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Quantum mechanics calculation for material science
By
Kunio TAKAHASHI
Tokyo Institute of Technology,
Tokyo 152-8552, JAPAN
Phone/Fax +81-3-5734-3915
http://www.mep.titech.ac.jp/KTakahashi/
This is a material for the class of Takahashi. Bonus point will be given to the student who has found some mistype etc… and report it to Takahashi. Thank you.
1. Classical mechanics to quantum mechanics ( keywords : analytical mechanics, matrix mechanics, wave mechanics )
Equation of motion
– Newton
– Hamilton’s canonical equations
Matter wave ( de Broglie wave )
Uncertainty relation
Real number to linear operator as quantity
Eigenvalue as observable and
Wave function which express a state of system
Schrödinger equation
When Hamiltonian is independent of time.
xmF i
i
dp
dH
dt
dq
i
i
dq
dH
dt
dp
H
ti )()( qq H
ph /
2/ pq
zip
yip
xip zyx
,,
dxdydzzyxzyx ),,(1),,(*
1),,(1),,(* dxdydzzyxzyx
dxdydzzyxzyx ),,(),,(* Χ
2. Equation to be solved Hartree Fock approximation: Materials we are considering are ...
Schrödinger equation
Hamiltonian
– Even if assuming only Coulomb interaction
Wave function; Slater determinant
– Anti-symmetric property of Fermion
– Molecular orbitals must be arbitrary.
Do you know exact solution ?
H
M
baba ba
baM
a
N
i ia
aN
jiji ji
N
i
iR
eZZ
r
eZ
R
e
m)(1, ,,i
2
1 1 ,
2
)(1, ,,e
2
01
22
4
1
2
H
Electrons
Ions
1, 2, 3 ,,, i ,,, j ,,, N-1, N
1, 2, 3 ,,, a ,,, b ,,, M-1, M
a+Z e
-e
ra,i
i,a,bR
e,i,jR
)()(
)()(
!
1),,(
1
111
1
NNN
N
NN
rr
rr
rr
3. Simple examples (1) Materials we are considering are …
One electron systems
– One ionic core : H ( neutral atom )
: He+, Li
2+, Be
3+ , B
4+ , C
5+ , N
6+ , O
7+ ,,, ( ions )
– Many ionic cores : H2
+ ( ion )
: charged molecules
Many electron systems
– One ionic core : He, Li, Be, B, C, N, O,,, ( isolated atoms )
– Many ionic cores : general problem we want to solve.
Jellium : approximation for metals
a+Z e
-e
a+Z e
-e
a+Z e-e
b+Z e
-e
-e
)()(
)()(
!
1),,(
1
111
1
NNN
N
NN
rr
rr
rr
M
baba ba
baM
a
N
i ia
aN
jiji ji
N
i
iR
eZZ
r
eZ
R
e
m)(1, ,,i
2
1 1 ,
2
)(1, ,,e
2
01
22
4
1
2
H
E
Positive charge density distribution
0
3. Simple examples (2) Materials we are considering are …
One electron systems
– One ionic core : H ( neutral atom )
: He+, Li
2+, Be
3+ , B
4+ , C
5+ , N
6+ , O
7+ ,,, ( ions )
– Many ionic cores : H2
+ ( ion )
: charged molecules
Many electron systems
– One ionic core : He, Li, Be, B, C, N, O,,, ( isolated atoms )
– Many ionic cores : general problem we want to solve.
Jellium : approximation for metals
M
baba ba
baM
a
N
i ia
aN
jiji ji
N
i
iR
eZZ
r
eZ
R
e
m)(1, ,,i
2
1 1 ,
2
)(1, ,,e
2
01
22
4
1
2
H
)()(
)()(
!
1),,(
1
111
1
NNN
N
NN
rr
rr
rr
4. Isolated H atom (1) as a one electron and one ion system
Born-Oppenheimer approximation r
e
m 0
22
2
42
H EH
)exp(2
1cos
!
!
2
12
exp2
})!{(2
)!1(2,,
0
12
00
3
3
0
,,
imPml
mll
na
rL
na
r
na
r
lnn
ln
nar
m
l
l
ln
l
mln
1,3,2,1 ln
ml ,2,1,0
,2,1,0m
2
2
00
4
ema
e
3
2)1(12
!2
211
!1
1
!1
!1
ln
lnlnlnl
ln
lnlnlnln
ln
ln
lnL
l
ml
ml
l
m
m
l zdz
d
l
zzP 1
!2
1 222
0
12
00
3
3
0
exp2
!2
!12
na
rL
na
r
na
r
lnn
ln
narR l
ln
l
rRrmln ,,,,
cos!
!
2
12 m
lpml
mll
)exp(2
1
im
2
2
0
2
4 1
42
n
meEn
+e
-e
; principal q. n.
; azimuthal q. n.
; magnetic q.n.
quantum numbers
;associated Legendre polynomials
;associated Laguerre polynomials
0 10 20 30 40
Distance r/a0
0
0.05
0.1
0.15Y
-AX
IS
0
12
00
3
3
0
exp2
!2
!12
na
rL
na
r
na
r
lnn
ln
narR l
ln
l
mlnmlnn ,,,,densityelectron *
Ele
ctro
n d
ensi
ty o
f s-
orb
ital
s
n=1
n=2
n=3 n=4
l=m=0
Spectral lines emitted from hydrogen plasma Balmer series (1885, Johann Jakob Balmer) n =2 ( Q: Why this is first ? )
Lymann series (1906, Theodore Lyman) n =1
Paschen series (1908, Ritz Paschen) n =3
Ref:Wikipedia
Spectral lines emitted from hydrogen plasma Balmer series (1885, Johann Jakob Balmer) n =2
Lymann series (1906, Theodore Lyman) n =1
Paschen series (1908, Ritz Paschen) n =3
Rydberg formula for hydrogen
Brackett series (1922) n =4
Pfunt series (1924) n =5
Humphreys series (1953) n =6
2
2
2
1
111
nnR
2
2
0
2
4 1
42
n
meEn
2
2
2
1
2
0
3
4
photonphoton
11
28
2
1
2
11112
nnc
me
EEc
Ec
Ehc
nn
chhE photon
5. Isolated ionic core with one electron (1) as a one electron and one ion system
Born-Oppenheimer approximation r
eZ
m
a
0
22
2
42
H EH
0
1
a 0a
Za
2
2
0
2
4
42
n
ZmeE a
n
0
12
00
3
3
0
exp2
!2
!12
na
rZL
na
rZ
na
rZ
lnn
ln
na
ZrR al
lna
l
aa rRrmln ,,,,
m
lpml
mll
!
!
2
12
)exp(2
1
im
a+Z e
-e
Quantum numbersn l m
Orbitals Shell
1 0 0 1s K K
2 0 0 2s L1
1 0
±12p L23
L
3 0 0 3s M1
1 0
±13p M23
2 0
±1
±2
3d M45
M
4 0 0 4s N1
1 0
±14p N23
2 0
±1
±2
4d N45
3 0
±1
±2
±3
4f N67
N
5 0 0 5s O1
1 0
±15p O23
2 0
±1
±2
5d O45
… … …
O
6 0 0 6s P 1
… … … …P
… … … … … …
s d p
1 2 1 2 3 4 5 6 7 8 9 10 1 2 3 4 5 6IA IIA IIIA IVA VA VIA VIIA VIII IB IIB IIIB IVB VB VIB BIIB 0
1 H He
2 Li Be B C N O F Ne
3 Na Mg Al Si P S Cl Ar
4 K Ca Sc Ti V Cr Mn Fe Co Ni Cu Zn Ga Ge As Se Br Kr
5 Rb Sr Y Zr Nb Mo Tc Ru Rh Pd Ag Cd In Sn Sb Te I Xe
6 Cs Ba * Hf Ta W Re Os Ir Pt Au Hg Tl Pb Bi Po At Rn
7 Fr Ra **
f
1 2 3 4 5 6 7 8 9 10 11 12 13 14
6 * La Ce Pr Nd Pm Sm Eu Gd Tb Dy Ho Er Tm Yb Lu
7 ** Ac Th Pa U Np Pu Am Cm Bk Cf Es Fm Md No Lr
Extrapolation of
“one ion - one electron model”
to isolated other neutral atoms
Quantum number and periodic table
Order of occupation
Energy depends on only principal quantum number n
2
20
2
4
42
n
ZmeE a
n a
a
r
eZ
m
2
0
22
4
1
2
H
Extrapolation of
“one ion - one electron model”
to isolated other neutral atoms
Order of occupation
considering electron-electron interaction
s d p
1 2 1 2 3 4 5 6 7 8 9 10 1 2 3 4 5 6IA IIA IIIA IVA VA VIA VIIA VIII IB IIB IIIB IVB VB VIB BIIB 0
1 H He
2 Li Be B C N O F Ne
3 Na Mg Al Si P S Cl Ar
4 K Ca Sc Ti V Cr Mn Fe Co Ni Cu Zn Ga Ge As Se Br Kr
5 Rb Sr Y Zr Nb Mo Tc Ru Rh Pd Ag Cd In Sn Sb Te I Xe
6 Cs Ba * Hf Ta W Re Os Ir Pt Au Hg Tl Pb Bi Po At Rn
7 Fr Ra **
f
1 2 3 4 5 6 7 8 9 10 11 12 13 14
6 * La Ce Pr Nd Pm Sm Eu Gd Tb Dy Ho Er Tm Yb Lu
7 ** Ac Th Pa U Np Pu Am Cm Bk Cf Es Fm Md No Lr
a
a
r
eZ
m
2
0
22
4
1
2
H
N
jiji ji
N
i ia
ai
N
jiji ji
N
i ia
aN
i
i
R
e
r
eZ
m
R
e
r
eZ
m
)(1, ,,e
2
01 ,
2
0
22
)(1, ,,e
2
1 ,
2
01
22
4
1
4
1
2
4
1
2
H
1s
2s
3s
2p
3p 3d
4s 4p
4d
5s 5p
Roothaan Hartree Fock by Clementi and Roetti
Atomic number Z
En
erg
y lev
el o
f o
rbit
als
fo
r is
ola
ted
ato
ms
0 5 10 15 20 25 30 35 40 45 50 55
-0.1
-1
-10
-100
-1000
2
20
2
4
42
n
ZmeE a
n
Shell K L M N O P Q
Principal Q.N. 1 2 3 4 5 6 7
Azimuthal Q.N. 0 0 1 0 1 2 0 1 2 3 0 1 2 3 0 1 2 0
Orbilals 1s 2s 2p 3s 3p 3d 4s 4p 4d 4f 5s 5p 5d 5f 6s 6p 6d 7s
L. Z
1 1 H 1
2 He 2
2 3 Li 2 1
4 Be 2 2
5 B 2 2 1
6 C 2 2 2
7 N 2 2 3
8 O 2 2 4
9 F 2 2 5
10 Ne 2 2 6
3 11 Na 2 2 6 1
12 Mg 2 2 6 2
13 Al 2 2 6 2 1
14 Si 2 2 6 2 2
15 P 2 2 6 2 3
16 S 2 2 6 2 4
17 Cl 2 2 6 2 5
18 Ar 2 2 6 2 6
4 19 K 2 2 6 2 6 1
20 Ca 2 2 6 2 6 2
21 Sc 2 2 6 2 6 1 2
22 Ti 2 2 6 2 6 2 2
23 V 2 2 6 2 6 3 2
24 Cr 2 2 6 2 6 5 1
25 Mn 2 2 6 2 6 5 2
26 Fe 2 2 6 2 6 6 2
27 Co 2 2 6 2 6 7 2
28 Ni 2 2 6 2 6 8 2
29 Cu 2 2 6 2 6 10 1
30 Zn 2 2 6 2 6 10 2
31 Ga 2 2 6 2 6 10 2 1
32 Ge 2 2 6 2 6 10 2 2
33 As 2 2 6 2 6 10 2 3
34 Se 2 2 6 2 6 10 2 4
35 Br 2 2 6 2 6 10 2 5
36 Kr 2 2 6 2 6 10 2 6
5 37 Rb 2 2 6 2 6 10 2 6 1
…
s d p
1 2 1 2 3 4 5 6 7 8 9 10 1 2 3 4 5 6IA IIA IIIA IVA VA VIA VIIA VIII IB IIB IIIB IVB VB VIB BIIB 0
1 H He
2 Li Be B C N O F Ne
3 Na Mg Al Si P S Cl Ar
4 K Ca Sc Ti V Cr Mn Fe Co Ni Cu Zn Ga Ge As Se Br Kr
5 Rb Sr Y Zr Nb Mo Tc Ru Rh Pd Ag Cd In Sn Sb Te I Xe
6 Cs Ba * Hf Ta W Re Os Ir Pt Au Hg Tl Pb Bi Po At Rn
7 Fr Ra **
f
1 2 3 4 5 6 7 8 9 10 11 12 13 14
6 * La Ce Pr Nd Pm Sm Eu Gd Tb Dy Ho Er Tm Yb Lu
7 ** Ac Th Pa U Np Pu Am Cm Bk Cf Es Fm Md No Lr
Electron configuration for neutral isolated atoms
1s
2s
3s
2p
3p 3d
4s 4p
4d
5s 5p
Roothaan Hartree Fock by Clementi and Roetti
Atomic number Z
En
erg
y lev
el o
f o
rbit
als
fo
r is
ola
ted
ato
ms
0 5 10 15 20 25 30 35 40 45 50 55
-0.1
-1
-10
-100
-1000
Shell K L M N O P Q
Principal Q.N. 1 2 3 4 5 6 7
Azimuthal Q.N. 0 0 1 0 1 2 0 1 2 3 0 1 2 3 0 1 2 0
Orbilals 1s 2s 2p 3s 3p 3d 4s 4p 4d 4f 5s 5p 5d 5f 6s 6p 6d 7s
L. Z
…
36 Kr 2 2 6 2 6 10 2 6
5 37 Rb 2 2 6 2 6 10 2 6 1
38 Sr 2 2 6 2 6 10 2 6 2
39 Y 2 2 6 2 6 10 2 6 1 2
40 Zr 2 2 6 2 6 10 2 6 2 2
41 Nb 2 2 6 2 6 10 2 6 4 1
42 Mo 2 2 6 2 6 10 2 6 5 1
43 Tc 2 2 6 2 6 10 2 6 5 2
44 Ru 2 2 6 2 6 10 2 6 7 1
45 Rh 2 2 6 2 6 10 2 6 8 1
46 Pd 2 2 6 2 6 10 2 6 10
47 Ag 2 2 6 2 6 10 2 6 10 1
48 Cd 2 2 6 2 6 10 2 6 10 2
49 In 2 2 6 2 6 10 2 6 10 2 1
50 Sn 2 2 6 2 6 10 2 6 10 2 2
51 Sb 2 2 6 2 6 10 2 6 10 2 3
52 Te 2 2 6 2 6 10 2 6 10 2 4
53 I 2 2 6 2 6 10 2 6 10 2 5
54 Xe 2 2 6 2 6 10 2 6 10 2 6
6 55 Cs 2 2 6 2 6 10 2 6 10 2 6 1
…
s d p
1 2 1 2 3 4 5 6 7 8 9 10 1 2 3 4 5 6IA IIA IIIA IVA VA VIA VIIA VIII IB IIB IIIB IVB VB VIB BIIB 0
1 H He
2 Li Be B C N O F Ne
3 Na Mg Al Si P S Cl Ar
4 K Ca Sc Ti V Cr Mn Fe Co Ni Cu Zn Ga Ge As Se Br Kr
5 Rb Sr Y Zr Nb Mo Tc Ru Rh Pd Ag Cd In Sn Sb Te I Xe
6 Cs Ba * Hf Ta W Re Os Ir Pt Au Hg Tl Pb Bi Po At Rn
7 Fr Ra **
f
1 2 3 4 5 6 7 8 9 10 11 12 13 14
6 * La Ce Pr Nd Pm Sm Eu Gd Tb Dy Ho Er Tm Yb Lu
7 ** Ac Th Pa U Np Pu Am Cm Bk Cf Es Fm Md No Lr
1s
2s
3s
2p
3p 3d
4s 4p
4d
5s 5p
Roothaan Hartree Fock by Clementi and Roetti
Atomic number Z
En
erg
y lev
el o
f o
rbit
als
fo
r is
ola
ted
ato
ms
0 5 10 15 20 25 30 35 40 45 50 55
-0.1
-1
-10
-100
-1000
Shell K L M N O P Q
Principal Q.N. 1 2 3 4 5 6 7
Azimuthal Q.N. 0 0 1 0 1 2 0 1 2 3 0 1 2 3 0 1 2 0
Orbilals 1s 2s 2p 3s 3p 3d 4s 4p 4d 4f 5s 5p 5d 5f 6s 6p 6d 7s
L. Z
…
54 Xe 2 2 6 2 6 10 2 6 10 2 6
6 55 Cs 2 2 6 2 6 10 2 6 10 2 6 1
56 Ba 2 2 6 2 6 10 2 6 10 2 6 2
57 La 2 2 6 2 6 10 2 6 10 2 6 1 2
58 Ce 2 2 6 2 6 10 2 6 10 1 2 6 1 2
59 Pr 2 2 6 2 6 10 2 6 10 3 2 6 2
60 Nd 2 2 6 2 6 10 2 6 10 4 2 6 2
61 Pm 2 2 6 2 6 10 2 6 10 5 2 6 2
62 Sm 2 2 6 2 6 10 2 6 10 6 2 6 2
63 Eu 2 2 6 2 6 10 2 6 10 7 2 6 2
64 Gd 2 2 6 2 6 10 2 6 10 7 2 6 1 2
65 Tb 2 2 6 2 6 10 2 6 10 9 2 6 2
66 Dy 2 2 6 2 6 10 2 6 10 10 2 6 2
67 Ho 2 2 6 2 6 10 2 6 10 11 2 6 2
68 Er 2 2 6 2 6 10 2 6 10 12 2 6 2
69 Tm 2 2 6 2 6 10 2 6 10 13 2 6 2
70 Yb 2 2 6 2 6 10 2 6 10 14 2 6 2
71 Lu 2 2 6 2 6 10 2 6 10 14 2 6 1 2
72 Hf 2 2 6 2 6 10 2 6 10 14 2 6 2 2
73 Ta 2 2 6 2 6 10 2 6 10 14 2 6 3 2
74 W 2 2 6 2 6 10 2 6 10 14 2 6 4 2
75 Re 2 2 6 2 6 10 2 6 10 14 2 6 5 2
76 Os 2 2 6 2 6 10 2 6 10 14 2 6 6 2
77 Ir 2 2 6 2 6 10 2 6 10 14 2 6 7 2
78 Pt 2 2 6 2 6 10 2 6 10 14 2 6 9 1
79 Au 2 2 6 2 6 10 2 6 10 14 2 6 10 1
80 Hg 2 2 6 2 6 10 2 6 10 14 2 6 10 2
81 Tl 2 2 6 2 6 10 2 6 10 14 2 6 10 2 1
82 Pb 2 2 6 2 6 10 2 6 10 14 2 6 10 2 2
83 Bi 2 2 6 2 6 10 2 6 10 14 2 6 10 2 3
84 Po 2 2 6 2 6 10 2 6 10 14 2 6 10 2 4
85 At 2 2 6 2 6 10 2 6 10 14 2 6 10 2 5
86 Rn 2 2 6 2 6 10 2 6 10 14 2 6 10 2 6
7 87 Fr 2 2 6 2 6 10 2 6 10 14 2 6 10 2 6 1
…
s d p
1 2 1 2 3 4 5 6 7 8 9 10 1 2 3 4 5 6IA IIA IIIA IVA VA VIA VIIA VIII IB IIB IIIB IVB VB VIB BIIB 0
1 H He
2 Li Be B C N O F Ne
3 Na Mg Al Si P S Cl Ar
4 K Ca Sc Ti V Cr Mn Fe Co Ni Cu Zn Ga Ge As Se Br Kr
5 Rb Sr Y Zr Nb Mo Tc Ru Rh Pd Ag Cd In Sn Sb Te I Xe
6 Cs Ba * Hf Ta W Re Os Ir Pt Au Hg Tl Pb Bi Po At Rn
7 Fr Ra **
f
1 2 3 4 5 6 7 8 9 10 11 12 13 14
6 * La Ce Pr Nd Pm Sm Eu Gd Tb Dy Ho Er Tm Yb Lu
7 ** Ac Th Pa U Np Pu Am Cm Bk Cf Es Fm Md No Lr
1s
2s
3s
2p
3p 3d
4s 4p
4d
5s 5p
Roothaan Hartree Fock by Clementi and Roetti
Atomic number Z
En
erg
y lev
el o
f o
rbit
als
fo
r is
ola
ted
ato
ms
0 5 10 15 20 25 30 35 40 45 50 55
-0.1
-1
-10
-100
-1000
Shell K L M N O P Q
Principal Q.N. 1 2 3 4 5 6 7
Azimuthal Q.N. 0 0 1 0 1 2 0 1 2 3 0 1 2 3 0 1 2 0
Orbilals 1s 2s 2p 3s 3p 3d 4s 4p 4d 4f 5s 5p 5d 5f 6s 6p 6d 7s
L. Z
…
54 Xe 2 2 6 2 6 10 2 6 10 2 6
6 55 Cs 2 2 6 2 6 10 2 6 10 2 6 1
56 Ba 2 2 6 2 6 10 2 6 10 2 6 2
57 La 2 2 6 2 6 10 2 6 10 2 6 1 2
58 Ce 2 2 6 2 6 10 2 6 10 1 2 6 1 2
59 Pr 2 2 6 2 6 10 2 6 10 3 2 6 2
60 Nd 2 2 6 2 6 10 2 6 10 4 2 6 2
61 Pm 2 2 6 2 6 10 2 6 10 5 2 6 2
62 Sm 2 2 6 2 6 10 2 6 10 6 2 6 2
63 Eu 2 2 6 2 6 10 2 6 10 7 2 6 2
64 Gd 2 2 6 2 6 10 2 6 10 7 2 6 1 2
65 Tb 2 2 6 2 6 10 2 6 10 9 2 6 2
66 Dy 2 2 6 2 6 10 2 6 10 10 2 6 2
67 Ho 2 2 6 2 6 10 2 6 10 11 2 6 2
68 Er 2 2 6 2 6 10 2 6 10 12 2 6 2
69 Tm 2 2 6 2 6 10 2 6 10 13 2 6 2
70 Yb 2 2 6 2 6 10 2 6 10 14 2 6 2
71 Lu 2 2 6 2 6 10 2 6 10 14 2 6 1 2
72 Hf 2 2 6 2 6 10 2 6 10 14 2 6 2 2
73 Ta 2 2 6 2 6 10 2 6 10 14 2 6 3 2
74 W 2 2 6 2 6 10 2 6 10 14 2 6 4 2
75 Re 2 2 6 2 6 10 2 6 10 14 2 6 5 2
76 Os 2 2 6 2 6 10 2 6 10 14 2 6 6 2
77 Ir 2 2 6 2 6 10 2 6 10 14 2 6 7 2
78 Pt 2 2 6 2 6 10 2 6 10 14 2 6 9 1
79 Au 2 2 6 2 6 10 2 6 10 14 2 6 10 1
80 Hg 2 2 6 2 6 10 2 6 10 14 2 6 10 2
81 Tl 2 2 6 2 6 10 2 6 10 14 2 6 10 2 1
82 Pb 2 2 6 2 6 10 2 6 10 14 2 6 10 2 2
83 Bi 2 2 6 2 6 10 2 6 10 14 2 6 10 2 3
84 Po 2 2 6 2 6 10 2 6 10 14 2 6 10 2 4
85 At 2 2 6 2 6 10 2 6 10 14 2 6 10 2 5
86 Rn 2 2 6 2 6 10 2 6 10 14 2 6 10 2 6
7 87 Fr 2 2 6 2 6 10 2 6 10 14 2 6 10 2 6 1
…
s d p
1 2 1 2 3 4 5 6 7 8 9 10 1 2 3 4 5 6IA IIA IIIA IVA VA VIA VIIA VIII IB IIB IIIB IVB VB VIB BIIB 0
1 H He
2 Li Be B C N O F Ne
3 Na Mg Al Si P S Cl Ar
4 K Ca Sc Ti V Cr Mn Fe Co Ni Cu Zn Ga Ge As Se Br Kr
5 Rb Sr Y Zr Nb Mo Tc Ru Rh Pd Ag Cd In Sn Sb Te I Xe
6 Cs Ba * Hf Ta W Re Os Ir Pt Au Hg Tl Pb Bi Po At Rn
7 Fr Ra **
f
1 2 3 4 5 6 7 8 9 10 11 12 13 14
6 * La Ce Pr Nd Pm Sm Eu Gd Tb Dy Ho Er Tm Yb Lu
7 ** Ac Th Pa U Np Pu Am Cm Bk Cf Es Fm Md No Lr
1s
2s
3s
2p
3p 3d
4s 4p
4d
5s 5p
Roothaan Hartree Fock by Clementi and Roetti
Atomic number Z
En
erg
y lev
el o
f o
rbit
als
fo
r is
ola
ted
ato
ms
0 5 10 15 20 25 30 35 40 45 50 55
-0.1
-1
-10
-100
-1000
Shell K L M N O P Q
Principal Q.N. 1 2 3 4 5 6 7
Azimuthal Q.N. 0 0 1 0 1 2 0 1 2 3 0 1 2 3 0 1 2 0
Orbilals 1s 2s 2p 3s 3p 3d 4s 4p 4d 4f 5s 5p 5d 5f 6s 6p 6d 7s
L. Z
…
86 Rn 2 2 6 2 6 10 2 6 10 14 2 6 10 2 6
7 87 Fr 2 2 6 2 6 10 2 6 10 14 2 6 10 2 6 1
88 Ra 2 2 6 2 6 10 2 6 10 14 2 6 10 2 6 2
89 Ac 2 2 6 2 6 10 2 6 10 14 2 6 10 2 6 1 2
90 Th 2 2 6 2 6 10 2 6 10 14 2 6 10 2 6 2 2
91 Pa 2 2 6 2 6 10 2 6 10 14 2 6 10 2 2 6 1 2
92 U 2 2 6 2 6 10 2 6 10 14 2 6 10 3 2 6 1 2
93 Np 2 2 6 2 6 10 2 6 10 14 2 6 10 4 2 6 1 2
94 Pu 2 2 6 2 6 10 2 6 10 14 2 6 10 6 2 6 2
95 Am 2 2 6 2 6 10 2 6 10 14 2 6 10 7 2 6 2
96 Cm 2 2 6 2 6 10 2 6 10 14 2 6 10 7 2 6 1 2
97 Bk 2 2 6 2 6 10 2 6 10 14 2 6 10 9 2 6 2
98 Cf 2 2 6 2 6 10 2 6 10 14 2 6 10 10 2 6 2
99 Es 2 2 6 2 6 10 2 6 10 14 2 6 10 11 2 6 2
100 Fm 2 2 6 2 6 10 2 6 10 14 2 6 10 12 2 6 2
s d p
1 2 1 2 3 4 5 6 7 8 9 10 1 2 3 4 5 6IA IIA IIIA IVA VA VIA VIIA VIII IB IIB IIIB IVB VB VIB BIIB 0
1 H He
2 Li Be B C N O F Ne
3 Na Mg Al Si P S Cl Ar
4 K Ca Sc Ti V Cr Mn Fe Co Ni Cu Zn Ga Ge As Se Br Kr
5 Rb Sr Y Zr Nb Mo Tc Ru Rh Pd Ag Cd In Sn Sb Te I Xe
6 Cs Ba * Hf Ta W Re Os Ir Pt Au Hg Tl Pb Bi Po At Rn
7 Fr Ra **
f
1 2 3 4 5 6 7 8 9 10 11 12 13 14
6 * La Ce Pr Nd Pm Sm Eu Gd Tb Dy Ho Er Tm Yb Lu
7 ** Ac Th Pa U Np Pu Am Cm Bk Cf Es Fm Md No Lr
1s
2s
3s
2p
3p 3d
4s 4p
4d
5s 5p
Roothaan Hartree Fock by Clementi and Roetti
Atomic number Z
En
erg
y lev
el o
f o
rbit
als
fo
r is
ola
ted
ato
ms
0 5 10 15 20 25 30 35 40 45 50 55
-0.1
-1
-10
-100
-1000
Quantum numbersn l m
Orbitals Shell
1 0 0 1s K K
2 0 0 2s L1
1 0
±12p L23
L
3 0 0 3s M1
1 0
±13p M23
2 0
±1
±2
3d M45
M
4 0 0 4s N1
1 0
±14p N23
2 0
±1
±2
4d N45
3 0
±1
±2
±3
4f N67
N
5 0 0 5s O1
1 0
±15p O23
2 0
±1
±2
5d O45
… … …
O
6 0 0 6s P 1
… … … …P
… … … … … …
Spectroscopic naming for orbitals
Principle of analyses
Electron Probe Micro Analyzer (EPMA)
Energy Dispersive X-ray Spectroscopy (EDS)
X-ray Photo-electron Spectroscopy (XPS)
Auger Electron Spectroscopy (AES)
1s
2s
3s
2p
3p 3d
4s 4p
4d
5s 5p
Roothaan Hartree Fock by Clementi and Roetti
Atomic number Z
En
erg
y lev
el o
f o
rbit
als
fo
r is
ola
ted
ato
ms
0 5 10 15 20 25 30 35 40 45 50 55
-0.1
-1
-10
-100
-1000
Electron Probe Micro Analyzer (EPMA)
Energy Dispersive X-ray Spectroscopy (EDS)
Secondary Electron Microscope (SEM)
X-ray Photo-electron Spectroscopy (XPS)
= Electron Spectroscopy for Chemical Analysis (ESCA)
Hemispherical Electrostatic Analyzer (HEA)
Ultra High Vacuum (UHV) and Introduction chamber
Ion sputtering
Auger Electron Spectroscopy (AES)
Secondary Electron Microscope (SEM)
Cylindrical Mirror Analyzer (CMA) or HEA
Ultra High Vacuum (UHV) and Introduction chamber
Ion sputtering
Chemical properties
Atomic radius
Ionic radius
Covalent radius
Metallic radius
Van der Waars radius
Ionization energy
( Work function )
Electro negativity
Pauling
Mulliken
Etc…
s d p
1 2 1 2 3 4 5 6 7 8 9 10 1 2 3 4 5 6IA IIA IIIA IVA VA VIA VIIA VIII IB IIB IIIB IVB VB VIB BIIB 0
1 H He
2 Li Be B C N O F Ne
3 Na Mg Al Si P S Cl Ar
4 K Ca Sc Ti V Cr Mn Fe Co Ni Cu Zn Ga Ge As Se Br Kr
5 Rb Sr Y Zr Nb Mo Tc Ru Rh Pd Ag Cd In Sn Sb Te I Xe
6 Cs Ba * Hf Ta W Re Os Ir Pt Au Hg Tl Pb Bi Po At Rn
7 Fr Ra **
f
1 2 3 4 5 6 7 8 9 10 11 12 13 14
6 * La Ce Pr Nd Pm Sm Eu Gd Tb Dy Ho Er Tm Yb Lu
7 ** Ac Th Pa U Np Pu Am Cm Bk Cf Es Fm Md No Lr
1s
2s
3s
2p
3p 3d
4s 4p
4d
5s 5p
Roothaan Hartree Fock by Clementi and Roetti
Atomic number Z
En
erg
y lev
el o
f o
rbit
als
fo
r is
ola
ted
ato
ms
0 5 10 15 20 25 30 35 40 45 50 55
-0.1
-1
-10
-100
-1000
Ref:Wikipedia
Do you have systematic feature of elements ? Calculation by yourself is essential. Please try it.
Material which shows …
the highest melting point ( or cohesive energy ),
lager electro-negativity ( or smaller ionization energy ),
close-pack structure ( fcc,hcp,bcc,sc,dia.,,, ),
chemical activity ( or non-activity )
s d p
1 2 1 2 3 4 5 6 7 8 9 10 1 2 3 4 5 6IA IIA IIIA IVA VA VIA VIIA VIII IB IIB IIIB IVB VB VIB BIIB 0
1 H He
2 Li Be B C N O F Ne
3 Na Mg Al Si P S Cl Ar
4 K Ca Sc Ti V Cr Mn Fe Co Ni Cu Zn Ga Ge As Se Br Kr
5 Rb Sr Y Zr Nb Mo Tc Ru Rh Pd Ag Cd In Sn Sb Te I Xe
6 Cs Ba * Hf Ta W Re Os Ir Pt Au Hg Tl Pb Bi Po At Rn
7 Fr Ra **
f
1 2 3 4 5 6 7 8 9 10 11 12 13 14
6 * La Ce Pr Nd Pm Sm Eu Gd Tb Dy Ho Er Tm Yb Lu
7 ** Ac Th Pa U Np Pu Am Cm Bk Cf Es Fm Md No Lr
1s
2s
3s
2p
3p 3d
4s 4p
4d
5s 5p
Roothaan Hartree Fock by Clementi and Roetti
Atomic number Z
En
erg
y lev
el o
f o
rbit
als
fo
r is
ola
ted
ato
ms
0 5 10 15 20 25 30 35 40 45 50 55
-0.1
-1
-10
-100
-1000
6. H2
+
LCAO approximation
+e
-e
+e
ra rb
R
bbaa CC
min
d
dE
H0
ba C
E
C
E
12 d
R
e
r
e
r
e
m ba
222
0
22
4
1
2
H EH
0,0,1
d
dE
H
dCC
dCCCC
bbaa
bbaabbaa
2
H
22
22
2
2
bbabaa
bbbaabaaaa
CdCCC
dCdCCdC
HHH
22
22
2
2
bbaa
bbbabbaaaa
CSCCC
HCHCCHC
dH aaaa H
d
R
e
r
e
r
e
ma
ba
a
0
2
0
2
0
22
2
4442
d
r
e
ma
a
a
0
22
2
42
d
r
ea
b
a
0
2
4
d
R
eaa
0
2
4
ISHE
d
r
ea
b
a
0
2
4 R
e
0
2
4
R
eJE ISH
0
2
4
d
r
eJ a
b
a
0
2
4
0222222
bbbabbaaaabbaa HCHCCHCECSCCC
R
ed
r
eEH b
a
bISHbb
0
2
0
2
44
R
eJE ISH
0
2
4
dH baab H
d
R
e
r
e
r
e
mb
ba
a
0
2
0
2
0
22
2
4442
d
r
e
mb
b
a
0
22
2
42
dr
eb
a
a
0
2
4
dR
eba
0
2
4
dE baISH
d
r
eb
a
a
0
2
4
dR
eba
0
2
4
SR
eKSE ISH
0
2
4
d
r
eK b
a
a
0
2
4
dS ba
d
r
eK b
a
a
0
2
4 dS ba
d
r
eJ a
b
a
0
2
4
0
3
0
exp1
a
r
a
aa
R
rr ba R
rr ba dddR
d 22
3
2
2
000 3
11exp
a
R
a
R
a
R
000
2 2exp11
4 a
R
a
R
R
e
0000
2
1exp4 a
R
a
R
a
e
0222222
bbbabbaaaabbaa HCHCCHCECSCCC
0 babaaa CHSECHE
0 aabbbb CHSECHE0
b
a
bbab
abaa
C
C
HEHSE
SEHE
12222
bbaa CSCCCdt 02
abbbaa
bbab
abaaHSEHEHE
HEHSE
HSEHE
0 abaaabaa HSEHEHSEHE
abaa
abaa
HSEH
HSEHE
12222
SCC aa
ba CS
C
22
112222
SCC aa
ba CS
C
22
1
S
ba
22
S
ba
22
bbaa HH
00
2
000
2
exp13
21exp
14 a
R
a
R
a
R
a
R
SR
eE ISH
00
2
000
2
exp13
21exp
14 a
R
a
R
a
R
a
R
SR
eE ISH
E
2
000 3
11exp
a
R
a
R
a
RS
0
ba C
E
C
E
2 4 6 8
Atomic distance R/a0 (a.u.)
-0.06
-0.04
-0.02
0
0.02
0.04
0.06
Tota
l en
ergy
of
H2+ s
yst
em E
H2+/E
H (
a.u.)
Bonding orbital
Anti-bonding orbital
00
2
H4 a
eE
00
2
000
2
exp13
21exp
14 a
R
a
R
a
R
a
R
SR
eE ISH
00
2
000
2
exp13
21exp
14 a
R
a
R
a
R
a
R
SR
eE ISH
E
kcal/mol 52H2H 2
kcal/mol 42.7
eV 84.1
a.u. 8064.0
kcal/mol 4.8527.42
: : Bonding state
: : Anti-bonding state
S
ba
22
S
ba
22
2
2
00
4
ema
e
: Bonding state
: Anti-bonding state
S
ba
22
S
ba
22
7. Two ionic core with one electron
LCAO approximation a+Z e b+Z e
-e
ra rb
R
Large binding energy is due to ...
large difference between energy levels
or
large overlap of wave functions
R
eZZ
r
eZ
r
eZ
m
ba
b
b
a
a
222
0
22
4
1
2
H
EH
bbaa CC
min
d
dE
H0
ba C
E
C
E
12 d
222
411212
2
bbaa
bbababaaabab
ab
bbaa
ab
ababbbaa
HH
HSHHSH
S
HH
S
HSHHE
dH aaaa
dH baab
dS baab
dH bbbb
a+Z e b+Z e
-e
ra rb
R
When : covalent bond
When : ionic bond
Large binding energy is due to ...
large difference between energy levels
or
large overlap of wave functions
R
eZZ
r
eZ
r
eZ
m
ba
b
b
a
a
222
0
22
4
1
2
H EH
222
411212
2
bbaa
bbababaaabab
ab
bbaa
ab
ababbbaa
HH
HSHHSH
S
HH
S
HSHHE
dH aaaa
dH baab
dS baab
dH bbbb
bbaa HH
EEab
1abS
abbbaa
ab HHH
EEE
2
bbaaab HHH 1abS
bbaa
abbb
bbaa
abaa
ab
HH
HH
HH
HH
EEE2
2
Ionic bond, Covalent bond, and Metallic bond consideration with “Tow ionic core with one electron model”
Models for each limitation
How understood with Q.M. ?
Difference between energy levels.
Large difference seems charge transfer.
Distribution of frontier electrons
Spherical or localized to directions
Ionic bond
Covalent bond Metallic bond
FrF
NaCl
ZnFe Cu
SnPb
SiO2
AlN
Si
1s
2s
3s
2p
3p 3d
4s 4p
4d
5s 5p
Roothaan Hartree Fock by Clementi and Roetti
Atomic number Z
En
erg
y lev
el o
f o
rbit
als
fo
r is
ola
ted
ato
ms
0 5 10 15 20 25 30 35 40 45 50 55
-0.1
-1
-10
-100
-1000
s d p
1 2 1 2 3 4 5 6 7 8 9 10 1 2 3 4 5 6IA IIA IIIA IVA VA VIA VIIA VIII IB IIB IIIB IVB VB VIB BIIB 0
1 H He
2 Li Be B C N O F Ne
3 Na Mg Al Si P S Cl Ar
4 K Ca Sc Ti V Cr Mn Fe Co Ni Cu Zn Ga Ge As Se Br Kr
5 Rb Sr Y Zr Nb Mo Tc Ru Rh Pd Ag Cd In Sn Sb Te I Xe
6 Cs Ba * Hf Ta W Re Os Ir Pt Au Hg Tl Pb Bi Po At Rn
7 Fr Ra **
f
1 2 3 4 5 6 7 8 9 10 11 12 13 14
6 * La Ce Pr Nd Pm Sm Eu Gd Tb Dy Ho Er Tm Yb Lu
7 ** Ac Th Pa U Np Pu Am Cm Bk Cf Es Fm Md No Lr
Ionic bond
Covalent bond Metallic bond
CsF
NaCl
ZnFe Cu
SnPb
SiO2
AlN
Si
There is neither
- purely-ionic-bond material,
- purely-covalent-bond material,
nor
- purely-metallic-bond material.
Shell K L M N O P Q
Principal Q.N. 1 2 3 4 5 6 7
Azimuthal Q.N. 0 0 1 0 1 2 0 1 2 3 0 1 2 3 0 1 2 0
Orbilals 1s 2s 2p 3s 3p 3d 4s 4p 4d 4f 5s 5p 5d 5f 6s 6p 6d 7s
L. Z
1 1 H 1
2 He 2
2 3 Li 2 1
4 Be 2 2
5 B 2 2 1
6 C 2 2 2
7 N 2 2 3
8 O 2 2 4
9 F 2 2 5
10 Ne 2 2 6
3 11 Na 2 2 6 1
12 Mg 2 2 6 2
13 Al 2 2 6 2 1
14 Si 2 2 6 2 2
15 P 2 2 6 2 3
16 S 2 2 6 2 4
17 Cl 2 2 6 2 5
18 Ar 2 2 6 2 6
4 19 K 2 2 6 2 6 1
20 Ca 2 2 6 2 6 2
21 Sc 2 2 6 2 6 1 2
22 Ti 2 2 6 2 6 2 2
23 V 2 2 6 2 6 3 2
24 Cr 2 2 6 2 6 5 1
25 Mn 2 2 6 2 6 5 2
26 Fe 2 2 6 2 6 6 2
27 Co 2 2 6 2 6 7 2
28 Ni 2 2 6 2 6 8 2
29 Cu 2 2 6 2 6 10 1
30 Zn 2 2 6 2 6 10 2
31 Ga 2 2 6 2 6 10 2 1
32 Ge 2 2 6 2 6 10 2 2
33 As 2 2 6 2 6 10 2 3
34 Se 2 2 6 2 6 10 2 4
35 Br 2 2 6 2 6 10 2 5
36 Kr 2 2 6 2 6 10 2 6
5 37 Rb 2 2 6 2 6 10 2 6 1
…
Difference between energy levels Large difference seems charge transfer.
Distribution of frontier electrons Spherical or localized to directions
Cohesion energy and Periodic table s d p
1 2 1 2 3 4 5 6 7 8 9 10 1 2 3 4 5 6IA IIA IIIA IVA VA VIA VIIA VIII IB IIB IIIB IVB VB VIB BIIB 0
1 H He
2 Li Be B C N O F Ne
3 Na Mg Al Si P S Cl Ar
4 K Ca Sc Ti V Cr Mn Fe Co Ni Cu Zn Ga Ge As Se Br Kr
5 Rb Sr Y Zr Nb Mo Tc Ru Rh Pd Ag Cd In Sn Sb Te I Xe
6 Cs Ba * Hf Ta W Re Os Ir Pt Au Hg Tl Pb Bi Po At Rn
7 Fr Ra **
f
1 2 3 4 5 6 7 8 9 10 11 12 13 14
6 * La Ce Pr Nd Pm Sm Eu Gd Tb Dy Ho Er Tm Yb Lu
7 ** Ac Th Pa U Np Pu Am Cm Bk Cf Es Fm Md No Lr
Shell K L M N O P Q
Principal Q.N. 1 2 3 4 5 6 7
Azimuthal Q.N. 0 0 1 0 1 2 0 1 2 3 0 1 2 3 0 1 2 0
Orbilals 1s 2s 2p 3s 3p 3d 4s 4p 4d 4f 5s 5p 5d 5f 6s 6p 6d 7s
L. Z
1 1 H 1
2 He 2
2 3 Li 2 1
4 Be 2 2
5 B 2 2 1
6 C 2 2 2
7 N 2 2 3
8 O 2 2 4
9 F 2 2 5
10 Ne 2 2 6
3 11 Na 2 2 6 1
12 Mg 2 2 6 2
13 Al 2 2 6 2 1
14 Si 2 2 6 2 2
15 P 2 2 6 2 3
16 S 2 2 6 2 4
17 Cl 2 2 6 2 5
18 Ar 2 2 6 2 6
4 19 K 2 2 6 2 6 1
20 Ca 2 2 6 2 6 2
21 Sc 2 2 6 2 6 1 2
22 Ti 2 2 6 2 6 2 2
23 V 2 2 6 2 6 3 2
24 Cr 2 2 6 2 6 5 1
25 Mn 2 2 6 2 6 5 2
26 Fe 2 2 6 2 6 6 2
27 Co 2 2 6 2 6 7 2
28 Ni 2 2 6 2 6 8 2
29 Cu 2 2 6 2 6 10 1
30 Zn 2 2 6 2 6 10 2
31 Ga 2 2 6 2 6 10 2 1
32 Ge 2 2 6 2 6 10 2 2
33 As 2 2 6 2 6 10 2 3
34 Se 2 2 6 2 6 10 2 4
35 Br 2 2 6 2 6 10 2 5
36 Kr 2 2 6 2 6 10 2 6
5 37 Rb 2 2 6 2 6 10 2 6 1
…
Difference between energy levels Large difference seems charge transfer.
Distribution of frontier electrons Spherical or localized to directions
Cohesion energy and Periodic table
1s
2s
3s
2p
3p 3d
4s 4p
4d
5s 5p
Roothaan Hartree Fock by Clementi and Roetti
Atomic number Z
En
erg
y lev
el o
f o
rbit
als
fo
r is
ola
ted
ato
ms
0 5 10 15 20 25 30 35 40 45 50 55
-0.1
-1
-10
-100
-1000
You have obtain a systematic feature of elements ? Calculation by yourself is essential. Please try it.
Material which shows …
the highest melting point ( or cohesive energy ),
lager electro-negativity ( or smaller ionization energy ),
close-pack structure ( fcc,hcp,bcc,sc,dia.,,, ),
chemical activity ( or non-activity )
s d p
1 2 1 2 3 4 5 6 7 8 9 10 1 2 3 4 5 6IA IIA IIIA IVA VA VIA VIIA VIII IB IIB IIIB IVB VB VIB BIIB 0
1 H He
2 Li Be B C N O F Ne
3 Na Mg Al Si P S Cl Ar
4 K Ca Sc Ti V Cr Mn Fe Co Ni Cu Zn Ga Ge As Se Br Kr
5 Rb Sr Y Zr Nb Mo Tc Ru Rh Pd Ag Cd In Sn Sb Te I Xe
6 Cs Ba * Hf Ta W Re Os Ir Pt Au Hg Tl Pb Bi Po At Rn
7 Fr Ra **
f
1 2 3 4 5 6 7 8 9 10 11 12 13 14
6 * La Ce Pr Nd Pm Sm Eu Gd Tb Dy Ho Er Tm Yb Lu
7 ** Ac Th Pa U Np Pu Am Cm Bk Cf Es Fm Md No Lr
1s
2s
3s
2p
3p 3d
4s 4p
4d
5s 5p
Roothaan Hartree Fock by Clementi and Roetti
Atomic number Z
En
erg
y lev
el o
f o
rbit
als
fo
r is
ola
ted
ato
ms
0 5 10 15 20 25 30 35 40 45 50 55
-0.1
-1
-10
-100
-1000
s d p
1 2 1 2 3 4 5 6 7 8 9 10 1 2 3 4 5 6IA IIA IIIA IVA VA VIA VIIA VIII IB IIB IIIB IVB VB VIB BIIB 0
1 H He
2 Li Be B C N O F Ne
3 Na Mg Al Si P S Cl Ar
4 K Ca Sc Ti V Cr Mn Fe Co Ni Cu Zn Ga Ge As Se Br Kr
5 Rb Sr Y Zr Nb Mo Tc Ru Rh Pd Ag Cd In Sn Sb Te I Xe
6 Cs Ba * Hf Ta W Re Os Ir Pt Au Hg Tl Pb Bi Po At Rn
7 Fr Ra **
f
1 2 3 4 5 6 7 8 9 10 11 12 13 14
6 * La Ce Pr Nd Pm Sm Eu Gd Tb Dy Ho Er Tm Yb Lu
7 ** Ac Th Pa U Np Pu Am Cm Bk Cf Es Fm Md No Lr
8. Neutral He atom (1) as an example for
isolated neutral atoms
Spin-orbital
Two electrons in 1s orbital.
Integration with spin coordinate
Ortho-normality
– orbital term
– spin term
dxdydzdsdVdsd ***
s11 s12
1)()( iii dsrr 1)()( iii dsrr 0)()( iii dsrr
dxdydzdsdVdsd
lkiilik d ,)()( rr
nmiinim dV ,)()( rr
)()(
)()(
!
1),,(
1
111
1
NNN
N
NN
rr
rr
rr
8. Neutral He atom (2) as an example for isolated neutral atoms
Schrödinger equation
Remember “one ion - one electron model”
e21
21
2
02
2
0
22
2
1
2
0
21
2
21
2
02
2
1
2
0
22
21
2
4
12
4
1
2
2
4
1
2
4
122
4
1
2
HHH
rrrr
rrrrH
ee
m
e
m
eee
m
)2()1(
)2()1(
!2
1
)()(
)()(
!2
1),(
22
11
2212
211121
rr
rrrr
H )()()( 11 iii s
)()()( 12 iii s
+2e
-e
r1r2
1 2
a+Z e
-e sssssss CCC 3322111
,3221 , , ,
2
spss
aZ
G3G3G2G2G1G11 CCCs
ddddE e21 **** HHHH
8. Neutral He atom (3) as an example for isolated neutral atoms
Total energy
d
d
d
d
d
dd
ssss
ssss
ssss
ssss
ssssssss
)2()2()1()1(*)1()1()2()2(2
1
)1()1()2()2(*)2()2()1()1(2
1
)1()1()2()2(*)1()1()2()2(2
1
)2()2()1()1(*)2()2()1()1(2
1
)1()1()2()2()2()2()1()1(*)1()1()2()2()2()2()1()1(2
1
)1()2()2()1(*)1()2()2()1(2
1*
11111
11111
11111
11111
111111111
2121121211
H
H
H
H
H
HH
)2()1(
)2()1(
!2
1
)()(
)()(
!2
1),(
22
11
2212
211121
rr
rrrr
s11
s12
1111
111112211
1111211
11111
)1(*)1(2
1
)1(*)1()1()1()2()2()2()2(2
1
)1()1(*)1()1()2()2()2()2(2
1
)2()2()1()1(*)2()2()1()1(2
1
dV
dVdsdsdV
dd
d
ss
ssss
ssss
ssss
H
H
H
H
1111
111112211
1111211
11111
)1(*)1(2
1
)1(*)1()1()1()2()2()2()2(2
1
)1()1(*)1()1()2()2()2()2(2
1
)1()1()2()2(*)1()1()2()2(2
1
dV
dVdsdsdV
dd
d
ss
ssss
ssss
ssss
H
H
H
H
ddddE e21 **** HHHH
11111 )1(*)1(* dd ss HH
21212 )2(*)2(* dd ss HH
d
d
d
d
d
ddH
ssss
ssss
ssss
ssss
ssssssss
)2()2()1()1(*)1()1()2()2(2
1
)1()1()2()2(*)2()2()1()1(2
1
)1()1()2()2(*)1()1()2()2(2
1
)2()2()1()1(*)2()2()1()1(2
1
)1()1()2()2()2()2()1()1(*)1()1()2()2()2()2()1()1(2
1
)1()2()2()1(*)1()2()2()1(2
1*
11111
11111
11111
11111
111111111
2121121211
H
H
H
H
H
H
0
)1(*)1()1()1()2()2()2()2(2
1
)1()1(*)1()1()2()2()2()2(2
1
)1()1()2()2(*)2()2()1()1(2
1
111112211
1111211
11111
dVdsdsdV
dd
d
ssss
ssss
ssss
H
H
H
0
)1(*)1()1()1()2()2()2()2(2
1
)1()1(*)1()1()2()2()2()2(2
1
)2()2()1()1(*)1()1()2()2(2
1
111112211
1111211
11111
dVdsdsdV
dd
d
ssss
ssss
ssss
H
H
H
1111 )1(*)1(2
1dVss H
)2()1(
)2()1(
!2
1
)()(
)()(
!2
1),(
22
11
2212
211121
rr
rrrr
2111e11
2111e11
11e11
11e11
2111e1111e11
2111e1111e11
1111e1111
2121e2121e
)1()2(*)1()2(2
1
)2()1(*)2()1(2
1
0)2()2()1()1(*)1()1()2()2(2
1
0)1()1()2()2(*)2()2()1()1(2
1
)1()2(*)1()2(2
1)1()1()2()2(*)1()1()2()2(
2
1
)2()1(*)2()1(2
1)2()2()1()1(*)2()2()1()1(
2
1
)1()1()2()2()2()2()1()1(*)1()1()2()2()2()2()1()1(2
1
)1()2()2()1(*)1()2()2()1(2
1*
dVdV
dVdV
d
d
dVdVd
dVdVd
d
dd
ssss
ssss
ssss
ssss
ssssssss
ssssssss
ssssssss
H
H
H
H
HH
HH
H
HH
ddddE e21 **** HHHH
2111e11
2111e11
2111e11e
)2()1(*)2()1(
)1()2(*)1()2(2
1
)2()1(*)2()1(2
1*
dVdV
dVdV
dVdVd
ssss
ssss
ssss
H
H
HH
2111e111111
e21
)2()1(*)2()1()1(*)1(2
****
dVdVdV
ddddE
ssssss
HH
HHHH
2111e11
2111e11
2111e11e
)2()1(*)2()1(
)1()2(*)1()2(2
1
)2()1(*)2()1(2
1*
dVdV
dVdV
dVdVd
ssss
ssss
ssss
H
H
HH
11111 )1(*)1(* dd ss HH 21212 )2(*)2(* dd ss HH
e21
21
2
02
2
0
22
2
1
2
0
21
2
21
2
02
2
1
2
0
22
21
2
4
12
4
1
2
2
4
1
2
4
122
4
1
2
HHH
rrrr
rrrrH
ee
m
e
m
eee
m
)()()()( 22,111,1
1
,11 icicici ss
L
j
jjss
9. Neutral isolated atoms Roothaan Hartree Fock approximation
E.Clementi and C.Roetti, Atomic Data and Nuclear Data Tables, 14, 177-478 (1974)
1s
2s
3s
2p
3p 3d
4s 4p
4d
5s 5p
Roothaan Hartree Fock by Clementi and Roetti
Atomic number Z
En
erg
y lev
el o
f o
rbit
als
fo
r is
ola
ted
ato
ms
0 5 10 15 20 25 30 35 40 45 50 55
-0.1
-1
-10
-100
-1000
Energy level of neutral atoms
Effect of e--e- interaction
One electron systems Multi-electron systems G.C.Pimentel, R.D.Spratley, “Chemical Bonding clarified through quantum mechanics”, Holden-day Inc.
2
2
0
2
4
42
n
ZmeE a
n
10. Diatomic molecules
LCAO
One-electron approximation
Multi-electron effect
We can imagine based on
Overlap of atomic wave functions
Sign of atomic wave functions
Do you know “-bond and -bond” ?
a+Z e b+Z e
-e
ra rb
R
a+Z e b+Z e
-e
ra rb
R
“-bond and -bond” At first, remember
When : covalent bond
When : ionic bond
Large binding energy is due to ...
large difference between energy levels
or
large overlap of wave functions
R
eZZ
r
eZ
r
eZ
m
ba
b
b
a
a
222
0
22
4
1
2
H EH
222
411212
2
bbaa
bbababaaabab
ab
bbaa
ab
ababbbaa
HH
HSHHSH
S
HH
S
HSHHE
dH aaaa
dH baab
dS baab
dH bbbb
bbaa HH
EEab
1abS
abbbaa
ab HHH
EEE
2
bbaaab HHH 1abS
bbaa
abbb
bbaa
abaa
ab
HH
HH
HH
HH
EEE
2
22
2
-bond”
“-bond”
s d p
1 2 1 2 3 4 5 6 7 8 9 10 1 2 3 4 5 6IA IIA IIIA IVA VA VIA VIIA VIII IB IIB IIIB IVB VB VIB BIIB 0
1 H He
2 Li Be B C N O F Ne
3 Na Mg Al Si P S Cl Ar
4 K Ca Sc Ti V Cr Mn Fe Co Ni Cu Zn Ga Ge As Se Br Kr
5 Rb Sr Y Zr Nb Mo Tc Ru Rh Pd Ag Cd In Sn Sb Te I Xe
6 Cs Ba * Hf Ta W Re Os Ir Pt Au Hg Tl Pb Bi Po At Rn
7 Fr Ra **
f
1 2 3 4 5 6 7 8 9 10 11 12 13 14
6 * La Ce Pr Nd Pm Sm Eu Gd Tb Dy Ho Er Tm Yb Lu
7 ** Ac Th Pa U Np Pu Am Cm Bk Cf Es Fm Md No Lr
0 10 20 30 40
Distance r/a0
0
0.05
0.1
0.15
Y-A
XIS
11. Organic molecules
Any Liner combination of atomic orbital is a solution of the wave equation.
Also atomic orbital can be approximated to be a LCAO, as is used in Roothaan Hartree Fock approximation.
A set of hybrid orbitals is another set of atomic orbitals.
Hybrid orbitals
sp3
sp2
sp
Hybrid orbitals
sp3
C : (2s)2(2p)2 -> (sp3)4
ex.
Methane (CH4), Ethane (H3C- CH3), Methyl group (H3C-), Si, C (diamond), etc…
sp2
sp
Hybrid orbitals
sp3
sp2
C : (2s)2(2p)2 -> (sp2)3(2pz)1
ex.
Ethylene (Methene, H2C=CH2), Methylene group (H2C=) , etc…
sp
Hybrid orbitals
sp3
sp2
sp
C : (2s)2(2p)2 -> (sp)2(2px)1(2py)
1
ex.
Acetylene (Ethyne, HCCH), Mtehine group (HC), etc…
Hybrid orbitals
sp3
Methane (CH4), Ethane (H3C- CH3), Methyl group (H3C-),
Si, C (diamond), etc…
sp2
Ethylene (Methene, H2C=CH2), Methylene group (H2C=) , etc…
sp
Acetylene (Ethyne, HCCH), Mtehine group (HC), etc…
Others
Benzene (C6H6), Cyclo-hexane (C6H12)
Methyl alcohol (CH3OH)
1-Buten (-Butylene, H2C=CHCH2CH3)
12. Multi-atomic molecules
13. Jellium
Positive charge density distribution
Electron distribution -> negative charge density distribution
Total charge density distribution
Electric field distribution
Potential energy that electrons see.
E
Positive charge density distribution
0
Surface energy
Surface tension
One electron approximation
Effective potential energy
Potential shift determined from charge neutrality
Analytic wave functions !!
Analytic formula for surface tension !!
Fermi level
Potential energy v
Distance xFermi level
x
F
V
F
V
effveff
H
eff2
2
2v
mH
Distance x/FR
elat
ive
elec
tro
n d
ensi
ty
Positive
back ground
SCF jellium
Shifted
Step Potential
rs = 5
(r = 2.35
= V/F)
-1.0 -0.5 0.0 0.5 1.0
0.0
0.5
1.0
by K.Takahashi, and T.Onzawa,
Physical Review B, 48, 5689 (1993)
%31035.35
)(5
)0( 24
F24
F2
s
m
krK
m
kT r
Theoretical approach for surface tension at 0 K
SCF-Jellium
Stabilized jellium
Al
ZnMg
Pb
Ca
Li
Sr
Ba
Na
K
Rb Cs
Shifted step potential
Effective electron density parameter rm (Bohr)
Su
rfac
e en
ergy
at z
ero
tem
pet
ratu
re
s (
mJ/
m2)
Be
GaCd
In
Hg
2 3 4 5 6
500
1000
1500
2000
2500
3000
100
Shifted step potential K.Takahashi, and T.Onzawa,
Physical Review B, 48, 5689 (1993)
Stabilized jellium J.P.Predew, H.Q.Tran and E.D.Smith,
Phys. Rev. B, 42, 11627 (1990).
SCF-jellium N.D.Lang and W.Kohn,
Phys. Rev. B, 1, 4555 (1970).
Surface energy (surface tension at 0 K) by K.F.Wojciechovski, Surface Science, 437, 285-288 (1999)
Shifted step potential K.Takahashi, and T.Onzawa,
Physical Review B, 48, 5689 (1993)
Stabilized jellium J.P.Predew, H.Q.Tran and E.D.Smith,
Phys. Rev. B, 42, 11627 (1990).
SCF-jellium N.D.Lang and W.Kohn,
Phys. Rev. B, 1, 4555 (1970). SCF-Jellium
Stabilized jellium
Al Al
ZnZn
MgMg
PbPb
Li
CaCa
Li
Sr
BaSr
Ba
Na
K
Rb
Cs
K
RbCs
Shifted step potential
Density parameter rs( ), rm( ) (Bohr)
Su
rfac
e en
ergy
s (
mJ/
m2)
2 3 4 5 6
200
400
600
800
1000
1200140016001800
SCF-Jellium
Stabilized jellium
Al Al
ZnZn
MgMg
PbPb
Li
CaCa
Li
Sr
BaSr
Ba
Na
K
Rb
Cs
K
RbCs
Shifted step potential
Density parameter rs( ), rm( ) (Bohr)
Su
rfac
e en
ergy
s (
mJ/
m2)
2 3 4 5 6
200
400
600
800
1000
1200140016001800
Limitation of density functional theory (DFT) by K.F.Wojciechovski, Surface Science, 437, 285-288 (1999)
Extrapolation for liquid as experimental values
Electron density from
Kittel, Introduction to Solid State Physics, Wiley, NewYork, 1986
to
Perrot,F., and Rasolt,M., J.Phys.: Cond.Matter, 6, 1473-1482, 1994
Density parameter
-
Electron density
Electron density correction for jellium approximation Density parameter from Kittel to Perrot
Kittel, Introduction to Solid State Physics, wiley, NewYork, 1986
Perrot,F., and Rasolt,M., J.Phys.: Cond.Matter, 6, 1473-1482, 1994
Valence
no.
Metal Electron
density
x1022
Density
parameter
Fermi
wave
vector
x108
Fermi
velocity
x108
Fermi
energy
Fermi
temp.BFF / kT
x104
(cm-3) (cm-1) (cm/s) (eV) (K)
1 Li 4.70 3.25 1.11 1.29 4.72 5.48
Na 2.65 3.93 0.92 1.07 3.23 3.75
K 1.40 4.86 0.75 0.86 2.12 2.46
Rb 1.15 5.20 0.70 0.81 1.85 2.15
Cs 0.91 5.63 0.64 0.75 1.58 1.83
Cu 8.45 2.67 1.36 1.57 7.00 8.12
Ag 5.85 3.02 1.20 1.39 5.48 6.36
Au 5.90 3.01 1.20 1.39 5.51 6.39
2 Be 24.2 1.88 1.93 2.23 14.14 16.41
Mg 8.60 2.65 1.37 1.58 7.13 8.27
Ca 4.60 3.27 1.11 1.28 4.68 5.43
Sr 3.56 3.56 1.02 1.18 3.95 4.58
Ba 3.20 3.69 0.98 1.13 3.65 4.24
Zn 13.10 2.31 1.57 1.82 9.39 10.9
Cd 9.28 2.59 1.40 1.62 7.46 8.66
3 Al 18.06 2.07 1.75 2.02 11.63 13.49
Ga 15.30 2.19 1.65 1.91 10.35 12.01
In 11.49 2.41 1.50 1.74 8.60 9.98
4 Pb 13.20 2.30 1.57 1.82 9.37 10.87
Sn(w) 14.48 2.23 1.62 1.88 10.03 11.64
Li
3.13
3.07
Be
1.86
1.85
Metal
rm
rs*
Na
3.68
3.67
Mg
2.78
2.58
Al
2.42
2.12
K
4.21
4.37
Ca
3.07
2.96
Sc
2.58
2.33
Ti
2.23
2.00
V
2.12
1.80
Cr
2.05
1.71
Mn
2.04
1.70
Fe
2.06
1.71
Co
2.08
1.74
Ni
2.14
1.83
Cu
2.25
1.95
Zn
2.49
2.11
Ga
2.51
2.28
Rb
4.46
4.68
Sr
3.34
3.16
Y
2.69
2.44
Zr
2.44
2.08
Nb
2.38
1.91
Mo
2.23
1.77
Tc
2.21
1.77
Ru
2.23
1.79
Rh
2.29
1.86
Pd
2.39
2.02
Ag
2.61
2.23
Cd
2.91
2.44
In
2.85
2.57
Sn
2.98
-
Sb
3.33
-
Cs
5.01
-
Ba
3.24
-
La
2.89
-
Hf
2.47
-
Ta
2.36
-
W
2.27
-
Re
2.21
-
Os
2.21
-
Ir
2.26
-
Pt
2.37
-
Au
2.54
-
Hg
2.90
-
Tl
3.04
-
Pb
3.11
-
Bi
3.48
-
rm : determined so as to describe grand state property of arbitrary defects by Perrot
rs* : determined from interstitial region by Moruzzi
Limitation of density functional theory (DFT) by K.F.Wojciechovski, Surface Science, 437, 285-288 (1999)
SCF-Jellium
Stabilized jellium
Al
ZnMg
Pb
Ca
Li
Sr
Ba
Na
K
Rb Cs
Shifted step potential
Effective electron density parameter rm (Bohr)
Su
rfac
e en
ergy
at z
ero
tem
pet
ratu
re
s (
mJ/
m2)
Be
GaCd
In
Hg
2 3 4 5 6
500
1000
1500
2000
2500
3000
100
Shifted step potential K.Takahashi, and T.Onzawa,
Physical Review B, 48, 5689 (1993)
Stabilized jellium J.P.Predew, H.Q.Tran and E.D.Smith,
Phys. Rev. B, 42, 11627 (1990).
SCF-jellium N.D.Lang and W.Kohn,
Phys. Rev. B, 1, 4555 (1970).
Limitation of DFT
Surface tension: Free energy required to create unit area of surface
Interfacial tension : Free energy required to create unit area of interface
+2S +
1 1
1
s1
+2S +
2 2
2
s2
1
2 1
2 1 2
+ + +2Si
1
2 1
2
+ +2Si
1
2
+ +2Si
surface
interface
+2S +
1 1
1
s1
+2S +
2 2
2
s2
1
2 1
2 1 2
+ + +2Si
1
2 1
2
+ +2Si
1
2
+ +2Si
1
2 1
2
+
1
2 1
2
+
1
2
+
1
2
1
+
2
+2S(s1 s2 i
interfacesurface2surface1
+S +
1
2
1
2
+)
-------------------------------------
+2S +
1 1
1
s1
+2S +
2 2
2
s2
1
2 1
2 1 2
+ + +2Si
1
2 1
2
+ +2Si
1
2
+ +2Si
1
2 1
2
+
1
2 1
2
+
1
2
+
1
2
1
+
2
+2S(s1 s2 i
interfacesurface2surface1
+S +
1
2
1
2
+)
-------------------------------------
Work of adhesion “Material constant”
from atomic interaction
Work of adhesion
Free energy required to separate unit area of adhered interface
related
Surface tension , Interfacial tension
Free energy required to create unit area of surface (interface)
+S +
1
2
1
2
s i
Temperature dependence
of interfacial/surface tension
Internal energy and entropy
1st law and 2nd law of thermodynamics
For bulk,
therefore
Variables for unit area of surface
For arbitrary area of surface,
Therefore,
p, TA
Vb
dApdVTdSdU btottot
sbtot UUU sbtot SSS
bbb pdVTdSdU
dATdSdU ss
AUU ss ASS
ss
0ssss TdSdUAdATSU
ss TSU ss TdSdU
pTS
s
T
p
dTT
U
TTU
TpTSTpUTp
0
ss
ss
1
),(),(),(
T
p
dTT
U
TTU
TpTSTpUTp
0
ss
ss
1
),(),(),(
surface (interfacial) free energy = surface (interfacial) tension
surface (interfacial) internal energy = surface (interfacial) energy = surface (interfacial) tension at 0 K.
T
p
dTT
U
TTU
TpTSTpUTp
0
ss
ss
1
),(),(),(
Theoretical approach for surface tension at 0 K
SCF-Jellium
Stabilized jellium
Al
ZnMg
Pb
Ca
Li
Sr
Ba
Na
K
Rb Cs
Shifted step potential
Effective electron density parameter rm (Bohr)
Su
rfac
e en
ergy
at z
ero
tem
pet
ratu
re
s (
mJ/
m2)
Be
GaCd
In
Hg
2 3 4 5 6
500
1000
1500
2000
2500
3000
100
Shifted step potential K.Takahashi, and T.Onzawa,
Physical Review B, 48, 5689 (1993)
Stabilized jellium J.P.Predew, H.Q.Tran and E.D.Smith,
Phys. Rev. B, 42, 11627 (1990).
SCF-jellium N.D.Lang and W.Kohn,
Phys. Rev. B, 1, 4555 (1970).
T
p
dTT
U
TTUTp
0
ss
1),(
trans.phase s,phonon s,electron s,s UUUU
Temperature dependence
of surface tension
Other contributions
( phonon, phase transformation )
=0, at 0 (zero) K.
T0 Tm
Phase transf.
Phonon +Electron
T0 Tm
Electron
Su
rfac
e en
ergy
U
Su
rfac
e te
nsi
on
s
Solid liquid
0,ext.
0
),(5
)(4
F2
electrons,
rK
m
kTU r
T0 Tm
Phase transf.
Phonon +Electron
T0 Tm
Electron
Su
rfac
e en
ergy
U
Su
rfac
e te
nsi
on
s
Solid liquid
0,ext.
0
Temperature T (K)
Al
Li
Na
K
Cs
Su
rfac
e te
nsi
on
s
(J
/m2)
Rb
Bi
Hg
Pb
Sn
Zn
0 500 1000 15000.0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1.0
1.1