Chapter 6.

Hydrogen Atom
Solving Schrdinger Equation for H Atom
- Laplacian in spherical coordinate
- Angular part similar to rotation case:
spherical harmonics
- Angular momentum operators
- Radial part associated Laguerre polynomials
- Orbitals Hydrogen-like wavefunctions
- 3-dimensional shapes of s, p, d orbitals
- Extension to Hellium atom

Schrdinger Equation for H Atom

=
H

Separation of variables:

Radial part:
Angular part:

Coulomb potential

Solving Angular Part of S-equation for H Atom

single-valued

x = cos sin = 1 x 2 ; ( ) = P ( x )
d dP dx d 2 d
=
=
;
2
d dx d d
d

d d d dx

d dx d d

= l( l + 1 )

( ) =

l = 0, 1, 2,... ( n 1 )
m = 0, 1, 2,.. l

from
radial
part

associated Legendre
polynomials

- Properties of (associated)
Legendre polynomials

orthogonal

- Total angular wavefunction: spherical harmonics

Table 6.3
orthonormal
Angular Momentum Square operator and spherical harmonics

2
also eigenfunctions of L

for rigid rotor (Ch5),

Angular Momentum Operators and States

z,L
2 , not for L
x,L
y
Yl m ( , ) : eigenfunctions for L
x , y ,z , L
2 = 0, L

x , L y = i = Lz , L y , Lz = i = Lx , Lz , Lx = i = L y
x , L y , L
z can not be determine d simultaneously
L
Dirac notation :

A d < | A | > " bra "," ket "

y
+ = L
x + iL
y ; lowering op : L
= L
x iL
raising op : L
L Yl m = = l ( l + 1 ) m ( m 1 ) Yl m 1

e. g . l = 1, m = 1, 0, 1 L2 = 1( 1 + 1 )= 2 | L |= = 2

2h

Lz = = , 0, = ; L > | Lz |, Lx 0, Ly 0, < Lx , y >= 0

"L precesses about the z- axis"

Solving Radial Part of S-equation for H Atom

d 2 2 d l( l + 1 ) 2me2
2mE
Veff(r) = Coulombic
R
(
r
)
+

+
+
=
0
dr 2 r dr
r2
=2
4 0= 2r
+ Centripetal

Trial function : R( r ) e r , r xe r " well behaved at r = 0, and R 0 as r "

2 2 l( l + 1 ) 2me2
me2
me4
2mE r
,E=

+
+ 2 e = 0 l = 0, =

2
2
2
2
r
r
r
4
=
=
4
=

( 0 ) 2=2

0
0
ground state energy

General solutions:

associated Laguerre polynomials

Bohr radius a0 = 4 0 = 2 / me 2 = 0.529

nlm ( r , , ) = Rnl ( r )Yl m ( , ) = | nlm >

 nlm ' s are orthonormal !

< nlm | nlm >= 1
< nlm | n' l ' m ' >= nn' ll ' mm '

Quantum Numbers (QN) and Orbitals of H Atom

- Spatial electronic quantum states are defined by (n l m)
n: principal QN; determine energies of quantum states
determine electronic shells; n = 1, 2, 3,
l: angular momentum QN; determine total angular momenta
determine orbitals (s, p, d,); l= 0, 1, 2, .(n-1) n
m: magnetic QN; determine z-component of angular
momenta and magnetic behaviors; determine
sub-orbitals (px,py,pz,..); m= 0,1,2,..l 2l+1
- s Orbitals are spherically symmetric

3
< r > 1 s = a0 , rmp = a0
2

< r > 2 s = 6a 0

3
2
<
r
>
=
a
n

2
0
n 00
*
< r >= r 3dr sin d d nlm
( r , , ) nlm ( r , , )
2
0
0
0
number of nodes : ( radial ) n l 1; ( angular ) l

 ns

Units of a0

2
ns

Real Wavefunction Representation: Chemists Choice

z

- Three p orbitals: l = 1, m=-1,0,1

= pz

++

++

px

py

pz

(a)

(b)

(c)

- Five d orbitals: l = 2, m= -2,-1,0,1,2

+
-+
+

++

-+

x
z

+ +
++
x

dx2 y2

+
+ -
+
-+

y
x

dxy

++

dz2

-+

+ -+

y
x

dxz

dyz

+
y

2
Plot of nlm

Plot of nlm

Probability contour plot

(10, 20,.. 90%)

- Shell Model
2

Plot of r R( r )

0.6
0.5
0.4

0.1

1s

r 2 [ R n l (r) ] 2 / a 0

2s

0.2

0.3

0.2

0.2

0.1

0.1

2p

0
0

10

15

a0
< rnl >= 3n 2 l ( l + 1 )
2

3s

0.1
0
0.1

Broad ring (QM) vs sharp ring (CM)

3s
1s
2s

3p

0
0.1

3d
0
0

10

15

20

r / a0

units of a0

25

Beyond H Atom: Hellium Atom

-e1

+2e
-e2

can not be solved exactly

due to interelectronic repulsion term
need to use approximation methods (Ch7):
Perturbation method or Variational method

If interelectronic repulsion term is ignored,

total energy = sum of the energies of H-like atoms
total wavefunction = product of two H-like wavefunctions

Plot of R( r )

Plot of r R( r )

R @ 1 ,0 D@ r D

r^2

R @1 ,0 D @r D^ 2
1

1s

0.8

0.6

0.4

0.2

R @ 2 ,0 D @r D

r^2

R @2 ,0 D @r D^ 2
0.35

1.5

0.3

2s

0.25
0.2
0.15

0.5

0.1

0.05

R @ 2 ,1 D@ r D

r^2

R @2 ,1 D @r D^ 2
0.35
0.3

0.3

2p

0.2

0.25
0.2
0.15
0.1

0.1

0.05
2

Plot of R( r )

R @ 4 ,0 D @ r D

r^ 2

Plot of r 2 R( r ) 2

R @4 ,0 D@ r D ^ 2
0.12

0.6
0.5

0.1

0.4

0.08

4s

0.3
0.2

0.06
0.04

0.1
0.02

r
5

10

15

20

-0.1

R @ 4 ,1 D@ r D

r^ 2

10

15

20

10

15

20

10

15

20

10

15

20

R @4 ,1 D@ r D ^ 2
0.12

0.125
0.1

0.1
0.075

0.08

4p

0.05

0.06

0.025

0.04

r
5

10

15

0.02

20

-0.025

-0.05

R @ 4 ,2 D@ r D

r^ 2

R @4 ,2 D@ r D ^ 2
0.12

0.06

4d

0.04

0.1
0.08
0.06

0.02

0.04

r
5

10

15

20

0.02

-0.02

R @4 ,3 D @r D

r^ 2

0.05

4f

0.04

0.03

R @4 ,3 D@ r D ^ 2
0.12
0.1
0.08
0.06

0.02
0.04
0.01

0.02

r
5

10

15

20

2px

1s

r2|2px|2

2pxHx,y,z=0L

1sHx,y,z=0L

1.5
4
1

2
0.5

-0.5
-2
-2

-1
-4
-4

-1

-0.5

0
x

0.5

1.5

-6

-4

3px

3pxHx, y,z=0L

-2

0
x

-6

-4

r2|3px|2

3pxHx, y,z=0L

10

10

y0

-1.5
-1.5

-5

-5

-10

-10
-15

-10

-5

0
x

10

15

-15

-10

-5

0
x

10

15

-2

Plot of R( r )

Plot of r R( r )

R @ 3 ,0 D @ r D

r^ 2

R @3 ,0 D@ r D ^ 2

1
0.8

0.15

3s

0.6

0.1
0.4
0.05

0.2

r
2

10

12

14

R @3 ,1 D @r D

r^ 2

10

12

14

10

12

14

10

12

14

R @3 ,1 D@ r D ^ 2

0.2

3p

0.15

0.15

0.1

0.1

0.05
0.05

r
2

10

12

14

-0.05
2

R @3 ,2 D@ r D

r^ 2

R @3 ,2 D@ r D ^ 2
0.2

0.1

3d

0.08
0.06

0.15

0.1

0.04
0.05
0.02

r
2

10

12

14

Contours in xy-plane (z=0)

4px

r2|4px|2

5px

5pxHx, y,z=0L

4pxHx, y,z=0L

20

20

10

10

10

-10

20

-20

-20
-20

-10

0
x

10

20

-10

-10

-20

-20

-10

0
x

3dxy

10

-30

20

-20

4dxy

3dxy

-10

0
x

10

20

30

20

30

5dxy

4dxy

10

5dxy

20

30

20
5

10

10

4pxHx, y,z=0L

-10
-5

-10
-20

-10

-20
-10

-5

0
x

10

-30
-20

-10

0
x

10

20

-30

-20

-10

0
x

10

Contours
3dx2-y2 in xy-plane (z=0)
3dx2 y2

4dx2-y2
4dx2 y2

15
20
10
10

-5

-10

-10
-20
-15
-15

-10

-5

0
x

3dz2

20

Contours
in xy-plane (z=1)

10

Contours
in xz-plane
(y=0)
20

-10

0
x

10

20

3dz2

10

10

-20

15

-10

-10

-20

-20

-20

-10

0
x

10

20

-20

-10

0
x

10

20

4dz2

20

Contours
in xz-plane (y=0)

10

-10

-20

-20

-10

0
x

10

20

Quantum Mechanical Virial Theorem

1
for Coulomb potentail ( ),
r
< V >= 2 < K >= 2 < E >
< K >=< K r > + < K rot
n

XK\

Ze 2 Z
< V >=
4 0 a0 n 2

=2 2
= 2 Z 2l ( l + 1 )
| n, l > +
>=< n, l |
r
2
2 r r r
2 a 2n3 ( l + 1 )
0
2
XE \
XC\
E

Z2 2
2 a2
Z2 2
8 a2
Z2 2
24 a2
Z2 2
18 a2
5 Z2 2
162 a2
Z2 2
90 a2
Z2 2
32 a2
Z2 2
48 a2
Z2 2
80 a2
Z2 2
224 a2

2
2
Z 2
a

Z2 2
12 a2

0
2 Z2 2
81 a2
2 Z2 2
45 a2

0
Z2 2
96 a2
3 Z2 2
160 a2
3 Z2 2
112 a2

Z2 2
4 a2
Z2 2
4 a2

Z2 2
9 a2
Z2 2
9 a2
Z2 2
9 a2

Z2 2
16 a2
Z2 2
16 a2

Z2 2
16 a2
Z2 2
16 a2

Z2 2
2 a2
Z2 2
8 a2
Z2 2
8 a2
Z2 2
18 a2
Z2 2
18 a2
Z2 2
18 a2
Z2 2
32 a2
Z2 2
32 a2
Z2 2
32 a2
Z2 2
32 a2