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• Basic considerations
HK
vext (r) n0 (r)
• Hohenberg-Kohn theorems
n ({r i }) 0 ({r i })
• Shortcomings of DFT
Forces à Vibrations
N dimer
Total energies Pt
Erhart, FKA091 11/2016
Some possible applications of DFT
Structure prediction and phase stability: Platinum series nitrides
Electronic structure
High pressure Low pressure
(single bonded nitrogen) (triple bonded nitrogen)
Erhart, FKA091 11/2016
Some possible applications of DFT
Defects: Thermodynamics, kinetics, electronic properties
Energetics – Which defects and how many
Vacancy level
Electronic structure
Total energies and forces à optical properties
Erhart, FKA091 11/2016
Some possible applications of DFT
Property prediction and screening: Substituted norbornadienes
donor
acceptor
Substitutions affect
position of absorption band
à can be tuned to solar spectrum
HOMO LUMO
Basic considerations
The Schrödinger equation
@
i = Ĥ nuclear R
@t electronic r
X ~2 X ~2
Ĥ = rn 2
r2i mixed
n
2M i
2me
| {z } | {z }
T̂R T̂r Kinetic terms
1 1 X Zn Zm e2 1 1X e2
+ +
4⇡✏0 2 |Rn Rm | 4⇡✏0 2 |r i r j |
n6=m i6=j
| {z } | {z }
V̂r V̂r
1 X Zn e2
+
4⇡✏0 i,n |r i Rn |
| {z }
V̂r,R Potential terms
Erhart, FKA091 11/2016
The Schrödinger equation
@
i = Ĥ (r 1 , r 2 , . . . , R1 , R2 , . . . ; t)
@t
Wavefunction is a function of
coordinates of all electrons and ions
(and depends parametrically on time)
Notational convenience:
(r 1 , r 2 , . . . , R1 , R2 , . . . ; t) Density functional theory in a nut shell:
Reduce 3N-dimensional problem
= ({r i }, {Ri }; t) to a 3-dimensional one
= (r, R; t)
Erhart, FKA091 11/2016
Born-Oppenheimer approximation
Expand many body wave function in a complete electronic basis set
that depends on positions of both nuclei and electrons
X
(r, R; t) = n (R; t) n (r, R)
n
Insert wave function ansatz into Schrödinger equation
@
i = Ĥ
@t
… and project onto the electronic basis: m (r, R)
@ ⇣ ⌘ X hD E i
i m = T̂R + V̂R m+ m (r, R) T̂r + V̂r + V̂R,r n (r, R) + V̂mn n
@t n
~2 ~2 ⌦ 2
↵
V̂mn = h m (r, R)|rRk | n (r, R)i · rRk + m (r, R)|rRk | n (r, R)
Mk 2Mk
Ĥe m (r; R)
= ✏m (R) m (r; R)
X1 1 X e 2 X Zn
Ĥe = r2i +
i
2 2 |r i r j | i,n
|r i Rn |
i6=j
| {z } | {z } | {z }
Tˆr V̂r V̂r;R
2. The nuclear problem: Solve for the nuclear degrees of freedom using
the derived potential energy surface (PES).
@
i m (R; t) = [T̂R + V̂R + ✏m (R)] m (R; t)
@t
Erhart, FKA091 11/2016
FKA091: Density functional theory
Theorem #1
• For any electronic system in an external potential
vext (r)
said potential is determined uniquely, safe for a constant,
by the ground state density n0 (r)
Corollary #1
• Since the Hamiltonian is thus fully determined, it follows that
the many-body wave functions for all states (ground and excited)
are determined.
• Thus all properties of the system are completely
determined given only the ground state density.
… and conversely Z
E0 < E + 0
[vext (r) vext (r)] n(r)dr
Corollary #2
• Said functional alone is sufficient to determine
the ground state energy and density.
• Excited states have to be determined by other means.
• DFT is a ground state theory
Energy functional: Z
E[n(r)] = F [n(r)] + vext (r)n(r)dr
universal system dependent
Non-interacting
Interacting electrons auxiliary
+ real potential particles in an
effective potential
Assumption:
• K-S assumes that the ground stateGround state density of interacting
density of the original interacting
system is equal
Walter Kohn Lu JeutoSham
that of some chosen non-interacting system that is
system is equal to that of some non-
exactly soluble, with all the difficult parts (exchange and
interacting system correlation)
that is exactly soluble,
included in some approximate functional of the density.
with all the difficult parts (exchange and
correlation) included in some
approximate functional of the density.
13. October 2010 6. The density functional theory 18
V. A. Fock
HK Kohn-Sham
vext (r) n0 (r) n0 (r) vKS (r)
Energy functional: Z
E[n(r)] = F [n(r)] + vext (r)n(r)dr
universal system dependent
KS orbital
• It is tempting to treat these states as KS eigenenergy
proper electronic (quasi) particle states;
but beware, this are fictitious states
HEG
"xc (n)
where is the exchange-correlation
energy of a homogeneous electron gas of density n
DFT
✓ ◆
1 2
r + vext (r) + vHxc (r) i (r) = ✏i i (r)
2
In practice
• a lot of numerics related to basis sets, treatment of core/valence
electrons, exchange-correlation, solving differential equations,
finding eigen values etc.
• Actual production DFT codes contain
tens to hundreds of thousands of lines of code
Kohn-Sham one-electron orbitals
KS orbital
• It is tempting to treat these states as KS eigenenergy
proper electronic (quasi) particle states;
but beware, this are fictitious states
silicon