اشترك بالحزمة الذهبية واحصل على وصول غير محدود شمرا أكاديميا
تسجيل مستخدم جديدHydrogen Diffusion and Trapping in {alpha}-Iron: The Role of Quantum and Anharmonic Fluctuations
37
0
0.0
(
0
)
اسأل ChatGPT حول البحث
ﻻ يوجد ملخص باللغة العربية
We investigate the thermodynamics and kinetics of a hydrogen interstitial in magnetic {alpha}-iron, taking account of the quantum fluctuations of the proton as well as the anharmonicities of lattice vibrations and hydrogen hopping. We show that the diffusivity of hydrogen in the lattice of BCC iron deviates strongly from an Arrhenius behavior at and below room temperature. We compare a quantum transition state theory to explicit ring polymer molecular dynamics in the calculation of diffusivity and we find that the role of phonons is to inhibit, not to enhance, diffusivity at intermediate temperatures in constrast to the usual polaron picture of hopping. We then address the trapping of hydrogen by a vacancy as a prototype lattice defect. By a sequence of steps in a thought experiment, each involving a thermodynamic integration, we are able to separate out the binding free energy of a proton to a defect into harmonic and anharmonic, and classical and quantum contributions. We find that about 30% of a typical binding free energy of hydrogen to a lattice defect in iron is accounted for by finite temperature effects and about half of these arise from quantum proton fluctuations. This has huge implications for the comparison between thermal desorption and permeation experiments and standard electronic structure theory. The implications are even greater for the interpretation of muon spin resonance experiments.
قيم البحث
اقرأ أيضاً
A theoretical study is reported of the molecular-to-atomic transition in solid hydrogen at high pressure. We use the diffusion quantum Monte Carlo method to calculate the static lattice energies of the competing phases and a density-functional-theory
-based vibrational self-consistent field method to calculate anharmonic vibrational properties. We find a small but significant contribution to the vibrational energy from anharmonicity. A transition from the molecular Cmca-12 direct to the atomic I4_1/amd phase is found at 374 GPa. The vibrational contribution lowers the transition pressure by 91 GPa. The dissociation pressure is not very sensitive to the isotopic composition. Our results suggest that quantum melting occurs at finite temperature.
Metal-organic frameworks show both fundamental interest and great promise for applications in adsorption-based technologies, such as the separation and storage of gases. The flexibility and complexity of the molecular scaffold poses a considerable ch
allenge to atomistic modeling, especially when also considering the presence of guest molecules. We investigate the role played by quantum and anharmonic fluctuations in the archetypical case of MOF-5, comparing the material at various levels of methane loading. Accurate path integral simulations of such effects are made affordable by the introduction of an accelerated simulation scheme and the use of an optimized force field based on first-principles reference calculations. We find that the level of statistical treatment that is required for predictive modeling depends significantly on the property of interest. The thermal properties of the lattice are generally well described by a quantum harmonic treatment, with the adsorbate behaving in a classical but strongly anharmonic manner. The heat capacity of the loaded framework - which plays an important role in the characterization of the framework and in determining its stability to thermal fluctuations during adsorption/desorption cycles - requires, however, a full quantum and anharmonic treatment, either by path integral methods or by a simple but approximate scheme. We also present molecular-level insight into the nanoscopic interactions contributing to the materials properties and suggest design principles to optimize them
In a reaction-diffusion system, fluctuations in both diffusion and reaction events, have important effects on the steady-state statistics of the system. Here, we argue through extensive lattice simulations, mean-field type arguments, and the Doi-Peli
ti formalism that the collision duration statistics -- i.e., the time two particles stay together in a lattice site -- plays a leading role in determining the steady state of the system. We obtain approximate expressions for the average densities of the chemical species and for the critical diffusion coefficient required to sustain the reaction.
Interplay between hydrogen and nanovoids, despite long-recognized as a central aspect in hydrogen-induced damages in structural materials, remains poorly understood. Focusing on tungsten as a model BCC system, the present study, for the first time, e
xplicitly demonstrated sequential adsorption of hydrogen adatoms on Wigner-Seitz squares of nanovoids with distinct energy levels. Interaction between hydrogen adatoms on the nanovoid surface is shown to be dominated by pairwise power law repulsion. A predictive model was established for quantitative prediction of configurations and energetics of hydrogen adatoms in nanovoids. This model, further combined with equation of states of hydrogen gas, enables prediction of hydrogen molecule formation in nanovoids. Multiscale simulations based on the predictive model were performed, showing excellent agreement with experiments. This work clarifies fundamental physics and provides full-scale predictive model for hydrogen trapping and bubbling in nanovoids, offering long-sought mechanistic insights crucial for understanding hydrogen-induced damages in structural materials.
The reported diffusion constants for hydrogen in silicon vary over six orders of magnitude. This spread in measured values is caused by the different concentrations of defects in the silicon that has been studied. Hydrogen diffusion is slowed down as
it interacts with impurities. By changing the material properties such as the crystallinity, doping type and impurity concentrations, the diffusivity of hydrogen can be changed by several orders of magnitude. In this study the influence of the hydrogen concentration on the temperature dependence of the diffusion in high energy proton implanted silicon is investigated. We show that the Arrhenius parameters, which describe this temperature dependence decrease with increasing hydrogen concentration. We propose a model where the relevant defects that mediate hydrogen diffusion become saturated with hydrogen at high concentrations. When the defects that provide hydrogen with the lowest energy positions in the lattice are saturated, hydrogen resides at energetically less favorable positions and this increases the diffusion of hydrogen through the crystal. Furthermore, we present a survey of different studies on the diffusion of hydrogen. We observed a correlation of the Arrhenius parameters calculated in those studies, leading to a modification of the Arrhenius equation for the diffusion of hydrogen in silicon.
سجل دخول لتتمكن من نشر تعليقات
التعليقات
جاري جلب التعليقات
سجل دخول لتتمكن من متابعة معايير البحث التي قمت باختيارها
