetic superconductors as a function of the interface potential z. We consider the ferromagnetic superconductor(FS) in three different Cooper pairing states: spin singlet s-wave pairing(SWP) state, spin triplet opposite spin pairing(OSP) state, and spin triplet equal spin pairing(ESP) state. We find that the critical Josephson current as a function of z shows clear differences among the SWP, OSP, and ESP states. The obtained results can be used as a useful tool for determining the pair symmetry of the ferromagnetic superconductors.     

Ground state properties of S = 1 antiferromagnetic chain systems studied by ESR

Electron spin resonance (ESR) was used to study the ground state properties of two kinds of spin (S) one Heisenberg antiferromagnetic chain systems, namely a uniform chain system (HAUC), which is well known as the Haldane system, and a bond alternating chain system (HABA). To investigate and compare the features of the ground state, two nickel chain compounds doped with non-magnetic Zn²⁺ impurities were studied. The HAUC was modelled with Ni(1,3-pn)₂(μ-NO₂)(ClO₄)(1,3-pn = 1,3-propanediamine), abbreviated as NINO, while the HABA was modelled with Ni(333-tet)(μ-NO₂)(ClO₄) (333-tet = bis-(3-aminopropyl)-1,3-propanediamine), abbreviated as NTENP. Both systems have a singlet ground state with an excitation gap. The ground state of NINO approximates well to the valence bond solid state, thus producing S = 1/2 spins at the sites neighbouring the impurities. The angular dependence of the ESR signals of NINO:Zn is explained by the anisotropy of the g tensor for spin 1/2. On the other hand, the ground state of NTENP is expected to be in the singlet dimer phase based on the ratio of alternating bond strengths. In this case, it is expected that the S = 1 spins will appear at the sites neighbouring the impurities without forming the singlet dimer. From ESR studies of NTENP:Zn was observed the triplet state (S = 1), induced by the impurity doping, which is consistent with the above picture.     

Theoretical study of mechanisms for NCO with CH3 reaction

A detailed computational study has been performed at the QCISD(T)/6-311++G(d,p)//B3LYP/6-311++G(d,p) level for the NCO with CH₃ reaction by constructing singlet and triplet potential energy surfaces (PES). The results show that the title reaction is more favorable for the singlet PES than the triplet PES. On the singlet PES, the dominant channel is the barrierless addition of the O or N atom to the C atom of the methyl group to form CH₃NCO (IM1) and CH₃OCN (IM2). On the triplet PES, the favorable channel is the barrierless addition of the N atom to the C atom of the methyl group to form an intermediate CH₃NCO (³IM2), which then undergoes a N–C bond scission process to give out CH₃N + CO.     

Time-dependent Hartree-Fock theory

The lowest singlet and triplet excited states of the two paired electrons in a chemical bond are treated by the time-dependent Hartree-Fock (H.F.) method, with the π electrons of the double bond in ethylene as an example. The results depend on a dimensionless parameter g which describes the strength of the electron correlation effects, and they are compared with a simple configuration interaction calculation. When g is small the frequencies and amplitudes of the Hartree-Fock oscillations give an accurate estimate of the energies and intensities of the two lowest transitions, the correlation energy and the pair distribution function of the gound state. The correlation energy is related to the zero-point energy of the oscillations. As g increases the H.F. method overestimates the correlation corrections and breaks down completely if g = 1. At this point the triplet oscillation becomes unstable, because the molecular orbital wave-function with two paired electrons ceases to be the state of lowest energy. When g is large the H.F. results violate spin conservation and the exclusion principle.     

Generalization of the Cooper pairing mechanism for spin-triplet in superconductors

A generalization of the Cooper pairing mechanism is proposed which allows for a triplet state of lower energy. This is achieved by incorporating spin into the canonical commutation relations and by modifying the δ potential contact interaction. The gap equation contain as solutions both singlet and triplet states. It is shown that the triplet state is lower in energy than the singlet state which may explain the spin-triplet superconductivity observed.     

撞击诱导硝基甲烷分子第一步分解反应的动力学计算

本文基于分子温度与压强的关系,计算在不同压强下基态和最低三态硝基甲烷的分子温度,对应计算其沿着CN键裂解反应的热化学和动力学参数.发现基态的硝基甲烷沿着CN键的分解反应是吸热反应,不具自发性,反应转换温度为1550.2 K,平衡常数在80-1202 K温度范围内很低.最低三态的硝基甲烷沿着CN键的裂解是放热反应,反应的Gibbs自由能在80-2558.5 K范围内为负,有好的自发性,且反应较为彻底.298.15-2558.5 K温度范围内反应活化能随着温度的升高而改变,使反应速率随着温度的升高而急剧增大.对应硝基甲烷爆压15 GPa,其分子温度为4617.6 K,该温度下三态分子分解反应的反应速率为1.088×10~8cm~3·mol~(-1)·s~(-1).推算硝基甲烷沿着CN键分解反应混合物的终态温度,当混合物为硝基、甲基和基态的硝基甲烷分子时,反应的终温为1611.37 K,等效能为1676.47 cm~(-1).当混合物为硝基、甲基、基态和最低三态的硝基甲烷分子时,反应的终温为1184.79 K,等效能为1232.65 cm~(-1).两种情况下终态等效能都足以维持硝基甲烷分子沿C-N键裂解反应的发生.这个能量也足以导致混合物中的NO_2分解为NO和O,这与实验检测的结论相一致.     

An investigation of the structure of free-base porphycene by time-resolved electron nuclear double resonance and density functional theory on the photoexcited triplet state

The photoexcited triplet state of free-base porphycene has been investigated by time-resolved electron nuclear double resonance spectroscopy at 10 K. In order to determine whether porphycene is cis or trans configured, experimentally determined A_zz hyperfine coupling tensor components are compared with those predicted from density functional theory. The structures of cis and trans porphycene, in both the singlet ground state and lowest excited triplet state were calculated using the Becke3-Lee-Yang-Parr composite exchange correlation functional and the 6–31G* basis set. Hyperfine couplings for these structures were then calculated using the same functional but with the extended EPR-II basis set. From the results it can be concluded that porphycene has a trans configuration in both the ground singlet and lowest excited triplet state. Additionally, the significant differences in structure between the singlet and triplet states are reflected in the calculated hyperfine couplings, with those for the trans conformation in the triplet state in reasonable agreement with the experimental values.