自旋三重态超导

超导体中的库珀对通常是由一对自旋相反总自旋为零(自旋单态)的电子组成.然而,在某些特殊情况下,超导体中的库珀对可以是自旋三重态,这类超导体被称之为自旋三重态超导体.自旋三重态超导是非常罕见的量子现象,在已经发现的上万种超导体中,仅有几个超导体可能具有三重态配对.近几年,随着拓扑物态研究的深入,三重态超导体因为可能是拓扑超导的载体而越来越多地引起关注.本文简要地总结了几类可能的自旋三重态超导体的物理性质.     

Supercurrent reversal in quantum dots

When two superconductors are electrically connected by a weak link--such as a tunnel barrier--a zero-resistance supercurrent can flow. This supercurrent is carried by Cooper pairs of electrons with a combined charge of twice the elementary charge, e. The 2e charge quantum is clearly visible in the height of voltage steps in Josephson junctions under microwave irradiation, and in the magnetic flux periodicity of h/2e (where h is Planck's constant) in superconducting quantum interference devices. Here we study supercurrents through a quantum dot created in a semiconductor nanowire by local electrostatic gating. Owing to strong Coulomb interaction, electrons only tunnel one-by-one through the discrete energy levels of the quantum dot. This nevertheless can yield a supercurrent when subsequent tunnel events are coherent. These quantum coherent tunnelling processes can result in either a positive or a negative supercurrent, that is, in a normal or a pi-junction, respectively. We demonstrate that the supercurrent reverses sign by adding a single electron spin to the quantum dot. When excited states of the quantum dot are involved in transport, the supercurrent sign also depends on the character of the orbital wavefunctions.     

Unconventional superconductivity in PuCoGa5

In the Bardeen-Cooper-Schrieffer theory of superconductivity, electrons form (Cooper) pairs through an interaction mediated by vibrations in the underlying crystal structure. Like lattice vibrations, antiferromagnetic fluctuations can also produce an attractive interaction creating Cooper pairs, though with spin and angular momentum properties different from those of conventional superconductors. Such interactions have been implicated for two disparate classes of materials--the copper oxides and a set of Ce- and U-based compounds. But because their transition temperatures differ by nearly two orders of magnitude, this raises the question of whether a common pairing mechanism applies. PuCoGa5 has a transition temperature intermediate between those classes and therefore may bridge these extremes. Here we report measurements of the nuclear spin-lattice relaxation rate and Knight shift in PuCoGa5, which demonstrate that it is an unconventional superconductor with properties as expected for antiferromagnetically mediated superconductivity. Scaling of the relaxation rates among all of these materials (a feature not exhibited by their Knight shifts) establishes antiferromagnetic fluctuations as a likely mechanism for their unconventional superconductivity and suggests that related classes of exotic superconductors may yet be discovered.     

Coexistence of superconductivity and ferromagnetism in URhGe

The discovery of superconductivity at high pressure (albeit over a restricted range) in the ferromagnetic material UGe2 raised the possibility that bulk superconductivity might be found in other ferromagnets. The exact symmetry of the paired state and the dominant mechanism responsible for the pairing, however, remain unidentified. Meanwhile, the conjecture that superconductivity could occur more generally in ferromagnets has been fuelled by the recent observation of a low-temperature transition that suggests an onset of superconductivity in high-quality crystals of the itinerant-ferromagnet ZrZn2 (ref. 2), although the thermodynamic signature of this transition could not be detected. Here we show that the ferromagnet URhGe is superconducting at ambient pressure. In this case, we find the thermodynamic signature of the transition-its form is consistent with a superconducting pairing of a spin-triplet type, although further testing with cleaner samples is needed to confirm this. The combination of superconductivity and ferromagnetism may thus be more common and consequently more important than hitherto realized.     

The a.c. and d.c. Josephson effects in a Bose-Einstein condensate

The alternating- and direct-current (a.c. and d.c.) Josephson effects were first discovered in a system of two superconductors, the macroscopic wavefunctions of which are weakly coupled via a tunnelling barrier. In the a.c. Josephson effect, a constant chemical potential difference (voltage) is applied, which causes an oscillating current to flow through the barrier. Because the frequency is proportional to the chemical potential difference only, the a.c. Josephson effect serves as a voltage standard. In the d.c. Josephson effect, a small constant current is applied, resulting in a constant supercurrent flowing through the barrier. In a sense, the particles do not 'feel' the presence of the tall tunnelling barrier, and flow freely through it with no driving potential. Bose-Einstein condensates should also support Josephson effects; however, while plasma oscillations have been seen in a single Bose-Einstein condensate Josephson junction, the a.c. Josephson effect remains elusive. Here we observe the a.c. and d.c. Josephson effects in a single Bose-Einstein condensate Josephson junction. The d.c. Josephson effect has been observed previously only in superconducting systems; in our study, it is evident when we measure the chemical potential-current relation of the Bose-Einstein condensate Josephson junction. Our system constitutes a trapped-atom interferometer with continuous readout, which operates on the basis of the a.c. Josephson effect. In addition, the measured chemical potential-current relation shows that the device is suitable for use as an analogue of the superconducting quantum interference device, which would sense rotation.     

Quantum supercurrent transistors in carbon nanotubes

Electronic transport through nanostructures is greatly affected by the presence of superconducting leads. If the interface between the nanostructure and the superconductors is sufficiently transparent, a dissipationless current (supercurrent) can flow through the device owing to the Josephson effect. A Josephson coupling, as measured by the zero-resistance supercurrent, has been obtained using tunnel barriers, superconducting constrictions, normal metals and semiconductors. The coupling mechanisms vary from tunnelling to Andreev reflection. The latter process has hitherto been observed only in normal-type systems with a continuous density of electronic states. Here we investigate a supercurrent flowing through a discrete density of states-that is, the quantized single particle energy states of a quantum dot, or 'artificial atom', placed between superconducting electrodes. For this purpose, we exploit the quantum properties of finite-sized carbon nanotubes. By means of a gate electrode, successive discrete energy states are tuned on- and off-resonance with the Fermi energy in the superconducting leads, resulting in a periodic modulation of the critical current and a non-trivial correlation between the conductance in the normal state and the supercurrent. We find, in good agreement with existing theory, that the product of the critical current and the normal state resistance becomes an oscillating function, in contrast to being constant as in previously explored regimes.     

超导电流的动量守恒与超导电子对隧道效应

讨论了稳恒电流的动量守恒现象,由此分析了直流约瑟夫森隧道效应。指出,描述约瑟夫森隧道效应的2个基本方程遵循稳恒电流动量守恒定律;约瑟夫森隧道结上的超导电子对质心定向运动速度比隧道结2侧超导体内的超导电子对质心定向运动速度大3个数量级：vS2～1 03 vS1;约瑟夫森隧道结上超导电子对的质心定向运动速度和动量很大的原因在于其运动遵循稳恒电流动量守恒定律;约瑟夫森隧道结上超导电子对质心定向运动速度可以达到费米速度的数量级、其定向运动动能可以达到费米能的数量级,从而使隧道结由超导态转变成正常态。     

Kondo effect in an integer-spin quantum dot

The Kondo effect--a many-body phenomenon in condensed-matter physics involving the interaction between a localized spin and free electrons--was discovered in metals containing small amounts of magnetic impurities, although it is now recognized to be of fundamental importance in a wide class of correlated electron systems. In fabricated structures, the control of single, localized spins is of technological relevance for nanoscale electronics. Experiments have already demonstrated artificial realizations of isolated magnetic impurities at metallic surfaces, nanoscale magnets, controlled transitions between two-electron singlet and triplet states, and a tunable Kondo effect in semiconductor quantum dots. Here we report an unexpected Kondo effect in a few-electron quantum dot containing singlet and triplet spin states, whose energy difference can be tuned with a magnetic field. We observe the effect for an even number of electrons, when the singlet and triplet states are degenerate. The characteristic energy scale is much larger than in the ordinary spin-1/2 case.     

Bose-Einstein condensation of the triplet states in the magnetic insulator TlCuCl3

Bose-Einstein condensation denotes the formation of a collective quantum ground state of identical particles with integer spin or intrinsic angular momentum. In magnetic insulators, the magnetic properties are due to the unpaired shell electrons that have half-integer spin. However, in some such compounds (KCuCl3 and TlCuCl3), two Cu2+ ions are antiferromagnetically coupled to form a dimer in a crystalline network: the dimer ground state is a spin singlet (total spin zero), separated by an energy gap from the excited triplet state (total spin one). In these dimer compounds, Bose-Einstein condensation becomes theoretically possible. At a critical external magnetic field, the energy of one of the Zeeman split triplet components (a type of boson) intersects the ground-state singlet, resulting in long-range magnetic order; this transition represents a quantum critical point at which Bose-Einstein condensation occurs. Here we report an experimental investigation of the excitation spectrum in such a field-induced magnetically ordered state, using inelastic neutron scattering measurements of TlCuCl3 single crystals. We verify unambiguously the theoretically predicted gapless Goldstone mode characteristic of the Bose-Einstein condensation of the triplet states.     

Thermal spin current from a ferromagnet to silicon by Seebeck spin tunnelling

Heat generation by electric current, which is ubiquitous in electronic devices and circuits, raises energy consumption and will become increasingly problematic in future generations of high-density electronics. The control and re-use of heat are therefore important topics for existing and emerging technologies, including spintronics. Recently it was reported that heat flow within a ferromagnet can produce a flow of spin angular momentum-a spin current-and an associated voltage. This spin Seebeck effect has been observed in metallic, insulating and semiconductor ferromagnets with temperature gradients across them. Here we describe and report the demonstration of Seebeck spin tunnelling-a distinctly different thermal spin flow, of purely interfacial nature-generated in a tunnel contact between electrodes of different temperatures when at least one of the electrodes is a ferromagnet. The Seebeck spin current is governed by the energy derivative of the tunnel spin polarization. By exploiting this in ferromagnet-oxide-silicon tunnel junctions, we observe thermal transfer of spins from the ferromagnet to the silicon without a net tunnel charge current. The induced spin accumulation scales linearly with heating power and changes sign when the temperature differential is reversed. This thermal spin current can be used by itself, or in combination with electrical spin injection, to increase device efficiency. The results highlight the engineering of heat transport in spintronic devices and facilitate the functional use of heat.     

Magnetic enhancement of superconductivity from electron spin domains

Since the discovery of superconductivity, there has been a drive to understand the mechanisms by which it occurs. The BCS (Bardeen-Cooper-Schrieffer) model successfully treats the electrons in conventional superconductors as pairs coupled by phonons (vibrational modes of oscillation) moving through the material, but there is as yet no accepted model for high-transition-temperature, organic or 'heavy fermion' superconductivity. Experiments that reveal unusual properties of those superconductors could therefore point the way to a deeper understanding of the underlying physics. In particular, the response of a material to a magnetic field can be revealing, because this usually reduces or quenches superconductivity. Here we report measurements of the heat capacity and magnetization that show that, for particular orientations of an external magnetic field, superconductivity in the heavy-fermion material CeCoIn(5) is enhanced through the magnetic moments (spins) of individual electrons. This enhancement occurs by fundamentally altering how the superconducting state forms, resulting in regions of superconductivity alternating with walls of spin-polarized unpaired electrons; this configuration lowers the free energy and allows superconductivity to remain stable. The large magnetic susceptibility of this material leads to an unusually strong coupling of the field to the electron spins, which dominates over the coupling to the electron orbits.     

UGe2在铁磁态下费米面

近些年发现UGe2在一定压强和温度下铁磁态与超导态共存,因为以前传统理论认为铁磁态与超导态之间是竞争关系,所以共存的可能性很小.这引起了人们的极大兴趣.由于超导凝聚电子对一般只发生在费米面附近,费米面的图像的研究,对于这个问题的研究有很重要的意义.本文重点介绍,材料UGe2在铁磁态下费米面的变化.     

Spin-based logic in semiconductors for reconfigurable large-scale circuits

Research in semiconductor spintronics aims to extend the scope of conventional electronics by using the spin degree of freedom of an electron in addition to its charge. Significant scientific advances in this area have been reported, such as the development of diluted ferromagnetic semiconductors, spin injection into semiconductors from ferromagnetic metals and discoveries of new physical phenomena involving electron spin. Yet no viable means of developing spintronics in semiconductors has been presented. Here we report a theoretical design that is a conceptual step forward-spin accumulation is used as the basis of a semiconductor computer circuit. Although the giant magnetoresistance effect in metals has already been commercially exploited, it does not extend to semiconductor/ferromagnet systems, because the effect is too weak for logic operations. We overcome this obstacle by using spin accumulation rather than spin flow. The basic element in our design is a logic gate that consists of a semiconductor structure with multiple magnetic contacts; this serves to perform fast and reprogrammable logic operations in a noisy, room-temperature environment. We then introduce a method to interconnect a large number of these gates to form a 'spin computer'. As the shrinking of conventional complementary metal-oxide-semiconductor (CMOS) transistors reaches its intrinsic limit, greater computational capability will mean an increase in both circuit area and power dissipation. Our spin-based approach may provide wide margins for further scaling and also greater computational capability per gate.     

Interplay of magnetism and high-Tc superconductivity at individual Ni impurity atoms in Bi2Sr2CaCu2O8+delta.

Magnetic interactions and magnetic impurities are destructive to superconductivity in conventional superconductors. By contrast, in some unconventional macroscopic quantum systems (such as superfluid 3He and superconducting UGe2), the superconductivity (or superfluidity) is actually mediated by magnetic interactions. A magnetic mechanism has also been proposed for high-temperature superconductivity. Within this context, the fact that magnetic Ni impurity atoms have a weaker effect on superconductivity than non-magnetic Zn atoms in the high-Tc superconductors has been put forward as evidence supporting a magnetic mechanism. Here we use scanning tunnelling microscopy to determine directly the influence of individual Ni atoms on the local electronic structure of Bi2Sr2CaCu2O8+delta. At each Ni site we observe two d-wave impurity states of apparently opposite spin polarization, whose existence indicates that Ni retains a magnetic moment in the superconducting state. However, analysis of the impurity-state energies shows that quasiparticle scattering at Ni is predominantly non-magnetic. Furthermore, we show that the superconducting energy gap and correlations are unimpaired at Ni. This is in strong contrast to the effects of non-magnetic Zn impurities, which locally destroy superconductivity. These results are consistent with predictions for impurity atom phenomena derived from a magnetic mechanism.     

均双核配合物Co(Ⅱ)-Co(Ⅱ)的密度泛函研究

用密度泛函方法,在ROB3LYP/SDD//ROB3LYP/LANL2MB水平上,对Co(Ⅱ)-Co(Ⅱ)均双核配合物进行了理论计算,优化得到了它的单、三重态的平衡几何构型,计算了它们的谐振动频率.结果表明:配合物分子的三重态比单重态稳定,电子自旋布居高度集中在两Co原子上,体系中存在较弱的自旋离域效应.配合物的磁轨道分析表明:体系的铁磁性耦合作用主要来自于d-π*-d反键的超交换作用.     

Generation and characterization of a fairly stable triplet carbene

Most molecules are held together by covalent bonds-electron pairs jointly shared by the two atoms that are linked by the bond. Free radicals, in contrast, have at least one unpaired electron. In the case of carbon-based radicals, the carbon atom at the radical centre no longer makes four bonds with other atoms as it would do in its normal, tetravalent state. The presence of unpaired electrons renders such radicals highly reactive, so they normally occur only as transient intermediates during chemical reactions. But the discovery by Gomberg in 1900 of triphenylmethyl, the first relatively stable free radical containing a central trivalent carbon atom, illustrated that radicals with suitable geometrical and electronic structures can be stable. Compounds containing a divalent carbon atom that uses only two of its four valence electrons for bonding are usually less stable than Gomberg-type radicals with trivalent carbon. Although the role of these so-called carbenes in chemical reactions has long been postulated, they were unambiguously identified only in the 1950s. More recently, stable carbenes have been prepared, but the singlet state of these molecules, with the two nonbonding valence electrons paired, means that they are not radicals. Carbenes in the second possible electronic state, the triplet state, are radicals: the two nonbonding electrons have parallel spins and occupy different orbitals. Here we report the preparation and characterization of a triplet carbene, whose half-life of 19 minutes at room temperature shows it to be significantly more stable than previously observed triplet carbenes.     

四苯基铁卟啉双氧加合物的密度泛函理论研究

采用密度泛函理论方法计算了自旋多重度为1、3、5的四苯基铁卟啉双氧加合物(FeTPPO2)的几何构型及电子性质。考察了四苯基铁卟啉对分子氧的活化。研究发现,FeTPPO2能量随自旋多重度升高而降低。五重态FeTPPO2的能量最低,但其铁卟啉对分子氧的活化效果最差。FeTPPO2中Oa—Ob键键长随自旋多重度变化的规律为三重态>单重态>五重态,说明三重态FeTPPO2中分子氧活化最明显。Fe—Oa键键长和Oa—Ob键键长呈负相关关系。电荷布居分析表明,FeTPPO2中分子氧活化程度与分子氧上所带负电荷多少有关,所带负电荷越多,分子氧活化越明显。分析自旋密度得知,三重态FeTPPO2中分子氧为单线态分子氧。三重态和五重态FeTPPO2中,铁离子均向分子氧转移了β电子,有利于铁氧键的形成。     

Resonance in the electron-doped high-transition-temperature superconductor Pr0.88LaCe0.12CuO4-delta

In conventional superconductors, the interaction that pairs the electrons to form the superconducting state is mediated by lattice vibrations (phonons). In high-transition-temperature (high-T(c)) copper oxides, it is generally believed that magnetic excitations might play a fundamental role in the superconducting mechanism because superconductivity occurs when mobile 'electrons' or 'holes' are doped into the antiferromagnetic parent compounds. Indeed, a sharp magnetic excitation termed 'resonance' has been observed by neutron scattering in a number of hole-doped materials. The resonance is intimately related to superconductivity, and its interaction with charged quasi-particles observed by photoemission, optical conductivity, and tunnelling suggests that it might play a part similar to that of phonons in conventional superconductors. The relevance of the resonance to high-T(c) superconductivity, however, has been in doubt because so far it has been found only in hole-doped materials. Here we report the discovery of the resonance in electron-doped superconducting Pr0.88LaCe0.12CuO4-delta (T(c) = 24 K). We find that the resonance energy (E(r)) is proportional to T(c) via E(r) approximately 5.8k(B)T(c) for all high-T(c) superconductors irrespective of electron- or hole-doping. Our results demonstrate that the resonance is a fundamental property of the superconducting copper oxides and therefore must be essential in the mechanism of superconductivity.     

气相中Ir^＋与CH4分子自旋禁阻反应中C—H键活化机理的理论研究

采用密度泛函理论和高级电子相关耦合簇方法,在CCSD（T）/6-311＋＋G（3df,3pd）//B3LYP/6-311＋G（d,p）的理论水平下,研究了3个自旋态势能面上自旋禁阻反应Ir^＋（^5F）＋CH4（^1A1）→IrCH2^＋（3A″）＋H2（1Σg^＋）的微观机理,通过自旋-轨道耦合的计算,讨论了势能面交叉和可能的自旋翻转过程.结果表明,Ir^＋与CH4的反应中不同势能面之间的“系间窜越”（ISC）将会发生,分子体系通过3次自旋翻转沿着热力学最有利的反应路径进行,最优的反应路径总放热量为44.64 kJ/mol.运用Harvey等的方法优化出最低能量交叉点（MECP）,并计算了MECP处相应的自旋-轨道耦合常数（SOC）,分别为346.95,2 545.62,2 990.98 cm^-1,较大的SOC值说明了自旋翻转是有效的.     

The origin of multiple superconducting gaps in MgB2

Magnesium diboride, MgB2, has the highest transition temperature (T(c) = 39 K) of the known metallic superconductors. Whether the anomalously high T(c) can be described within the conventional BCS (Bardeen-Cooper-Schrieffer) framework has been debated. The key to understanding superconductivity lies with the 'superconducting energy gap' associated with the formation of the superconducting pairs. Recently, the existence of two kinds of superconducting gaps in MgB2 has been suggested by several experiments; this is in contrast to both conventional and high-T(c) superconductors. A clear demonstration of two gaps has not yet been made because the previous experiments lacked the ability to resolve the momentum of the superconducting electrons. Here we report direct experimental evidence for the two-band superconductivity in MgB2, by separately observing the superconducting gaps of the sigma and pi bands (as well as a surface band). The gaps have distinctly different sizes, which unambiguously establishes MgB2 as a two-gap superconductor.