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Lecture 1

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Tùng Nguyễn Hoàng
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14 views20 pages

Lecture 1

Uploaded by

Tùng Nguyễn Hoàng
Copyright
© © All Rights Reserved
We take content rights seriously. If you suspect this is your content, claim it here.
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Computational Chemistry:

A DFT crash course


Useful Material
Books
 A chemist’s guide to density-functional theory
Wolfram Koch and Max C. Holthausen (second
edition, Wiley)
 The theory of the cohesive energies of solids
G. P. Srivastava and D. Weaire
Advances in Physics 36 (1987) 463-517
 Gulliver among the atoms
Mike Gillan, New Scientist 138 (1993) 34
Web
 www.nobel.se/chemistry/laureates/1998/
 www.abinit.org
Version 4.2.3 compiled for windows, install and
good tutorial
Outline: Part 1,
The Framework of DFT
DFT: the theory
 Schroedinger’s equation
 Hohenberg-Kohn Theorem
 Kohn-Sham Theorem
 Simplifying Schroedinger’s
 LDA, GGA
Elements of Solid State Physics
 Reciprocal space
 Band structure
 Plane waves
And then ?
 Forces (Hellmann-Feynman theorem)
 E.O., M.D., M.C. …
Outline: Part2
Using DFT
Practical Issues
 Input File(s)
 Output files
 Configuration
 K-points mesh
 Pseudopotentials
 Control Parameters
 LDA/GGA
 ‘Diagonalisation’

Applications
 Isolated molecule
 Bulk
 Surface
The Basic Problem
Dangerously
classical
representation

Core
s

Electron
s
Schroedinger’s Equation
  2 
   V   Ri , ri   . Ri , ri 
 2m 
Potential Energy Wave function
Kinetic Energy Coulombic interaction
External Fields
Energy levels

Hamiltonian operator

Very Complex many body Problem !!


(Because everything interacts)
First approximations
Adiabatic (or Born-Openheimer)
 Electrons are much lighter, and faster
 Decoupling in the wave function

 Ri , ri   Ri . ri 


Nuclei are treated classically
 They go in the external potential
H.K. Theorem
The ground state is unequivocally
defined by the electronic density

Ev   F    vr  r dr
Universal
functional
•Functional ?? Function of a
function
•No more wave functions here

•But still too complex


K.S. Formulation
Use an auxiliary system
 Non interacting electrons
 Same Density
 => Back to wave functions, but simpler this time
(a lot more though)
N K.S. equations
  2 
(KS1     Veff  i r   i . i r  (ONE particle in a box
 2m  really)
)
 r  Exchange correlation
(KS2) Veff r  V r   dr    XC  r  potential
r  r

 r    i r 
2
(KS3
) i
Self consistent loop
Initial
density
From density, work
out Effective
potential
Solve the independents
K.S. =>wave functions

Deduce new density from


w.f.
N New density ‘=‘
O input density ??

YES Finita la
DFT energy functional
1  r 
E   TNI     r vr dr   drdr   E XC  
2 r  r

Exchange correlation
funtional Electrons are fermions
(antisymmetric wave function)
Contains:
Exchange
Correlation
Interacting part of K.E.
Exchange correlation
functional
At this stage, the only thing we need is:E XC  

Still a functional (way too many variables)


#1 approximation, Local Density Approximation:
Homogeneous electron gas
Functional becomes function !! (see KS3)
LDA
Very good parameterisation for E  
XC

Generalised Gradient Approximation:


E XC  ,  
GGA
DFT: Summary
The ground state energy depends
only on the electronic density (H.K.)
One can formally replace the SE for
the system by a set of SE for non-
interacting electrons (K.S.)
Everything hard is dumped into Exc
Simplistic approximations of Exc work !
LDA or GGA
A little bit of Solid State
Physics
Crystal Periodicity
structure
Reciprocal space
ai b j 2 . ij
(Inverting effect)

sin(k.r)
Reciprocal Space
Real
Brillouin bi
Space
Zone
ai k-vector (or k-point)
See X-Ray diffraction for instance
Also, Fourier transform and Bloch
Band structure
E Energy
levels
(eigenvalues of SE)

Molecul Crystal
e
The k-point mesh

Brillouin Corresponds to a
Zone supercell 36 time
bigger than the
primitive cell

Question:
Which require a finer
(6x6) mesh mesh, Metals or
Insulators ??
Plane waves
Project the wave functions on a basis set
Tricky integrals become linear algebra
Plane Wave for Solid State
Could be localised (ex: Gaussians)

+ + =

Sum of plane waves of increasing


frequency (or energy)

One has to stop: Ecut


Solid State: Summary

Quantities can be calculated in the


direct or reciprocal space
k-point Mesh
Plane wave basis set, Ecut
Now what ?
We have access to the energy of a
system, without any empirical input
With little efforts, the forces can be
computed, Hellman-Feynman theorem

Fi   r vi r  i dr

Then, the methodologies discussed for atomistic


potential can be used
Energy Optimisation
Monte Carlo
Molecular dynamics

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