Version: 20110812

BO HF HF
DFT

SCF

1. 2.

[1] Richard M Martin, Electronic Structure: Basic Theory and Practical

Methods. Cambridge University Press, Cambridge, 2004.
[2] Christopher J Cramer, Essentials of Computational Chemistry:
Theories and Models. 2nd Ed. Wiley, England, 2004.

(STM)

1.1
1.1.1 -(BO)
1 amu (12C/12)
1822.83
BO

H r, R E r, R

e2 Z I Z J
e2 Z I
2
2 2
e2
2

I
i

H -
riI
rIJ
I 2 mI
i 2 mi
i
I
i j rij
I J

BO

r, R N R el r;R

H el R el r E R el r

H el R
N R

el r; R
POSCAR E R (PES)

BO
E1 E2

C-C

1.1.2
BO

H hi
i

hi

e2 Z I
2
i

riI
2mi
I

hi i ii
i (MO) i

HP 12 ... n
E i
i

Hartree (HP)
Hamiltonian HP
( H el )

hi

e2 Z I
2 2
i
vi
riI
2mi
I

vi
ji

j
rij

drj

j j e

hi i HP
E

HP

| i |2 | j |2 e2
1
i
dri dr j
2 i j
rij
i

N
0

i hi
1

(0)

i i hi i
n 1

(1)

(SCF)EDIFF

1.1.3 Slater Hatree-Fock

HP

H h1 h2

h1

2 2
1 v r1
2m
5

h2

2 2
2 v r2
2m

E a b , a 1 b 2

P12 a 1 b 2 a 2 b 1 a 1 b 2

1
a 1 b 2 a 2 b 1
2

SD

1 a 1 b 1
2 a 2 b 2

Slater (SD) N

1
N!

S D r1 , r2 , , r N

1 1
1 2

2 1
2 2

N 1
N 2

1 N

2 N

N N

1, 2 N

SD 0 Pauli
Fock Hartree-SCF Slater

SD

1
SD dr1dr2 J ab K ab
r12

J ab HP

1
1
HP dr1dr2 a2 1 b2 2 dr1dr2
r12
r12

K ab a 1 b 1

1
a 2 b 2 dr1dr2
r12

Kab Slater HP
Roothann HFSCF

det(F-ES)=0 f Fock

2 2
1
1

Z I P
rI
2me
2

e2
1 1 r 2 2 dr1dr2
12
occ

P 2 ai a i
i

Fock
HartreeFork

1.1.4 post-HF
HF
HF
Slater Pauli

HF Ecorr=E-EHF
0.3~2%

HF
CIConfigurationInteraction
CCCoupledclustermethod
MPxMollerPlessetperturbationtheory
DFTDensityfunctiontheory
HF postHF DFT

1. CI

vir occ

vir occ

| C0 | 0 Cia | ia Cijab | ijab ...

a

a b i j

S, D, T, Q
(CIS)CIS
FullCI

Fermi
(CAS)(RAS)
CI
(MCSCF)

MCSCF CICI HF MCSCF

MRCI
2. Coupled-Cluster

ansatz

cc eT HF
T T

T T1 T2 T 3 ....
T2 HF

occ vir

t
i j a b

ijab FullCI : (1 T ) HF

ab
ij

CCD CCD (1 T2

T22 T23

) HF
2! 3!
8

Fermion ,

3. MP
CI
Muller Plesset HF
MP

H H (0) V
Fock

H (0) fi
i

(0) HF
occ 2
occ
e
1

V ( Jij K ij )
2
j i rij
i, j

HF MP CI
MP MP
MP MP MP2
MRCI MCSCF CASPT2
CASSCF
PostHF HF<MP2~MP3~CCD<
CISD<CCSD<MP4<CCSD(T) G2G3
PostHF

1.2 DFT
v(r) (rr ...r ) (observables)

n(r) N dr2 dr3... drn * (rr2...rn ) (rr2 ...rn )

| o | * (r1r2 rN ) oi (r1r2 rN )dr1dr2 drN

i

(r )
N (r1r2 rN )o1 (r1r2 rN )dr1dr2 drN dron
*

1.2.1HohenbergKohn [1]
n
n(r) v(r) observables
va vb n0
1

P.HohenbergandW.Kohn,Phys.Rev.1964,136,B864

Ea0 b0 | H a | b0
b0 | H a H b H b | b0
b0 | va vb | b0 Eb0
va vb

Eao dr[va vb ]n0 (r) Eb0

Ebo dr[vb va ]n0 (r) Ea0

Ea0 Eb0 Ea0 Eb0

n
v F[n] n

Ev [n] drv(r )n(r ) F [n]

n n0
Levi
E m in | H | m in m in | H |

m in[ m in | T U |
n

m in{ F [ n ]
n

d r v ( r ) n ( r )]

d r v ( r ) n ( r )}

1.2.2KohnSham [2]
Levi

F [n] T [n] U [n]

TS [n]

2 n
dri* (r ) 2i (r )

2m i

U[n]

U H [ n]

1
n(r)n(r')
dr dr'

2
| r r' |

E XC Etot TS V U H (T TS ) (U U H )

occ

n (r ) | i (r ) | dr
i

W.KohnandL.J.Sham,Phys.Rev.1965,140,A1133.

10

2
vext (r) vH (r) v XC (r)]i ii
2m

DFT HF DFT KS
HF Slater
DFT
DFT
KS KS
KS
HF DFT

1.2.3
Pauli

E X [n] nSD | U | nSD U H [n]

nSD | T U | nSD TS [n] U H [n] E X [n]
EC [n] F [n] (TS [n] U H [n] E X [n])

min | T U | min SD | T U | SD
n

EC<0 Hartree
EXC[n]

()Jacob

Jacobi

aLDA

LDA
E XC
[n] drn(r ) XC (n)

XC (n) n Jacobi
LDA LDA

EXLDA drn 3 (r)

QMC n
LDA LSDALDA
LDA
bGGA
Jacobi

E XC drf (n, n)

11

GGA GGA
s

| n |
GGA Becke
n 4/3

Perdew
GGA PBE[3]
revPBE( )RPBE( Fx(s))PBEsol( )GGA LDA
overbinding
cmetaGGA Jacobi
metaGGA metaGGA TPSS

vXC EXC / n

vxc [n](r)

Excorb [{i }]
n(r)

E orb [{i }] i (r) vs (r)

d r d r[ xc
c.c]
i (r) vs (r) n(r)
i
3

OEP OPM
KohnSham OEP KS
Slater KLI CEDA KLI

dHF KS HF
DFT Jacobi

GGA
EXC aEXexact (1 a) EXC

adiabaticconnection =0
=1 n

F [n] | T Vee |

EXC [n] F1[n] F0 [n] EH [n]

d EH [n]

EXC , [n]d
0

(a=0.5)
( GGA ) B3LYP[4]

J.P.Perdew,K.Burke,andM.Ernzerhof,Phys.Rev.Lett.1996,77,3865.
4
P.J.Stephens,F.J.Devlin,C.F.Chabalowski,M.J.Frisch,J.Phys.Chem.1994,98,11623.

12

B 3 LYP
EXC
a0 EXexact (1 a0 ) EXslater aX EXB ac ECVWN (1 ac ) ECLYP

1 1 erf(r ) erf(r )

r
r
r
(SR)(LR) HSE

HSE
EXC
aEXHF , SR (1 a) EXPBE , SR EXPBE , LR ECPBE

e Beck

B3
LDA
EXC
EXC
c1 ( EXexact EXLDA ) c2 EXGGA c3ECGGA

DH
LDA
EXC
EXC
c1 ( EXexact EXLDA ) c2 EXGGA c3 ( ECPT 2 ECLDA ) c4 ECGGA

PT2 doubleexcitation

ECPT 2

| i j | vee | |2
1

4 ij i j

Jacob

()
a) Hartree
EC [ n] 0 EX [n] EH [n]
(SIC)
N

SIC
E XC
[ n] E XC [ n] ( EH [ ni ] E XC [ ni ])
i

b H2+ 0.5
0 1

HF

13

c H2

HeitlerLondon

H2

()DFT+X
aDFT+U
(Mott
) d Hubbard

H t

i , j ,

(ci, c j , h.c.) U ni ni
i 1

onsite DFT+U

E DFT U E DFT U eff ( nmi mi nm1m2 nm 2 m1 )

mi

m1m2

bDFT+D DFT
DFT

EDFT D EKS C6 R 6 f dmp ( R )

LDA nl

EvdW DF E GGA ( EcLDA Ecnl EcGGA )

nl

Ecnl

1
d 3r1d 3r2 n (r1 ) (r1 , r2 ) n (r2 )

vdWDF vdWDF

exchangecorrelation

1.3 Pseudopotential
Two facts about atom electronic structure: 1.
2.

The idea of Psp PspPOTCAR

14

1.3.1 NCPP
NCPP
1. (r ) [ul ( r ) / r ]Ylm
2. (r )
ps

3.

d 2 ps
u r
2 l

(
1)

l
l
vltot ( r ) l
dr ps

2
ul r
2me r

4.
ps

3 l v

lm

vl ( r ) Ylm

lm

1.
2.
3. rc
4.norm conserving
23 Big enough to make
soft PspSmall enough to keep good transferabilityNot too small to be very close to the outmost
radial node
Troullier-Martines(TM)[5]

PS
l

RlAE ( r ) r rcl
l p( r )
r rcl
r e

p( r ) c0 c2 r c4 r ...... c12 r
2

12

N.TroullierandJ.L.Martins,Phys.Rev.B1991,43,1993

15

PS

vl
v [ ] v [
xc

xc

core

vltot v H [ 0PS ] v xc [ 0PS ] 0

0PS ] v xc [ core ] v xc [ 0 ] v xc [ ]

Core Correction: v xc [ 0PS ] v xc [ core 0PS ]

Partial core Correction

ocore (r) r r nlc

l
ocore (r)
l
nlc
c

o ci r r r

i 3
r

nlc

Wigner-Seitz

1.3.2 Kleinman-Bylander [6]

ab initio

v PS | Ylm vl (r )Ylm |
lm

PS

vl ( r ) Z/r v ( r )
Local vloc ( r ) Z/rZ
local non-local
vl ( r ) vloc ( r ) vl ( r )
vloc ( r )

| Y

lm

lm

vloc (r )Ylm | vloc (r ) | Ylm Ylm | vloc (r )

lm

PS

v PS vloc ( r ) | Ylm vl ( r )Ylm |

lm

semi-local
| Ylm vl ( r )Ylm |

j (kr) v(r) j (k r)r drP (cos

2

kk

Kleinman Bylander non-local

| Y

lm

lm

v1 ( r )Ylm | | lmKB ElKB lmKB |

lm

L.KleinmanandD.M.Bylander,Phys.Rev.Lett.1982,48,1425.

16

j(kr ) (r )r dr j (k r ) ( r )r drP (cos

2

kk

N {|Gi>} N(N+1)/2
N KB (Wronskian)
l
ghost state ghoststate
[PRB1990, 41, 12264]

1.3.3.USPPPAW
vNL

| i i |

i | ips

| i ( i T vloc ) | ips
Bij i | j , | i ( B 1 ) ji | j , v NL Bij | i j |
j

ij

(T vloc vNL ) | ips i | ips

Qij i | j R i | j R 0 Bij vNL
ps

ps

2p
[Phys. Rev. B 1990, 41, 7892]

NCPP
[7]

S 1 Qij | i j |
ij

vNL ( Bij jQij ) | i j |

ij

D.Vanderbilt,Phys.Rev.B1990,41,7892

17

i | S | j R i | j R
ps

ps

(T vloc vNL ) | ips i S | ips

USPP Q |
1994 Blchl PAW(Projector augmented wave)[8]

T ps , T I TR
R

USPP PAW
| |

ps

{| m | mps }

cm m |
T I

{|

ps

| mps } m |

T,

A T AT

1.4

HF

1.4.1 HF
HF N4
HF 1. 2.
3.
1.CNDO(completeneglectofdifferentialoverlap)
CNDO S v v

( v | ) v ( | ) ( | ) AB

AA IPA EAA
AB

AA BB
2 rAB ( AA BB )

Z
1
| 2 k | =-IP -Z k - Z A Zk
Ak
2
k rk
k

P.E.Blochl,Phys.Rev.B1994,50,17953.

18

( B )Sv
Z
1
| 2 k | = A

2
2
k rk
CNDO PPP CNDO
CNDO

2.INDO(intermediateneglectofdifferentialoverlap)
CNDO INDO
(ss|ss)=Gss(ss|pp)=Gsp,(pp|pp)=Gpp,(pp|pp)=Gpp
(sp|sp)=LspZerner INDO
INDO/S ZINDO/SINDO/S
d>d INDO 3MINDO/3

s p AB
3.NDDO(neglectofdiatomicdifferentialoverlap)
INDO CNDO
NDDO ( v | ) , A , , B NDDO
MNDO,AMI,PM3,PM6
(1) MNDO(modifiedneglectofdifferentialoverlap)
Fock

1
F U Z B ( | sB sB ) Pvv [( | vv) ( v | v)] P ( | )

2
B A
v A
B B B
A
B

1
1
F ( v ) S v P ( | v )
2
2 A B
MINDO/3
MNDO

VN Z k Z l ( sk sk | sl sl )(1 e k rkl e l rkl )

k l

(2) AM1(AustinModel1)
Gaussian
MNDO
VN ( A, B ) VAB

Z AZB
rAB

[a
i 1

A,i

bA ,i ( rAB c A ,i )2

a B ,i e

bB ,i ( rAB cB ,i )2

(3) PM3(parameterizedmodel3)
AM1 4

19

PM5 d PM6(2007)

VNPM6 ( A, B) Z A Z B ( s A s A | sB sB )(1 AB e AB ( rAB 0.0003rAB ) )

(4) PDDG(pairwisedistancedirectedGaussianfunction)

VNPDDG ( A, B) (

2
2
1
[( r D D )2 /10]

) (nA Pi , A nB Pj , B )e AB i , A j ,B
nA nB i 1 j 1

1.4.2
tightbinding,TB ExtendedHuckelTheory(ETH)
STO S

H VSIP

1
H v C v ( H H vv ) S v
2
C v 1.75EHT
TB Slater KosterSK TB
[Phys.Rev.1954,94,1498] Brillouin
Hamiltonian Brillouin
Hamiltonian (1)(2)
(3) (4) Hamiltonian


*
3
Bloch H n (r R i )hm (r R j )d r

SK s,p,d
SK 14 ss,sp,pp,pp,sd,pd,pd,dd,dd,dd,ps,ds,dp,dp
SK TB

1.4.1NRLTB[J.Phys.:Condens.Matter2003,15,R413]
SK Lowdin

Hamiltonian SK
Lowdin
NRLTB

DFT

d 3k
n (k ) F [n(r)]
(2 )3 n

Fermi F F

20

n '(k ) n (k )

F [n(r )]

Ne

onsite

I e R F ( RIJ ) F ( R)
2

IJ

( RC R)
1 e

R RC

Hamiltonian onsite
2

hIl al bl 3 cl 3 dl 2
SK

hll ( R) (ell fll R gll R 2 )e

hll2 R

F ( R)

93

sll ( R) ( ll pll R qll R 2 rll R3 )e

sll2 R

F ( R)

1.4.2DFTB[Phys.Stat.Sol.B2000,217,41]
DFTB

Etot EBS Vrep (R IJ )

I J

DFT

1
E[ n] f a a | 2 vext vH [n0 ] vxc [n0 ] | a
2
a
2 Exc [n0 ]
1
1

drdr

n n

2
|
|
r
r

1
drvH [n0 ](r )n0 (r ) Exc [n0 ] EII drvxc [n0 ](r )n0 (r )
2

EBS Hamiltonian onsite

r
[T veff [ nI0 ] ( ) 2 ]v (r ) vv (r )
r0
Hamiltonian
0
h
T veff [nI0 nJ0 ] I , J

DFT

21

NP
n
d n ( RC R)
Vrep ( R) n 2

R RC

otherwise

DFT

E2 nd Ecoul

1 N
qI qJ IJ IJ
2 I ,J

Hubbard UU
Janak

II U I

E at [ I0 ] HOMO

2 qI
nHOMO

IJ

'

16
1 I3 I r ' R I J3 J r R J
I U I
e
e
5
8
r r ' 8

Guass
IJ Ecoul 1/ RIJ
Ewald

1 N
PIl PIl 'WIll '
2 I lI l 'I

W Janak

1
WIll ' l l
2 nl ' nl ' P 0
Mulliken
occ

qI ni ci ci ni ci ci S qI0
I

occ

PIl ni ci ci ni ci ci S
i

Hamiltonian
0
h h

N
1
1
S IK JK qK S WIll '' WIl ' l '' PIl '' I , J
2
2
K
l ''I

22

SCCDFTBSCCDFTB Enscc Escc Erep Enscc

c c h
f

Escc E coul

23

*
n

2.1

a { }

s,p,d,(LCAO)

( r , , ) Rn ( r )Ylm ( , )
Ylm Rn(r) Slater Gaussian

1.Slatertypeorbital(STO)
STO

r , , r n1e rYlm
n
Slater
ADF Slater ,
Slater Slater

2.Gaussiantypeorbital(GTO)
Slater HartreeFock
1950 Boys Gaussian
Gaussian spxpypz
dxydyzdzx Gaussian

( x , y , z ) x i y j z k e r

ijk
i

=0

=1

dxy

px

dxz

Py

dyz

pz

dx2

dy2

=2

2
2

dz2
2

x +y +z d 5 d xy, yz, xz, x -y , 3z -r

GTO

24

A B Gaussian P Gaussian P A B
Gaussian AB
Gaussian
Slater Gaussian Slater r
r (x2+y2+z2)1/2 xy z Gaussian
r2 x2+y2+z2

Slater Gaussian r ,
(cusp)GTO

3. STOnG
Gaussian Gaussian
Slater ( Contracted ) r
n GTO STOnG
STO GTO Primitive
N

C a GTO X , Y , Z ; a , i , j , k
a

STO3G STO3G

4. splitvalencemulti
STO
STO STO
STO
321G valence double 3 contracted GTO
STO STO 2 1
GTO
5. Polarizationfunction

NH3 H2Odxy

25

631G(d) ( 631G*) d
631G(d,p) ( 631G**) p d
6311G(3df,3pd) d f p
d
6. Diffusionfunction
s p (
: Anion
excitedstate
631+G s p
631++G s s p
6311++G(3df,2pd) H2O GTO
7.
ccpVDZ cc correlationconsistent HF but calculations with
correlation, augccpVDZ: one set of diffuse
functionforeachangularmomentum

8. NumericalAtomicBasisSet
exactly
ConfiningPotential,energyshift,
Dmol3 (DN)(DNP)
d (DND)Siesta DZP TZP

2.2

n r Cn (g)eigr dg
g=0 g
(PBC)(1D)(2D)
supercell slab PBC Bloch

2.2.1
Step 1Bloch

nk r unk (r)eikr
unk (r )

2 2
h
v r
2m
26

[t, h] 0

r n1R tn (r) n r
1

n1 n2 n1 n2 exp(ik Rn )
Bloch

nk r Cn ,k G eik G r
G

G b ai b j 2 ij k

G
cutoff
energyENCUT
Bloch : k k
:
occ

n*k r nk r drdk
n BZ

Step 2Born-von Karman

BornvonKarman k

n N n eikNR 1 k

2
N N
m m , ( , )
NR
2 2

(0, N 1) k N k

Gcut

: BornvonKarman

27

2.2.2 Wrap around error

Gm
2Gm
veff
2Gm

G | veff | G veff (G n ) G G ,G n
n

2Gm Gm
3Gm 3Gm FFT wraparound error(WAE)
Gm
NGX/NGY/NGZ FFT
WAE 2Gm FFT WAE
1G 1G

2.2.3
(BZ)

BZ

BZ

nk ( nk ) dk

-
k

1
BZ

BZ

28

k k
N 2

f 2 ( k ) A0 A1 sin( k ) A2 sin(2k )

f 2 ( k )dk A0

f 2 (k

) f 2 (k

3
)
2

k 2
k k
k
Monkhorst-Pack[9] MP BZ
nk 1 nk 2 nk 3 KPOINTSMP k

ur (2r nk 1) / 2nk

r 1, 2,3,..., nk

Monkhorst-Pack k-grid

nk 8
MPGammak
k-sampling to define the Fermi surface precisely

H.J.MonkhorstandJ.D.Pack,Phys.Rev.B1976,13,5188.

29

2.3 (SCF)

Hartree

v H (r )

n(r)
dr
| r r |

Hartree

2vH 4

2.3.1

NBANDSIALGO

R[ ] ( h I) | Rayleigh
ap

ap

ap

ap

ap | h | ap

ap | ap

R[ ap ] R[ ap ] (h ap I) 0

(h ap I)1 R[ ap ]
(preconditioning)
K

30

G G

{ , } 2x2
ap

{ , ,
(1)

ap

(2)

, (3) ,...}

b Davidson RMM-DIIS
n n
2nx2n Davidson
RMMDIIS
R[n1 ]| R[n1 ] RMM

RMM-DIIS

c Lanczos
Lanczos Krylov Krylov
Krylov
Krylov Lanczos
Krylov

1 Lanczos 2 c2 (h1 h111 )

h11 1 | h | 1 n 1 cn 1 (h n hnn n hn ,n 1 n 1 )

Lanczos spurious solution Lanczos disease

2.3.2
Partial Occupation

BZ

BZ

n ( k ) | X | n ( k ) ( nk )dk

k
ISMEAR

1) Fermi-Dirac

31

f ( )

kBT

2) Gauss

f ( )

1
1 erf
2

k
T
B

T=0 E (T 0) E0

1
( F E )
2

k BT
E

F E k S ( f nk )
nk

F
0.05
3) Methfessel & Paxton
MP Gaussian
MP 0 MP F

1meV/atomMP 1
4tetrahedron method
k
k
f nk Blochl
1
2
3

SCF Legendre
KS

32

EKS TS [n ] E pot [n ]
E pot drvext (r )n(r ) EH [n ] E XC [n ]
TS [n ] ES drv in (r )n out (r )

ES i
i

KS

EKS [v in ] ES [v in ] drv in (r )n out (r ) E pot [n out ]

Harris-Foulkes
in

v[n ] vnin

EHF [nin ] ES [vn ] drvn (r )nin (r ) E pot [nin ]

in

in

n in n out HF KS HF
n out
HF KS

2.3.3SCF mixing
SCF nin n out
mixingIMIX

a Linear mixing

niin1 niout (1 )niin

niin (niout niin )

AMIX

n n nKS

nout ( 1) nin
1

n out n out v in

n in v in n in

ni 1 nKS nKS
in

nKS niin 1 (niout niin )

linearmixing

(r , r ) m f m (r ) f m (r )
m

m optimal

f m (r ) SCF

33

2 min

1
max

(polarizability)

v out G G, G v in G

G=0

G , G 1 Si 12
12 G
charge sloshing problem
mixing

1 G
min
b Mixing
ThomasFermi Kerker Mixing

2
G Gmax

Gmax BMIX
F(x)=x R[x]=F(x)-x Jacobian

R
x

Quasi-Newton-Raphson xi+1=xi-J-1Ri linear mixing

Broyden mixing quasi-Newton Jacobian
J0=I Jacobian
mixing Pulay
mixingMinimize the normal of the residue vector subject to the
constraint of conserving the number of electron (DIIS like). mixing
Kerker Mixing

mixing Broyden mixing

34

3.1 Charge density related
Differential charge density
Bonding type

3.1.1 Population analysis ()

Mulliken

occ

c P c c
i

i, j

N Tr ( PS )

( PS )

S |

q A Z A ( PS ) Mulliken
A

Lwdin
Mulliken r

1/2
rs s

(NPA)
Occupancy-weighted NAO
,
(ESP fitting)

vESP
k

qk

| r rk |

(a) conformational dependence for flexible molecules.

(b) ill-conditioned, especially for inner atoms.

Hirshfeld

35

d (r ) (r R )

q d (r )W (r )dr W (r ) (r R )[ (r R )]1

AIM by Bader (Bader )

zero flux surface: n 0

3.1.2
P P not well-defined

Well-defined P (r , t ) n (r , t )
Berry
slab

ext (r )

4
[ z a3 ( z0 z )] 0 z a3

z0 xy slab
(r )

ext

(r )

E FI [n ] Z I ( R I )

3.1.3
SDFT( DFT)

n (r )

| (r ) |

n(r) n n m(r ) n n i (r )

2 2
veff )i (r) ii (r)
2m

36

veff

n(r)
E xc ( n , n )

d
r

v
(
r
)

v
(
r
)

(
)
v
ext
xc
xc
| r r |
n

vext
(r ) B H +

(FM)(AFM)(SDW)

(non-colinear)

3.2

Molecular-orbital related

3.2.1 Band structure & DOS

k (DOS)

D ( )
n

dk
( n (k ))
4 3

37

channel

()

()

(Doping state)

m* 2

E 2

k 2

38

4 Band folding

/a

/a

/2a

/2a

/a

k E (k ) E ( k )
Band folding E(k) k=0
Band folding

Band crossing
avoiding crossing

5 IP()AE()WF()
Evac

Evac

LUMO

HOMO

Ef

(IP)(EA)

veff
wrap around error
IP EA SCF Koopmans theoremMO Slater
(SD)()

3.2.2 Instabilities
Large DOS at Ef suggests an instability
Peierls

39

Stoner
m (r ) n (r )
0
0
(r ) m(r )v[n(r )] v xc
(r )
v xc (r ) v xc

1
IM
2

m(r )dr I (Stoner )

1
2

nk (r) n0k (r) nk n0k IM

EF

M [n 0 ( E

1
1
IM ) n 0 ( E IM )]dE F ( M )
2
2

F ( 0) 1 In ( EF ) 1
0

W3d W4 d W5d n3d n4 d n5 d 3d

0

3.3

Total Energy related

3.3.1
minimization

40

BO Schrdinger H (R) (r ) E (R) (r) g

dE
F HellmanndR

-Feynman

E
H
|
|
R
R
(1) | H (2) |

| 0
R

MP2CC

3.3.2
Cij

Cij
Fi
2E

R j Ri R j
MIMJ

(1) Frozen phonon(2)

Response theory

n (r ) n (r ) vext

Ri
vext Ri

n(r )
DFPT i v KS
Vext

3.3.3 Stress
EOSEOS
P

dE

dP
d 2E
B

d
d 2
Elasticitystress-strain relation
r ( )r

C ;

41

1 E

4.1
A

A(p

Aave lim

, r N ) (p N , r N )d N pd N r

A(p N , r N ) dt

ergodic hypothesis
A Aave

4.2 Monte Carlo

MC Monaco

I f ( x )dx
0

1 f ( x ( u ))
f ( x)
w( x )dx
du
0 w( x ( u ))
w( x )

dr e
A
dr e

N E( rN )/kT

A(rN )

N E( rN )/kT

drN N(rN ) A(rN )

(0 n )

N (0) (0 n) N (n) (n 0)
n

N (0) (0 n ) N ( n ) ( n 0)

(0 n ) (0 n ) acc (0 n )
(0 n ) ( n 0)

acc(0 n ) N ( n )

e ( E ( n ) E (0))/ kT
acc( n 0) N (0)
Metropolis accept

42

1 N (n) / N (0) 1

acc(0 n)
N (n) / N (0) N (n) / N (0) 1

4.3 Molecular Dynamics

1Ehrenfest MD

(t ) | H |
MI R
I
I
e
i

H e
t

2Born-Oppenheimer MD

(t ) min{ | H | } B-O
MIR
I
I
0
e
0
0

E0 0 H e 0

SCF

3Car-Parrinello MD

(t ) | H |
MI R
I
I
e
ii (t )

| H e |
{constants }
*
i
i*

CPMD BO
MD
MD

1
M

x y
i 1

xi yi

<A(0)A(t)>

C xy

Cxy (t ) x(0) y (t )
I ( )
D

1
2

<A2>

dteit (0) (t )

<A>2

Time

1
dt i (t ) i (0)
3 0

4.4
MD rare time event.
1TST
A

k1
k1

A A

43

A
k1 k

k
A
A

[ A ]
k e ( G GA )/ kBT
[ A]
MEP

VTST

2
(1) Constrained Minimization R
R
R(2) Eigenvector following
Hessian (3) Dimer method

(1) Synchronous Transit (LST/QST)

(2) Nudged elastic band

44

(r , t )

E h

(r, t ) (r, t ) (r, t )

F
r p E F F

F | F | * F dr
A1.

H
t

H E

(r, t ) e

i
Ht

(r) e

i
Et

(r)

A2

i j Pij

Pij (r1 , r2 ,..., ri ,..., r j ,..., rN ) (r1 , r2 ,..., r j ,..., ri ,..., rN )

Pij

Pij (r1 , r2 ,..., ri ,..., r j ,..., rN ) (r1 , r2 ,..., ri ,..., r j ,..., rN )

Pij

45

Pij2 (r1 , r2 ,..., ri ,..., r j ,..., rN ) Pij (r1 , r2 ,..., ri ,..., r j ,..., rN )
2 (r1 , r2 ,..., ri ,..., r j ,..., rN )
Pij 1 1,
2

1 1 1

1
Pij 1
Pij

Pauli
Pauli

A3.
H (r1 , r2 ,...rN ) E (r1 , r2 ,...rN )

E0 E1 E2 En 0 , 1 , 2 , n

n
N

Ci i
i

H dr E
E
dr
*

1 , 2 , , n
n

ak k
k 1

ak

H kl *k H l dr ,

Skl *k l dr

a aH

k ,l 1
n

*
k l

a aS

k ,l 1

*
k l

46

kl

kl

E
0 (l 1, 2 n)
al

a (H
k 1

kl

ES kl ) 0

det( H kl ESkl ) 0
A4.
H H0 H H0

H 0 n(0) En(0) n(0) H H 0 | | 1 H H 0 W H

E E (0) E (1) 2 E (2)

(0) (1) 2 (2)

Schrodinger Ek H kk
(1)

k(1)
nk

H nk
(0)
(0) n
E En
(0)
k

Ek(2)
nk

|
| H nk
E En(0)
(0)
k

B1.

F (k )

f ( x )e 2 ikx dx

f ( x ) F (k )e2 ikx dk

f ( x ) F ( k ) F ( k ) F ( k ) cos(2 x )

1
2

[ (k 1) (k 1)]

47

N 1

1
F (k )
N

f ( x )e

2
ikx
N

x 0

N 1

f ( x) F (k )e

2
ikx
N

k 0

f ( x ) N 1 k

N 1

N 1
N
0 N f ( x )
2
2
2N

f ( x) g ( x)

f ( ) g ( x )d

Fourier

f (k )
0

f (k )

0 k N1 1
N1 k M 1

g (k )
0

g (k )

0 k N2 1
N2 k M 1

f (k ) g (k )

1
M

M 1

f (m) g (k m)

m 0

M N1 N2 1 wraparounderror M f ( k ) g ( k )
3G 3G x
3G 2 x

48

B2.

1. steepest descent

F ( x )
|x xi

x
i 1
xi 1 xi gi

Brent 6

NumericalRecipes.

2. conjugated gradient

49

u
u v u
u

f (x) f (P)
i

f
1
2 f
xi
xi x j ...
xi
2 i , j xix j

1
c b x x A x
2
f Ax b; (f ) A x

u
u [ (f )] 0 u A v 0

hi 1 g i 1 i hi

i
i i

g i 1 g i 1
gi gi

( g i 1 g i ) g i 1

gi gi

3. quasi Newton

Hessian Taylor

1
f ( x ) f ( x ) f ( x ) A
2

f ( x ) 0 f ( x ) / f ( x )

f (x ) 0 A1f (x)

A lim H i A Hi
Broyden BFGS

50