اشترك بالحزمة الذهبية واحصل على وصول غير محدود شمرا أكاديميا
تسجيل مستخدم جديدJoint Density-Functional Theory of the Electrode-Electrolyte Interface: Application to Fixed Electrode Potentials, Interfacial Capacitances, and Potentials of Zero Charge
292
0
0.0
(
0
)
اسأل ChatGPT حول البحث
ﻻ يوجد ملخص باللغة العربية
This work explores the use of joint density-functional theory, a new form of density-functional theory for the ab initio description of electronic systems in thermodynamic equilibrium with a liquid environment, to describe electrochemical systems. After reviewing the physics of the underlying fundamental electrochemical concepts, we identify the mapping between commonly measured electrochemical observables and microscopically computable quantities within an, in principle, exact theoretical framework. We then introduce a simple, computationally efficient approximate functional which we find to be quite successful in capturing a priori basic electrochemical phenomena, including the capacitive Stern and diffusive Gouy-Chapman regions in the electrochemical double layer, quantitative values for interfacial capacitance, and electrochemical potentials of zero charge for a series of metals. We explore surface charging with applied potential and are able to place our ab initio results directly on the scale associated with the Standard Hydrogen Electrode (SHE). Finally, we provide explicit details for implementation within standard density-functional theory software packages at negligible computational cost over standard calculations carried out within vacuum environments.
قيم البحث
اقرأ أيضاً
Density Functional Theory (DFT) calculations have been widely used to predict the activity of catalysts based on the free energies of reaction intermediates. The incorporation of the state of the catalyst surface under the electrochemical operating c
onditions while constructing the free energy diagram is crucial, without which even trends in activity predictions could be imprecisely captured. Surface Pourbaix diagrams indicate the surface state as a function of the pH and the potential. In this work, we utilize error-estimation capabilities within the BEEF-vdW exchange correlation functional as an ensemble approach to propagate the uncertainty associated with the adsorption energetics in the construction of Pourbaix diagrams. Within this approach, surface-transition phase boundaries are no longer sharp and are therefore associated with a finite width. We determine the surface phase diagram for several transition metals under reaction conditions and electrode potentials relevant for the Oxygen Reduction Reaction (ORR). We observe that our surface phase predictions for most predominant species are in good agreement with cyclic voltammetry experiments and prior DFT studies. We use the OH$^*$ intermediate for comparing adsorption characteristics on Pt(111), Pt(100), Pd(111), Ir(111), Rh(111), and Ru(0001) since it has been shown to have a higher prediction efficiency relative to O$^*$, and find the trend Ru>Rh>Ir>Pt>Pd for (111) metal facets, where Ru binds OH$^*$ the strongest. We robustly predict the likely surface phase as a function of reaction conditions by associating c-values to quantifying the confidence in predictions within the Pourbaix diagram. We define a confidence quantifying metric using which certain experimentally observed surface phases and peak assignments can be better rationalized.
External potentials play a crucial role in modelling quantum systems, since, for a given inter- particle interaction, they define the system Hamiltonian. We use the metric space approach to quantum mechanics to derive, from the energy conservation la
w, two natural metrics for potentials. We show that these metrics are well defined for physical potentials, regardless of whether the system is in an eigenstate or if the potential is bounded. In addition, we discuss the gauge freedom of potentials and how to ensure that the metrics preserve physical relevance. Our metrics for potentials, together with the metrics for wavefunctions and densities from [I. DAmico, J. P. Coe, V. V. Franca, and K. Capelle, Phys. Rev. Lett. 106, 050401 (2011)] paves the way for a comprehensive study of the two fundamental theorems of Density Functional Theory. We explore these by analysing two many- body systems for which the related exact Kohn-Sham systems can be derived. First we consider the information provided by each of the metrics, and we find that the density metric performs best in distinguishing two many-body systems. Next we study for the systems at hand the one-to-one relationships among potentials, ground state wavefunctions, and ground state densities defined by the Hohenberg-Kohn theorem as relationships in metric spaces. We find that, in metric space, these relationships are monotonic and incorporate regions of linearity, at least for the systems considered. Finally, we use the metrics for wavefunctions and potentials in order to assess quantitatively how close the many-body and Kohn-Sham systems are: We show that, at least for the systems analysed, both metrics provide a consistent picture, and for large regions of the parameter space the error in approximating the many-body wavefunction with the Kohn-Sham wavefunction lies under a threshold of 10%.
We propose a method to decompose the total energy of a supercell containing defects into contributions of individual atoms, using the energy density formalism within density functional theory. The spatial energy density is unique up to a gauge transf
ormation, and we show that unique atomic energies can be calculated by integrating over Bader and charge-neutral volumes for each atom. Numerically, we implement the energy density method in the framework of the Vienna ab initio simulation package (VASP) for both norm-conserving and ultrasoft pseudopotentials and the projector augmented wave method, and use a weighted integration algorithm to integrate the volumes. The surface energies and point defect energies can be calculated by integrating the energy density over the surface region and the defect region, respectively. We compute energies for several surfaces and defects: the (110) surface energy of GaAs, the mono-vacancy formation energies of Si, the (100) surface energy of Au, and the interstitial formation energy of O in the hexagonal close-packed Ti crystal. The surface and defect energies calculated using our method agree with size-converged calculations of the difference between the total energies of the system with and without the defect. Moreover, the convergence of the defect energies with size can be found from a single calculation.
Local field potentials (LFPs) sampled with extracellular electrodes are frequently used as a measure of population neuronal activity. However, relating such measurements to underlying neuronal behaviour and connectivity is non-trivial. To help study
this link, we developed the Virtual Electrode Recording Tool for EXtracellular potentials (VERTEX). We first identified a reduced neuron model that retained the spatial and frequency filtering characteristics of extracellular potentials from neocortical neurons. We then developed VERTEX as an easy-to-use Matlab tool for simulating LFPs from large populations (>100 000 neurons). A VERTEX-based simulation successfully reproduced features of the LFPs from an in vitro multi-electrode array recording of macaque neocortical tissue. Our model, with virtual electrodes placed anywhere in 3D, allows direct comparisons with the in vitro recording setup. We envisage that VERTEX will stimulate experimentalists, clinicians, and computational neuroscientists to use models to understand the mechanisms underlying measured brain dynamics in health and disease.
Density-functional theory (DFT) has revolutionized computational prediction of atomic-scale properties from first principles in physics, chemistry and materials science. Continuing development of new methods is necessary for accurate predictions of n
ew classes of materials and properties, and for connecting to nano- and mesoscale properties using coarse-grained theories. JDFTx is a fully-featured open-source electronic DFT software designed specifically to facilitate rapid development of new theories, models and algorithms. Using an algebraic formulation as an abstraction layer, compact C++11 code automatically performs well on diverse hardware including GPUs. This code hosts the development of joint density-functional theory (JDFT) that combines electronic DFT with classical DFT and continuum models of liquids for first-principles calculations of solvated and electrochemical systems. In addition, the modular nature of the code makes it easy to extend and interface with, facilitating the development of multi-scale toolkits that connect to ab initio calculations, e.g. photo-excited carrier dynamics combining electron and phonon calculations with electromagnetic simulations.
سجل دخول لتتمكن من نشر تعليقات
التعليقات
جاري جلب التعليقات
سجل دخول لتتمكن من متابعة معايير البحث التي قمت باختيارها
