Use features like bookmarks, note taking and highlighting while reading recent progress in orbitalfree. The new functional is implemented in orbitalfree planewave density functional method, in which a conjugategradient linesearch scheme of electronic minimization is incorporated. Performance of semilocal kineticenergy functionals for. Carter,2 1department of mechanical and aerospace engineering, princeton university, princeton, new jersey 085445263, usa 2program in applied and computational mathematics and andlinger center for energy and the. Abstract this letter proposes a scheme of orbital free density functional theory ofdft calculation for optimizing electron density based on a semilocal machinelearned ml kinetic energy density functional kedf. We have used density functional theory in an orbitalfree, implementation to calculate the properties of pure fcc al, hcp and bcc mg, and the metastable alloy phase. Five linearresponsebased kinetic energy density functionals have been used, one of which has a densitydependent dd response kernel. The first order fragment approach does not contain data or parameters that are fitted to the final outcome of the molecular orbitalfree calculation and thus represents a parameterfree implementation of orbitalfree density functional theory, although it. Jul 10, 2019 the first order fragment approach does not contain data or parameters that are fitted to the final outcome of the molecular orbital free calculation and thus represents a parameter free implementation of orbital free density functional theory, although it requires the precalculation of atomic data. Dynamic kinetic energy potential for orbitalfree density functional theory article pdf available in the journal of chemical physics 414.
Using this theory, the properties of a manyelectron system can be determined by using. The first order atomic fragment approachan orbitalfree. Nonlocal orbitalfree kinetic energy density functional. The atomic fragment approach is an abinitio, parameterfree implementation of orbitalfree density functional theory which is based on the bifunctional formalism, i.
However, all these positive features come at a price. Kinetic energy density functionals kedfs are central to orbitalfree density functional theory. Density functional df theory has proved to be a powerful way to determine the ground state energy of atoms, molecules, and extended systems. For the bandgap, calculated with the modified beckejohnson mgga potential, the deorbitalization has a larger impact on the results. Based on the same perturbation apqm methods in many. Chapter 5 orbitalfree kineticenergy density functional.
Alharbi and sabre kais march 2017 international journal of quantum chemistry, vol. New orbital free simulation method based on the density. Orbitalfree density functional theory ofdft1,2 is starting to become an attractive. This has been the main stumbling block for the development of a generalpurpose framework on this basis. Orbitalfree density functional theory calculation applying. The exact form of the kinetic energy functional has remained elusive in orbitalfree models of density functional theory dft. Trivial constraints on orbitalfree kinetic energy density functionals kai luo1, and s. Kinetic energy density for orbital free density functional calculations by axiomatic approach fahhad h. In orbital free density functional theory the kinetic potential kp, the functional derivative of the kinetic energy density functional, appears in the euler equation for the electron density and may be more amenable to simple approximations. Densitydecomposed orbitalfree density functional theory. In orbitalfree density functional theory the kinetic potential kp, the functional derivative of the kinetic energy density functional, appears in the euler equation for the electron density and may be more amenable to simple approximations.
The motivation for this objective is straightforward. Download citation orbitalfree kineticenergy density functional theory in the beginning of quantum mechanical densityfunctional theory dft, there was the thomasfermi tf model, which. Therefore, the effect of the exchangecorrelation treatment must be considered in the design of orbitalfree density functional approximations for the. Orbitalfree kineticenergy density functional theory. Progress in theoretical chemistry and physics, vol 5. With this theory, the properties of a manyelectron system can be determined by using functionals, i. Orbitalfree density functional theory ofdft this page introduces the orbitalfree dft method in a comprehensive way. Nevertheless, the last two decades have witnessed a. Recent progress in orbitalfree density functional theory recent. Orbitalfree density functional theory ofdft is both grounded in quantum physics and suitable for direct simulation of thousands of atoms. The atomic fragment approach is an abinitio, parameter free implementation of orbital free density functional theory which is based on the bifunctional formalism, i. Nonlocal kinetic energy density functional via line integrals and its.
The aim of orbitalfree dft is to avoid the need to solve the \ n \ equations by removing the explicit dependence of the kinetic energy term on the orbitals, effectively obtaining a kinetic energy functional \ tn \ that depends explicitly only on the density. Orbitalcorrected orbitalfree density functional theory. Performance of semilocal kinetic energy functionals for orbital. Trivial constraints on orbitalfree kinetic energy density. Consequently, ofdft reduces the degrees of freedom in the computation from 3n to 3, greatly simplifying the formalism.
Machinelearned kinetic energy density functional and kinetic potential are employed. Recent progress in orbitalfree density functional theory. Density functional theory dft is a computational quantum mechanical modelling method used in physics, chemistry and materials science to investigate the electronic structure principally the ground state of manybody systems, in particular atoms, molecules, and the condensed phases. We assess several generalized gradient approximations ggas and laplacianlevel metaggas llmgga kinetic energy ke functionals for orbital free density functional theory calculations of bulk metals and semiconductors, considering equilibrium distances, bulk moduli, total and kinetic energies, and the electron densities. Apr 04, 2003 we have used density functional theory in an orbitalfree, implementation to calculate the properties of pure fcc al, hcp and bcc mg, and the metastable alloy phase. Outline basics of functional derivatives i principles of orbitalfree densityfunctional theory basics of densityfunctional theory motivation for ofdft basics of the numerical implementation ii approximations to the kineticenergy. A \bf 89, 022503 2014, the average density approximation ada was implemented to develop a parameterfree, nonlocal kinetic energy functional to be used in the orbitalfree densityfunctional theory of an inhomogenous, twodimensional 2d, fermi gas. If you are already familiar with the theory and want to learn how to use the orbitalfree gpaw module you can skip the introduction and go directly to the section running the code. Orbitalfree kineticenergy density functionals with a. Abstract this letter proposes a scheme of orbitalfree density functional theory ofdft calculation for optimizing electron density based on a semilocal machinelearned ml kinetic energy density functional kedf. A 96, 052512 2017 showed that the deorbitalization procedure replacing the exact kohnsham kineticenergy density by an approximate orbitalfree expression applied to exchangecorrelation functionals of the metageneralized gradient approximation mgga can lead to important changes in the results for molecular properties. Dynamic kinetic energy potential for orbitalfree density functional.
This project focuses on the advancement, implementation, and use of finitetemperature density functional theory, especially in orbitalfree form, to achieve simulations primarily ab initio molecular dynamics but also beyond to approximate quantum dynamics of matter under extreme conditions. Orbitalfree density functional theory is, at present, less accurate than kohnsham density functional theory models, but has the advantage of being fast, so that it can be applied to large systems. The aim of orbital free dft is to avoid the need to solve the \ n \ equations by removing the explicit dependence of the kinetic energy term on the orbitals, effectively obtaining a kinetic energy functional \ tn \ that depends explicitly only on the density. Orbitalfree tensor density functional theory igor v. The noninteracting kinetic energy functional t s n of the electron density n is used in two distinct ways in a ks calculation 1, as illustrated in fig. Alvarellos, approach to kinetic energy density functionals. Densitydecomposed orbitalfree density functional theory for.
An efficient and objectoriented platform for orbitalfree dft. Trickey2, y 1quantum theory project, department of physics, university of florida, gainesville, fl 32611 2quantum theory project, departments of physics and of chemistry, university of florida, gainesville, fl 32611 dated. However, the work of kohn and sham shifted interest away from ofdft to orbital based dft or later its equivalent, density matrix dft, due to the improved description of the kinetic energy. Besides, it is demonstrated that the orbitalfree version of the density functional theory may be used for finding equilibrium configurations of multiatomic systems with covalent bonding. Equilibrium bond lengths from orbitalfree density functional. The theories deal with tensors that characterize the oneparticle density matrix and consequently the kinetics of the particles. Density functional theory dft is a computational quantum mechanical modelling method used in physics, chemistry and materials science to investigate the electronic structure or nuclear structure principally the ground state of manybody systems, in particular atoms, molecules, and the condensed phases. Orbitalfree approximations to the kineticenergy density. Density functional for the kinetic energy and its applications in orbital free dft simulations. Orbital free density functional theory ofdft is both grounded in quantum physics and suitable for direct simulation of thousands of atoms.
The core structure of screw and edge dislocations in fcc al was investigated using orbitalfree density functional theory ofdft. Ofdft can be made to scale quasilinearly o nlnn with system size by solving directly for the electron density instead of introducing an auxiliary set of oneelectron orbitals, as is done in. Density functional theory for matter under extreme conditions. This project focuses on the advancement, implementation, and use of finitetemperature density functional theory, especially in orbital free form, to achieve simulations primarily ab initio molecular dynamics but also beyond to approximate quantum dynamics of matter under extreme conditions.
The optimized density and electronic energy are evaluated. Density functional theoryintroduction wikibooks, open. The core structure of screw and edge dislocations in fcc al was investigated using orbital free density functional theory ofdft. An introduction to orbitalfree density functional theory. This work presents an investigation to model chemical bonding in various dimers based on the atomic fragment approach. Testing the nonlocal kinetic energy functional of an. An alternative firstprinciples quantum mechanics method that is considerably less expensive than ksdft is orbitalfree density functional theory ofdft. Wang y a and carter e a 2000 orbitalfree kinetic energy density functional theory theoretical methods in condensed phase chemistry progress in theoretical chemistry and physics ed s d schwartz dordrecht. Dynamic kinetic energy potential for orbitalfree density. Bypassing the kohnsham equations with machine learning. Orbitalfree approximations to the kineticenergy density in exchangecorrelation mgga functionals. Tfw tends, however, to definitely overestimate the kinetic energy, despite eq 3 being satisfied only when.
Oct 11, 2017 the noninteracting kinetic energy functional t s n of the electron density n is used in two distinct ways in a ks calculation 1, as illustrated in fig. Orbitalfree approximations to the kineticenergy density in. Recent progress in orbitalfree density functional theory recent advances in computational chemistry book 6 kindle edition by wesolowski, tomasz a, yan alexander wang, tomasz a wesolowski, yan alexander wang. Orbitalfree density functional theory calculation applying semilocal.
Density functional theory dft has been firmly established as one of the most widely used firstprinciples quantum mechanical methods in many fields. Exact orbitalfree kinetic energy functional for general manyelectron systems. Orbitalfree density functional theory ofdft holds great promise for large scale simulations since there is a linear scaling for the. Each of the two ways of solving the dft problem, i. Orbitalfree density functional theory for materials. I principles of orbitalfree densityfunctional theory basics of densityfunctional theory motivation for ofdft basics of the numerical implementation ii approximations to the kineticenergy functional the thomasfermi approximation the vonweizsacker term linearresponse theory combination of tf and vw the. Aug 04, 2017 besides, it is demonstrated that the orbital free version of the density functional theory may be used for finding equilibrium configurations of multiatomic systems with covalent bonding. Orbitalfree density functional theory calculations of the. For metals, the orbitalfree scheme is even more rewarding, because the need for brillouinzonekpoint.
Madsen and peter blaha 14 oct 2018 the journal of chemical physics, vol. Download it once and read it on your kindle device, pc, phones or tablets. Download citation an introduction to orbitalfree density functional theory. Outline basics of functional derivatives i principles of orbitalfree densityfunctional theory basics of density functional theory motivation for ofdft basics of the numerical implementation ii approximations to the kineticenergy. Orbitalfree density functional theory for materials research. Semilocal approximations for the kinetic energy recent. Orbitalfree density functional theory calculation applying semilocal machine learned kinetic energy density functional and kinetic potential. For a system of n electrons in an external potential v ext, the total energy e can be expressed as a functional of the density. It is shown that depending on the mgga, common orbital free approximations to the kinetic energy density can be sufficiently accurate for the lattice constant, bulk modulus, and cohesive energy.
A scheme for orbitalfree density functional theory calculation is implemented. A dynamic kinetic energy potential dkep is developed for timedependent orbitalfree tdof density function theory applications. We propose a density decomposition scheme using a wanggovindcarter wgc based kinetic energy density functional kedf to accurately and ef. This article describes the application of ofdft for materials research over roughly the past two decades, highlighting computational studies that would have been impractical or impossible to perform with other techniques. Orbitalfree density functional theory simulations of. Pdf a new method for defining an energy density for the noninteracting kinetic energy of density functional theory is given. This is in fact possible, and it is the goal of orbitalfree density functional theory ofdft. Chapter 5 orbitalfree kineticenergy density functional theory. The equilibrium interatomic distances, interbonding angles and binding energies for si3 and c3 clusters are found in good accordance with known data.
Hybridized kinetic energy functional for orbitalfree. Exact orbitalfree kinetic energy functional for general manyelectron. Introduction to orbitalfree densityfunctional theory ralf gehrke fhi berlin, february 8th 2005. Density functional for the kinetic energy and its applications in orbitalfree dft simulations. Limitations on the spatial derivative dependencies of kedfs have been claimed from differential virial theorems.
Nonlocal orbitalfree kinetic energy density functional for. However, the work of kohn and sham shifted interest away from ofdft to orbitalbased dft or later its equivalent, densitymatrix dft, due to the improved description of the kinetic energy. Introduction to orbitalfree densityfunctional theory. An important part of the theory requires one to determine the kinetic energy of the ground state of a system of n noninteracting electrons in a general external field. We also considered the effects of the pseudopotentials, the vacancy. Detailed calibrations of kinetic energy density functionals kedfs and local pseudopotentials were performed to reproduce accurately the energies of several phases of bulk al, as well as the elastic moduli and stacking fault energies of fcc al.
1586 1157 14 1296 683 607 1066 469 1535 969 809 233 97 1206 113 293 888 432 1435 269 1555 1629 946 59 519 345 1005 229 1272 172 98 103 300 676 880 860 492