Related papers: Grand canonical electronic density-functional theo…
We present a numerical method for grand canonical density functional theory (DFT) tailored to solid-state systems, employing Gaussian-type orbitals as the primary basis. Our approach directly minimizes the grand canonical free energy using…
Simulating electrochemical interfaces using density functional theory (DFT) requires incorporating the effects of electrochemical potential. The electrochemical potential acts as a new degree of freedom that can effectively tune DFT results…
Using the example of a proton adsorption process, we analyze and compare two prominent modelling approaches in computational electrochemistry at metallic electrodes - electronically canonical, constant-charge and electronically…
Classical density functional theory for finite temperatures is usually formulated in the grand-canonical ensemble where arbitrary variations of the local density are possible. However, in many cases the systems of interest are closed with…
Density-functional theory (DFT) has revolutionized computer simulations in chemistry and material science. A faithful implementation of the theory requires self-consistent calculations. However, this effort involves repeatedly diagonalizing…
As interest in nanomaterials grows, ab initio simulations play a crucial role in designing electrochemical catalysts. Electrochemical reactions depend on electrode potential, highlighting the importance of the grand canonical…
A theoretical scheme for the treatment of an open molecular system with electrons and nuclei is proposed. The idea is based on the Grand Canonical description of a quantum region embedded in a classical reservoir of molecules. Electronic…
How does an electrochemical interface respond to changes in the electrode potential? How does the response affect the key properties of the system - energetics, excess charge, capacitance? Essential questions key to ab-initio simulations of…
Linear scaling density functional theory approaches to electronic structure are often based on the tendency of electrons to localize even in large atomic and molecular systems. However, in many cases of actual interest, for example in…
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…
We argue that the success of DFT can be understood in terms of a semiclassical expansion around a very specific limit. This limit was identified long ago by Lieb and Simon for the total electronic energy of a system. This is a universal…
In this work we give a comprehensive derivation of an exact and numerically feasible method to perform ab-initio calculations of quantum particles interacting with a quantized electromagnetic field. We present a hierachy of…
We present a computationally efficient approach to perform large-scale all-electron density functional theory calculations by enriching the classical finite element basis with compactly supported atom-centered numerical basis functions that…
It is shown that in adiabatic approximation for nuclei the many-component Coulomb system cannot be described on the basis of the grand canonical ensemble. Using the variational Bogolyubov's procedure for the free energy, the Hohenberg-Kohn…
We present an ab-initio approach for grand canonical ensembles in thermal equilibrium with local or nonlocal external potentials based on the one-reduced density matrix. We show that equilibrium properties of a grand canonical ensemble are…
We exploit a prescription to observe directly the physical properties of the thermodynamic limit under continuously applied field in one-dimensional quantum finite lattice systems. By systematically scaling down the energy of the…
We present an efficient computational approach to perform real-space electronic structure calculations using an adaptive higher-order finite-element discretization of Kohn-Sham density-functional theory (DFT). To this end, we develop an…
We present an improved field-theoretic approach to the grand-canonical potential suitable for linear scaling molecular dynamics simulations using forces from self-consistent electronic structure calculations. It is based on an exact…
In the exact Kohn-Sham density-functional theory (DFT), the total energy versus the number of electrons is a series of linear segments between integer points. However, commonly used approximate density functionals produce total energies…
Combining classical density functional theory (cDFT) with quantum mechanics (QM) methods offers a computationally efficient alternative to traditional QM/molecular mechanics (MM) approaches for modeling mixed quantum-classical systems at…