Anomalous behavior of proton zero point motion in water confined in carbon nanotubes

The momentum distribution of the protons in ice Ih, ice VI, high density amorphous ice, and water in carbon nanotubes has been measured using deep inelastic neutron scattering. We find that at 5 K the kinetic energy of the protons is 35 meV less than that in ice Ih at the same temperature, and the high momentum tail of the distribution, characteristic of the molecular covalent bond, is not present. We observe a phase transition between 230 and 268 K to a phase that does resemble ice Ih. Although there is yet no model for water that explains the low temperature momentum distribution, our data reveal that the protons in the hydrogen bonds are coherently delocalized and that the low temperature phase is a qualitatively new phase of ice.     

Quantum and classical relaxation in the proton glass

The hydrogen-bond network formed from a crystalline solution of ferroelectric RbH2PO4 and antiferroelectric NH4H2PO4 demonstrates glassy behavior, with proton tunneling the dominant mechanism for relaxation at low temperature. We characterize the dielectric response over seven decades of frequency and quantitatively fit the long-time relaxation by directly measuring the local potential energy landscape via neutron Compton scattering. The collective motion of protons rearranges the hydrogen bonds in the network. By analogy with vortex tunneling in superconductors, we relate the logarithmic decay of the polarization to the quantum-mechanical action.     

(1)H and (87)Rb nuclear magnetic resonance study of the order-disorder phase transition of RbHSeO(4) single crystals

The ferroelectric phase transition at T(C2) (=370K) in RbHSeO(4) has been studied by (1)H and (87)Rb solid-state NMR. Although not large, the spin-lattice relaxation time, T(1), and the spin-spin relaxation time, T(2), of rubidium and of the alpha- and beta-type protons show distinct change near the phase transition. The intensity of the signal due to the alpha-type protons decreases with increasing temperature, and the intensity of alpha-type protons is quite weak above 330K: at a temperature which is about 40K lower than the phase transition temperature, the ordering of the alpha-type protons occurs. The alpha-type protons in the ferroelectric phase lead to a noticeable change in the proton magnetic resonance spectra. Our study of the (1)H spectra shows that the ferroelectric phase transition in RbHSeO(4) is of order-disorder type and is due to the ordering of protons in hydrogen bonds.     

Direct observation of tunneling in KDP using Neutron Compton scattering

Neutron Compton scattering measurements presented here of the momentum distribution of hydrogen in KH2PO4 just above and well below the ferroelectric transition temperature are sufficiently sensitive to show clearly that the proton is coherent over both sites in the high temperature phase, a result that invalidates the commonly accepted order-disorder picture of the transition. The Born-Oppenheimer potential for the hydrogen, extracted directly from data for the first time, is consistent with neutron dif-fraction data, and the vibrational spectrum is in substantial agreement with infrared absorption measurements. The measurements are sensitive enough to detect the effect of surrounding ligands on the hydrogen bond, and can be used to study the systematic effect of the variation of these ligands in other hydrogen bonded systems.     

Electrical properties and proton conduction of gadolinium doped ceria

The electrical properties and proton conduction of Gd_0.1Ce_0.9O_1.95 (10GCO) were investigated via impedance spectroscopy in different atmospheres and various gas concentration cells. In oxygen atmosphere, GCO is nearly a pure oxygen ionic conductor, while in hydrogen GCO behaves as a mixed conductor of oxygen ions, electrons and protons. Depending on the temperature, the total conductivity is usually enhanced by one to two orders of magnitude in hydrogen than in air/oxygen due to mixed conduction. By examining ionic transport properties of oxygen ions and protons using gas concentration cells we have discovered that the ionic transport properties depend largely on the gas atmospheres and change from one type to the other. Proton conduction generally exists in GCOs, and becomes significant in hydrogen atmospheres, which normally results in a contribution between 5 to 10 % of the total conductivity for 10 GCO. A maximum value of 17 % of the contribution by protons has been observed. The reduction of Ce⁴⁺ to Ce³⁺ of the sample in reduced atmospheres causes the formation of additional oxygen vacancies and electrons, associated also with the creation of protons. All these charge carriers are responsible for the electrical and transport properties of the investigated GCO materials. Paper presented at the 5th Euroconference on Solid State Ionics, Benalmádena, Spain, Sept. 13–20, 1998.     

The configuration of the hydrogen atoms in HfV2Hx compounds at low temperatures: A NMR study

The ⁵¹V nuclear electric quadrupole interaction and the shape of the proton resonance line in the low temperature phase of the HfV₂H_x (0≤x≤4) compounds has been studied by NMR. The data yield information about the hydrogen arrangement in the low temperature phase. They confirm the results of recent neutron diffraction studies that for x=4 and ordered super lattice of the hydrogen atoms exists, with the hydrogen atoms occupying only tetrahedral interstitial sites formed by two Hf and two V atoms. Our results show that in the lower concentration compound the hydrogen atoms most probably also occupy the same type of interstices, but without crystallographic order.     

Molecular dynamics study of a two-dimensional model of squaric acid

The vibrational properties of the two-dimensional model of squaric acid are studied. Intermolecular and intramolecular interactions are taken to be either harmonic or of Lippincot-Schroeder type. Special attention is paid to the influence of the anharmonicity on the infrared active vibrations of the protons in the hydrogen bonds. The potential for the proton is chosen in such a way that in the room temperature phase the protons are found in an asymmetric position between two neighbouring oxygens. In the high temperature phase a symmetric distribution of protons is accessible indicating that a structural phase transition can occur.     

Low-field carrier transport properties in biased bilayer graphene

Based on a semiclassical Boltzmann transport equation in random phase approximation, we develop a theoretical model to understand low-field carrier transport in biased bilayer graphene, which takes into account the charged impurity scattering, acoustic phonon scattering, and surface polar phonon scattering as three main scattering mechanisms. The surface polar optical phonon scattering of carriers in supported bilayer graphene is thoroughly studied using the Rode iteration method. By considering the metal–BLG contact resistance as the only one free fitting parameter, we find that the carrier density dependence of the calculated total conductivity agrees well with that observed in experiment under different temperatures. The conductivity results also suggest that in high carrier density range, the metal–BLG contact resistance can be a significant factor in determining the BLG conductivity at low temperature, and both acoustic phonon scattering and surface polar phonon scattering play important roles at higher temperature, especially for BLG samples with a low doping concentration, which can compete with charged impurity scattering.     

Low temperature magnetic structure of MnSe

In this paper we report low temperature neutron diffraction studies on MnSe in order to understand the anomalous behaviour of their magnetic and transport properties. Our study indicates that at low temperatures MnSe has two coexisting crystal structures, high temperature NaCl and hexagonal NiAs. NiAs phase appears below 266 K and is antiferromagnetically ordered at all temperatures while the NaCl phase orders antiferromagnetically at 130 K.     

库仑作用对同位旋分馏过程的影响

利用同位旋相关的量子分子动力学模型研究了中能重离子碰撞中库仑作用对同位旋分馏过程的影响.研究结果表明,在所研究的能区,无论是丰(缺)中子碰撞系统或者轻(重)反应系统,库仑作用都使同位旋分馏过程减弱,而这种影响主要来自于库仑作用对质子的排斥作用,使更多的质子发射,从而降低了气相中子–质子比所导致     

中能重离子碰撞中前平衡核子发射的同位旋效应

利用同位旋相关的输运理论,研究了中能重离子碰撞中丰中子和缺中子碰撞系统在较宽能区范围内前平衡发射核子的同位旋效应.结果表明除低能区外,在100MeV/u以上核子–核子碰撞动力学效应起主要作用的能区,前平衡发射的中子–质子比仍然对介质中核子–核子碰撞截面的同位旋效应不灵敏,然而对于对称势的改变非常灵敏.故从低能量到较高能量的较大能区内,前平衡发射的中子–质子比的理论值与实验值的比较是提取对称势形式和强度的灵敏探针.     

Quasielastic neutron scattering of hydrated BaZr0.90A0.10O2.95 (A = Y and Sc)

Proton motions in hydrated proton conducting perovskites BaZr_0.90A_0.10O_2.95 (A = Y and Sc) have been investigated using quasielastic neutron scattering. The results reveal a localized motion on the ps time scale and with an activation energy of ~ 10–30 meV, in both materials. The temperature dependence of the total mean square displacement of the protons shows an onset of this motion at a temperature of about 300 K. The low activation energy, much lower than the activation energy for the macroscopic proton conductivity, suggests that this motion is not the rate-limiting process for the long-range proton diffusion, i.e. it is not linked to the two materials significantly different proton conductivities. In fact, a comparison of the QENS results with density functional theory calculations indicates that for both materials the observed motion may be ascribed to intra-octahedral proton transfers occurring close to a dopant atom.     

质子和中子在硅中位移损伤等效性计算

基于蒙特卡罗软件Geant4,探讨质子与硅的库仑散射和核反应及中子与硅的核反应产生反冲原子沉积非电离能量的过程,建立质子和中子在硅中的非电离能量阻止本领计算方法。在此方法中,描述了原子间库仑散射的物理过程,模拟带电粒子与晶格原子之间的屏蔽库仑散射。计算得到不同能量质子和中子在硅中因库仑散射和核反应产生反冲原子的非电离能量沉积及阻止本领的等效性,计算结果与中子ASTM标准及文献计算得到的质子数据符合很好。     

Frustrated superexchange interaction versus orbital order in a LaVO3 crystal

Measurements of magnetic, transport properties, thermal conductivity, and magnetization under pressure as well as neutron diffraction have been made on a single crystal and powder sample of LaVO3. The Néel temperature was found to mark a transition from the phase with both frustrated superexchange interaction and spin-orbit lambdaL.S coupling to the phase where the Jahn-Teller orbital-lattice coupling dominates. The dramatic reduction of absolute entropy in the paramagnetic phase is explained in terms of forming a long-range coherent state due to the interference between frustrated orbits and spins.     

中能重离子碰撞中的气–液相变和同位旋分馏

利用核物质理论研究气–液相变结果表明,气–液相变中临界温度T_c随系统质量的增加而增加,但随碰撞系统同位旋的增加而减小.利用改进的同位旋相关的量子分子动力学模型,研究了中能重离子碰撞过程中同位旋分馏强度随碰撞系统的同位旋和系统质量的变化,结果表明,同位旋分馏强度与气–液相变临界温度T_c有对应的关系,特别是气–液相变和同位旋分馏都发生在正常核密度以下低密度的spinodal不稳定区.这表明气–液相变和同位旋分馏具有相类似的动力学行为和内在联系,也预示着可以通过对同位旋分馏强度的研究和测量来揭示中能重离子碰撞过程中气–液相变的动力学特征     

Bonding in the superionic phase of water

The predicted superionic phase of water is investigated via ab initio molecular dynamics at densities of 2.0--3.0 g/cc (34-115 GPa) along the 2000 K isotherm. We find that extremely rapid (superionic) diffusion of protons occurs in a fluid phase at pressures between 34 and 58 GPa. A transition to a stable body-centered cubic O lattice with superionic proton conductivity is observed between 70 and 75 GPa, a much higher pressure than suggested in prior work. We find that all molecular species at pressures greater than 75 GPa are too short lived to be classified as bound states. Up to 95 GPa, we find a solid superionic phase characterized by covalent O-H bonding. Above 95 GPa, a transient network phase is found characterized by symmetric O-H hydrogen bonding with nearly 50% covalent character. In addition, we describe a metastable superionic phase with quenched O disorder.     

“Symmetrical” phase and collective excitations in the proton system of ice

A model of the ice proton system taking into account quantum-mechanical tunneling of protons along hydrogen bonds has been formulated and investigated. When the tunneling amplitude is small the quantum ground state of the proton system is degenerate, like the classical ground state. At higher tunneling amplitudes, however, a transition to a nondegenerate state with a symmetrical distribution of protons on hydrogen bonds (a symmetrical phase of ice) is possible. Collective excitations of protons in the nonsymmetrical phase have been considered, and an equation that determines their spectrum has been derived. Zh. éksp. Teor. Fiz. 115, 2207–2213 (June 1999)     

Hydrogen bond dynamics in dodecanoic acid studied by QNS and NMR

The dynamics of hydrogen atoms in the hydrogen bonds of molecular dimers in dodecanoic acid (c phase) have been studied by quasi-elastic neutron scattering and pulsed nuclear magnetic resonance. Q-dependence measurements of the intensity of the quasi-elastic peak have established that the hydrogen atoms move along a line connecting the two oxygen atoms in the hydrogen bond. The correlation time for this motion has been studied by temperature dependence measurements of the width of the quasi-elastic line and of the proton spin-lattice relaxation time,T ₁. These studies reveal the quantum mechanical nature of the dynamics in the low temperature region. The dynamical parameters which characterise the motion have been determined by fitting the data to a model which invokes phonon assisted tunnelling. The frequency dependence ofT ₁ at low temperature is anomalous because the gradient of the ln(T ₁) vs 1/T curve is dependent on the applied magnetic field.     

Hydrogen isotopic replacement and microstructure evolution in zirconium deuteride implanted by 150 keV protons

Zirconium tritiated(ZrT_x) is an alternative target material for deuteron–triton(D-T) reaction neutron generator. The isotopic replacement and microstructure evolution induced by hydrogen isotope implantation could significantly affect the performance of the target film. In this work, the zirconium deuteride film deposited on Mo/Si substrate was implanted by 150 ke V protons with fluence from 1×10~(16) to 1×10~(18) protons/cm~2. After implantation, the depth profiles of retained hydrogen(H) and deuterium(D) in these target films were analyzed by elastic recoil detection analysis(ERDA), and time of flight-secondary ion mass spectrometry(To F-SIMS). Additionally, the microstructure evolution was also observed by x-ray diffraction(XRD) and scanning electron microscope(SEM). The D concentration in the Zr Dx film decreased versus the proton implantation fluence. An analytical model was proposed to describe the hydrogen isotopic trapping and exchange as functions of incident protons fluence. Additionally, the XRD analysis revealed that no new phase was formed after proton implantation. Furthermore, circular flakings were observed on the ZrD_x surface from SEM images at fluence up to 1×10~(18) protons/cm~2, and this surface morphology was considered to associate with the hydrogen atoms congregation in Mo/Si boundary.     

Investigation of the proton migration mechanism in the perovskite proton conductor Ba3Ca1.18Nb1.82H0.2O8.83 by means of quasielastic neutron scattering

We investigated the recently discovered high temperature proton conductor BaCa_1.18Nb_1.82H_0.2O_8.83 by means of quasielastic neutron scattering (QENS) using cold and thermal neutrons. From the former experiment we were able to propose models for the diffusion of the hydrogen whereas the latter measurement reveals the geometry of a localized motion of the protons. Paper presented at the 2nd Euroconference on Solid State Ionics, Funchal, Madeira, Portugal, Sept. 10–16, 1995