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Introduction to Density Functional Theory

Shobhana Narasimhan Theoretical Sciences Unit JNCASR, Bangalore shobhana@jncasr.ac.in

What is DFT?
A very •(groundsuccessful approach to calculating the state) properties of many-electron systems from first principles

•Features:
- Ab

initio (only I/P = Z, A)

- Quantum Mechanical - Numerical - Approximate (could be exact, in principle?)

Nice things about DFT
•Ab initio, no empirical information •Predictive power
most •Very accurate fortypically < materials (errors few %)

lots of properties •Can calculatetechnological of scientific / interest

•Computationally intensive. Therefore •scales. (currently) limited to small length / time
For computational reasons, introduce further •approximations, might not always work.... Not very successful in strongly-correlated systems •(e.g., high-T superconductors).
c

Not-so-nice things about DFT

•Problems with van der Waals interactions, etc.

Numerical techniques and approximations •What one gets out of calculations .Kohn-Sham equations •How to solve the problem .Outline of talk •How to set up the problem .Hohenberg-Kohn theorem .

How to set up the problem .I.

…rN) – Solutions must also be properly antisymmetrized •Don’t know how to solve!! (to satisfy Pauli Exclusion Principle) .The Basic Problem •Many-electron system: Nn nuclei {Zi. condensed matter •Want to solve Many-electron Schrödinger Equation: HΨ (r1.…rN) = E Ψ (r1. atoms. r2. molecules. r2. Ri} + N electrons {rj} •Interact via Coulomb interaction Examples: •systems.

g. in practice ● No free parameters ● Solve numerically ● .?? Many-particle Schrödinger Equation Many-body Theory Retain many-body nature ● Use model Hamiltonian (e. ● Exact. Ising model. in principle ● Approximate. Hubbard model) ● Use suitable parametrization ● Solve numerically / analytically ● Density Functional Theory Map onto 1-particle Schrödinger Eq..How to deal with manyparticle Schrödinger Eq.

Ψmany-particle all properties of system n(r) = Ψ*Ψ   .Collection of particles in external potential v(r) . Rev.Hohenberg-Kohn Theorem -I •[Phys.Usually: v(r) Solve many-particle Schrödinger Eq.Hohenberg & Kohn showed (simple 3-line proof!) 1-1 mapping n(r) system exists v(r) all properties of . 136 B 864 (1964)] •Density as basic variable: .

with some free parametersathat have to be determined. The value •minimizingof the parameters is determined by some quantity. Fermat’s principle in optics. one guesses a solution of given form •(ansatz).. There are sophisticated numerical techniques •available for minimization problems.Variational Formulations When solving various complicated •might be possible to formulate the problems. Typically. Rayleigh-Ritz variational principle in Quantum Mechanics).g. itterms problem in of the calculus of variations (e. .

Ev [n] ≡ F [n] + ∫ v(r) n(r) dr has its minimum value when n(r) = nGS(r) → density of system in ground state . Etot .Ev [n = nGS] = EtotGS → total energy in ground state •Note: only proof of existence of F [n] . such that: . •IF F [n] were known… … then have converted many-electron pbm. we don’t know form. to one of minimizing a functional → n (r).II •Variational Principle: There exists a universal functional F [n] .Hohenberg-Kohn Theorem .

What have we achieved? . EGS δn(r) ∫ { δEv[n(r)] δn(r) } dr = 0 . r2.… rN)  maps exactly Density Functional Theory if F [n] known Variational Principle Minimize Ev [n] to find nGS.I N-electron Schrödinger Equation Solve for ΨGS(r1.

.What would we want now? •Approximation for F [n] •Ansatz for form of n(r) •Good prescription for minimizing E [n] wrt v  variations in n(r) OR an alternative to this.

due to nuclei) •For a non-interacting system. F [n] ≡ T0[n] + ½ n(r) n(r’) dr dr’ ∫∫r – r’| | + Exc[n] Hartree [Coulomb] Exchange-Correlation ..F[n]: non-interacting & interacting systems •Recall: Ev [n] ≡ F [n] + ∫ v(r) n(r) dr External potential (e. F [n] = T0[n] •For an interacting system.g.

F[n]: non-interacting & interacting systems •Recall: Ev [n] ≡ F [n] + ∫ v(r) n(r) dr External potential (e. F [n] = T0[n] • ∫ For an interacting system..g. F [n] ≡ T0[n] + ½ n(r) n(r’) dr dr’ ∫∫r – r’| | + Exc[n] | r – r’| Hartree [Coulomb] Exchange-Correlation . due to nuclei) Hartree potential VH(r)= n(r’)   dr’ •For a non-interacting system.

Rev.Kohn-Sham Equations •[Phys. 140 A 1133 (1965)] Non-interacting system Using H-K theorem ∫δn(r){δT   + v(r)}dr =0 0 δn .

2 + v (r)] ψ i(r) = εi ψ i(r) .Kohn-Sham Equations •[Phys. 140 A 1133 (1965)] Non-interacting system Using H-K theorem ∫δn(r){δT   + v(r)}dr =0 0 δn ∆ Solving [-½ Schrödinger Eq. Rev.

2 + v (r)] ψ i(r) = εi ψ i(r) .Kohn-Sham Equations •[Phys. Rev. 140 A 1133 (1965)] Non-interacting system Interacting system Using H-K theorem ∫δn(r){δT   + v(r)}dr =0 ∫δn(r){δT   + V (r) + δE  + v(r)}dr =0 0 0 H xc δn δn δn ∆ Solving [-½ Schrödinger Eq.

Kohn-Sham Equations •[Phys. Rev. 2 + v (r)] ψ i(r) = εi ψ i(r) 2 + veff (r)] ψ i(r) = εi ψ i(r) . 140 A 1133 (1965)] Non-interacting system Interacting system Using H-K theorem ∫δn(r){δT   + v(r)}dr =0 ∫δn(r){δT   + V (r) + δE  + v(r)}dr =0 0 0 H xc δn δn δn [-½ ∆ ∆ Solving [-½ Schrödinger Eq.

Kohn-Sham Equations •[Phys. 140 A 1133 (1965)] Non-interacting system Interacting system Using H-K theorem ∫δn(r){δT   + v(r)}dr =0 ∫δn(r){δT   + V (r) + δE  + v(r)}dr =0 0 0 H xc δn δn δn [-½ (1-electron eqns. Kohn-Sham equations + v (r)] ψ i(r) = εi ψ i(r) 2 2 + veff (r)] ψ i(r) = εi ψ i(r) . for interacting system!) ∆ ∆ Solving [-½ Schrödinger Eq. Rev.

What have we achieved? II N-electron Schrödinger Equation Solve for ΨGS(r1. EGS if Exc known Effective one-electron equations Solve to get nGS. EGS .… rN)  maps exactly if F [n] known Variational Principle Minimize Ev [n] to find nGS. r2.

What have we achieved? III indifferent like hate love like adore dislike dislike love hate love hat e dislike hate dislike adore dislike .

What have we achieved? III indifferent like hate love Where? like adore dislike dislike love hate love hat e dislike hate dislike adore dislike .

How to Solve the Problem .II.

Determining K-S Hamiltonian Want to solve: [-½ where                veff (r) = VH[n(r)] + Vxc[n(r)] + v(r) 2 + veff (r)] ψi(r) = εi ψi(r) •Problem 1: V . xc ∆ xc ← n ← solution of problem! . V H •Problem 2: Form of V [n] not known….

Self-Consistent loop v known/constructed Initial guess n(r) Generate new n(r) Calculate VH[n] & VXC[n] veff(r)= Vion(r) + VH (r) + VXC (r)  Hψ i(r) = [­1/2∇ 2 + veff(r)] ψ i(r) = ε i ψ i(r) Calculate new n(r) = Σ i|ψ i(r)| 2 Problem Diagonalizing Problem Mixing No Self-consistent? Ye s Problem solved! Can now calculate energy. . etc. forces.

›Approximate n(r) . one where ionic positions slightly different).Initial Choice of n(r) Various possible choices.from solving problem in a smaller/different ›Random numbers.. ›Superpositions of atomic densities.. e. .g. basis.g..: ›Converged n(r) from a closely related calculation (e. e.g.

analytical approximations] xc xc homogeneous electron gas.Exchange-Correlation Potential • V ≡ δE /δn contains all the many-body information. from Quantumfor Carlo . •Local Density Approximation: Exc[n] = ∫ n(r) VxcHOM [n(r)] dr Replace Surprisingly successful! Generalized Gradient Approximation(s): Include •(r) ∆ n . Known Monte •various [numerically.

convenient.Localized sets (atomic orbitals. Gaussians.) .Have to diagonalize a matrix of size Nb x Nb •Various possible choices of basis: .Choice of Basis •Can choose to expand wavefunctions in a basis set: ψi(r) = Σα ciα fα(r) •Eigenvalue equation then becomes: Σβ Hαβ ciβ = εi ciα . etc.Choose so that calculation is fast.Plane waves . accurate. .

(Numerical) Advantages when solving Kohn-Sham eqns.: •Have to solve for fewer eigenvalues.a weaker potential than the Further tailor this so that wavefunctions •behave ‘properly’ potential of interest. When solving using a basis plane •waves). remove core-electron degrees of Valence electrons see •full Coulomb potential.Pseudopotentials Frozen core: •freedom. •No Coulomb singularity (cusp in wavefunction) at . yet in region computationally cheap. basis size drastically(especially(smaller reduced matrices to diagonalize).

. but should be convincing enough to produce desired results…. works like a Don’t •works care about internal structure as long as it right! •But cheaper!! •Obviously it can’t reproduce all the functions of a real cop.Pseudopotentials: An analogy! “Dummy •agencies!cops” used by many law-enforcement Stick a the •it looks mannequinitin uniform bycop! highway … if like a cop.

Replace exact •diagonalizationdiagonalization by iterative / minimization.fictitious molecular dynamics (CarMixing •loop. Map onto •Parrinello). techniques when updating in iterative SCF Fast Fourier back •between realtransforms to gospace.Numerical Techniques •Lots of further tricks to speed up calculations….and forth and reciprocal .

by Iterative Diagonalization + Mixing Linear Broyden DIIS Modified Broyden Molecular Dynamics Direct (Car-Parrinello) Minimization Davidson Conjugate Gradient Steepest Descent Conjugate Gradient DIIS (and lots of ‘etc.Fast. new(ish) methods for iterative solution Minimize energy functional Solve Kohn-Sham eqns.’s scattered plentifully about!) .

III. What can we calculate? .

using Local Spin Density Approximation) • Ferroelectric properties (e..g.. etc. using Berry’s phase formulation) • Excited state properties (using Time Dependent Density Functional Theory) • etc..! .g. by Density Functional Perturbation Theory) • Magnetic properties (e.What we can calculate • Total energy in the ground state • Density in the ground state • Forces on nuclei • Eigenvalues (not rigorously exact) • Vibrational frequencies (e.g..

elastic moduli.pressure derivative of bulk modulus . activation energies.… From this curve.Total Energy •Very useful quantity! Can use to get structures.lattice constant . can get . vibrational frequencies.bulk modulus . •adsorption energies. heats of formation. diffusion barriers.

vibrational frequencies.g. Can use in molecular dynamics (e. •transitiontostates (saddle points). on nuclei using Hellmann-Feynman •Particularly easy to obtain with plane wave basis.Forces Born-Oppenheimer approximation: separate •electronic and nuclear degrees of freedom. •properties at finite temperatures).. Can use obtain equilibrium structures (minima). to get . Obtain forces •theorem.

• Typically. no empirical input! Few correlated •wherefailures: stronglyinteractions systems.I Can reproduce experimental results . errors are less than few %.Why we love DFT. systems van der Waals are important… •Work in progress! . • Recall. can do few 1000 atoms computers. Can do ~ •on bigger 100 atoms on PC.

and others not? .Why are some materials reactive and others not? .etc.Why do some materials/objects melt at low temperatures.Why we love DFT.Why do bizarre structures form on surfaces of some metals? .Why do some materials show thermal expansion.II Can use •diversity to understand complicated observations of . . and others thermal contraction? .

Solvents (Balasubramanian) ..etc. e.g.III Can use to •properties design new materials with desired Better / cheaper / cleaner / harder / more •efficient… .Ferroelectrics (Waghmare) ..Catalysts (Narasimhan) . etc.Why we love DFT. suggestions for materials harder than •diamonds! .

Why we love DFT..g. planetary interiors… Is the earth’s core liquid? Is Jupiter’s core metallic? .IV Can study conditions •expensive to measurethat are impossible / experimentally •e.

Conclusions Density Functional Theory is a very successful approach to calculating the properties of manyelectron systems from first principles. .

Cambridge.Conclusions Density Functional Theory is a very successful approach to calculating the properties of manyelectron systems from first principles. 2004 …and references therein. . Bibliography Richard Martin: “Electronic Structure. Basic Theory & Practical Methods”.

JNCASR.it/smr.php?1783 Deadline: March 1 2006 .ictp. Bangalore Theory Lectures (focus on DFT methods) ●3-day International Conference ●Hands-on computer tutorials (using Quantum ESPRESSO) ● Application forms available at http://agenda.NEW!!! FORTHCOMING SUMMER SCHOOL! Summer School and Workshop on Electronics Structure Methods and their Applications 10-22 July 2006.