DFT
DFT
DFT
Rubn Prez Departamento de Fsica Terica de la Materia Condensada, Universidad Autnoma de Madrid, Spain ruben.perez@uam.es
Mtodos Computacionales en Fsica de la Materia Condensada Master en Fsica de la Materia Condensada y Nanotecnologa Curso 2007/8
Outline
Motivation: limitations of the standard approach based on the wave function. The electronic density n(r) as the key variable: Functionals & Thomas-Fermi theory. Density functional theory (DFT): Hohenberg-Kohn (HK) Theorem Kohn-Sham equations. Total Energy Interpretation of the KS eigenvalues Exchange-Correlation functional: Local density approximation (LDA): Limitations. Generalized Gradients Approximations (GGA) and beyond. Making DFT practical: Basis sets, Supercells and K-sampling
Motivation
Goals
Born-Oppenheimer Approximation
Hamiltonian for M nuclei and N electrons M >> m ionic and (much faster) electronic motions can be decoupled
electrons relaxed to GS for a given ionic configuration. nuclei move in a potential given by electronic GS energy
Hamiltonian for an N-electron system: Whether it is an atom, a molecule or a solid depends only on v(ri)
Hartree-Fock (HF) |> is a Slater determinant HF includes all the exchange effects Configuration Interaction (CI) : includes correlation |>: linear combination of Slater determinants Problem: factorial growth of the number of determinants with the number of electrons.
The general theory of quantum mechanics is now almost complete. The underlying physical laws necessary for the mathematical theory of a large part of physics and the whole of chemistry are thus completely known, and the difficulty is only that the exact application of these laws leads to equations much too complicated to be soluble. (Dirac,1929)
Condensed Matter Physics Approach: the density n(r) as the key variable
QC DFT
DFT provides a viable alternative, less accurate perhaps, but more versatile DFT recognizes that systems differ only by their potential v(r) and provides a prescription to deal with T and Vee maps the many-body problem with Vee onto a single-body problem without Vee . Knowledge of n(r) implies knowledge of and v(r), and hence of all other observables.
Practical implementation?
t (r ) =
Local approximation GS minimization of energy functional with the constraint:
3 (3 2 ) 2 3 n(r )5 3 10
dr n ( r ) =
...We do not expect an accurate description of chemical bonding with the Local Density Approximation (LDA)... (Kohn & Sham, 1965)
R.P., M.C. Payne & A.D. Simpson, PRL 75, 4748 (1995)
(2)
(and, thus, the excited states!!) ((2) not true in spin-DFT,.. )
Some subtleties...
How do I know, given an arbitrary function n(r), that it is a density coming from an antisymmetric N-body wave function (r1,...,rN)? N-representability Solved: any square-integrable nonnegative function satisfies it How do I know, given an arbitrary function n(r), that it is the ground state density of a local potential v(r)? V-representability Not so simple: Constrained-search formalism (Levy-Lieb), but unicity of the potential is lost.
Hartree describes GS of atoms much better than TF (reproduces the shell structure)
Independent electrons
(r1 , L , r
= det{i (r )} =
1 (r1 ) L (r1 )
M O M ! 1 (r ) L (r )
1 2 (r1 , L, r ) T (r1 , L, r ) = i (r ) i (r ) 2 i =1
( r1 ,L , r ) = det{i (r )}
Kohn-Sham equations
+ Eion-ion
+ Eion-ion
HF vs LSD
(assuming that rest of orbitals due not change significantly when the occupation changes)
N+1KS (N+1) = - A ; A electron affinity of the N-body system (B3LYP works very well)
Only valid for the exact Exc functional; test for approximate functionals.
works better with extended states; problems with localized states. I & A can be rigorously calculated as total-energy differences:
I = E0(N-1) E0(N)
A = E0(N) E0(N+1)
Supercells
vacuum
Molecule
Defect
Surface
K-point sampling
H. J. Monkhorst and J. D. Pack PRB 13, 5188 (1976); 16, 1748 (1977) J. Moreno and J. M. Soler PRB 45, 13891 (1992)
Solution of the Kohn-Sham equations: Basis set to expand the Kohn-Sham Orbitals Effective implementations for large systems: Car-Parrinello approach and iterative minimization methods.
Simple argument: spherical hole of constant depth n/2 around the electron Rx n/2
LSD: performance
EX : 5% smaller ; EC : 100% larger (EXC << T, VH, Vne ; but EXC 100% bonding energy) Cohesive (atomization) energies: 15% larger ( 1.3 eV overbinding) bond lengths: 1% smaller ; bulk moduli (elastic constants) 5 % Favors close-packed structures Energy barriers: 100% too low (no chemical accuracy) wrong description of magnetic systems: Fe LDA is fcc paramagnetic (exp: BCC ferromagnetic) Poor description of weak bonding (van der Waals, hydrogen bonds). Atoms & Clusters VXCLSD : exponetial decay with n(r)**(1/3) instead of -1/r negative ions: generally unstable (electron affinities: 20% error)
nXC describes the effect of e- e- repulsion: the presence of an ein r reduces the probability of finding another e- in r electronic charge defect (effective positive charge) EXC : coulomb interaction (attractive) between an e- and its XC-hole
nX nC nXC = nX + nC
Fermi hole Coulomb hole
Two different strategies to determine f(n,n) ... Semiempirical (Becke): fitted to reproduce molecular results (but they fail for delocalized systems) Chemistry (BLYP) Non-empirical, based on general arguments and capable of describing different types of bonding (Perdew) Physics (PBE)
Perdew, Burke & Ernzerhof, PRL 77, 3865 (1996) (Older version: PW91; Perdew & Wang, PRB 46, 6671 (1992))
EC from Lee, Yang & Parr (PRB 37, 785 (1988)): nC does not
satisfied some basic constraints.
The combination (BLYP) works extremely well for chemical applications (empirical)
GGA: major improvement over LDA, chemical accuracy not too far away
Nonlocal functionals
ADA, WDA
Reuter and his colleagues show just how close science has come to using ab initio theoretical methods to calculate net catalytic reaction rates on complex solid surfaces. They have applied an elegant method that they call ab initio statistical mechanics, which involves two stages first, using first-principles quantum mechanics to calculate the activation barriers and transition-state vibrational frequencies for all the relevant elementary surface reactions; second, to couple these through statistical mechanical methods involving transition-state theory and kinetic Monte Carlo simulations of the reaction process.
Vibrational frequencies are used to incorporate entropy considerations Kinetic Monte Carlo , allowing efficient sampling of the tremendous range of different timescales necessary to describe all the different elementary steps, and thus simulate the kinetics of the whole system.
In this way, Reuter et al. were able to calculate net catalytic reaction rates on solid surfaces under conditions similar to those used in industrial processes. News & Views, Nature 432, 282 (2004)
Density-functional theory (DFT) for energetics of all relevant processes: motion of the gas-phase molecules, dissociation, adsorption, surface diffusion, surface chemical reactions, and desorption. Statistical mechanics problem solved by kinetic Monte Carlo Narrow region of highest catalytic activity: Kinetics builds an adsorbate composition that is not found anywhere in the thermodynamic surface phase diagram. K. Reuter et al, PRL 93, 116105 (2004)
The quantum method used by Reuter et al. is a version of density functional theory (DFT) that achieves nearly state-of-the-art accuracy in predicting the energies of such systems. Nevertheless, the authors admit that this can still be off by as much as 30 kJ per mol in estimating activation barriers. Given this drawback, it is surprising that they were able to achieve such impressive accuracy in their calculated carbon monoxide oxidation rates over RuO2 .They attribute this agreement with experimental rates to an effect they imply is generic to catalytic reactions the combined action of many elementary steps that simultaneously affect the rate. News & Views, Nature 432, 282 (2004)
References
R.M. Martin. Electronic Structure: Basic Theory and Practical Methods. (Cambridge University Press, Cambridge, 2004). W. A. Harrison. Electronic Structure and The Properties of Solids. (Dover, New York, 1989). A. P. Sutton. Electronic Structure of Materials. (Clarendon, Oxford, 1993).
K. Capelle. A Birds-Eye View of Density Functional Theory. arXiv:condmat/0211443 v5 (2006). M. C. Payne et al. Iterative minimization techniques for ab-initio totalenergy calculations. Review of Modern Physics 64, 1045 (1992). R. O. Jones & O. Gunnarson. The density functional formalism, its application and prospects. Review of Modern Physics 61, 689 (1989).