5.

61 Fall 2007

Lecture #21

page 1

HYDROGEN ATOM
Schrodinger equation in 3D spherical polar coordinates:

!2 1 2
1

1
2
r
+
sin

r, , + U r, , r, , = E r, ,
2 r 2 r r r 2 sin
r 2 sin 2 2

with Coulomb potential

U (r) =

) (

Ze2
4 0 r

Rewrite as

2 2

r
+ 2 r 2 U r E r, , + L2 r, , = 0
!

r r

()

function of r only

r is separable

function of , only
is separable

Angular momentum: solutions are spherical harmonic wavefunctions

() ( )
( , ) = ! l ( l + 1)Y ( , )

r, , = R r Yl m ,
with

L2Yl m

l = 0,1,2,...

Radial equation for the H atom:

()

!2 d 2 dR r ! l l + 1

r
+
+
U
r

R r = 0

dr 2 r 2
2 r 2 dr

()

()

()

Solutions R r are the H atom radial wavefunctions

Simplest case: l = 0 yields solution
Z
R r = 2
a0

()

32

Zr a0

ml

exponential decay away from nucleus

5.61 Fall 2007

Lecture #21

page 2

with
E = Z 2 e2 8 0 a0

lowest energy eigenvalue

Bohr radius

a0 0 h2 e2

General case: solutions are products of (exponential) x (polynomial)

Energy eigenvalues:
Z 2 e2
Z 2 e4
=
8 02 h2 n2
8 0 a0 n2

E=

n = 1,2,3,...

Radial eigenfunctions:

Rnl

12

l +3 2

n l 1 ! 2Z

Z r na0 2l +1 2 Zr

r
=
r le
Ln+ l

na
na0

0
2n
n
+
l
!

()

)
)

where L2ln++1l 2Zr na0 are the associated Laguerre functions, the first few of which are:

n=1

l=0

L11 = 1

n=2

l=0

L12 = 2! 2 Zr
a0

l =1

L33 = 3!

n=3 l=0

2 2
L13 = 3! 3 2Zr + 2Z r
2
a0
9a0

l =1

L34 = 4! 4 2Zr
3a0

l=2

L55 = 5!

Normalization:
Spherical harmonics

Radial wavefunctions

( ) ( )

d d sin Yl m* , Yl m , = 1
0

() ()

dr r 2 Rnl* r Rnl r = 1

5.61 Fall 2007

Lecture #21

page 3

TOTAL HYDROGEN ATOM WAVEFUNCTIONS

() ( )

nlm r, , = Rnl r Yl m ,
principle quantum number
angular momentum quantum number
magnetic quantum number
ENERGY depends on n:

n = 1,2,3,...
l = 0,1,2,..., n 1
m = 0, 1, 2,..., l

E = Z 2 e2 8 0 a0 n2

ORBITAL ANGULAR MOMENTUM depends on l:

L = ! l l +1

ANGULAR MOMENTUM Z-COMPONENT depends on m:

Lz = m!

Total H atom wavefunctions are normalized and orthogonal:

*
d sin d r 2 dr nlm
r, , n ' l ' m ' r, , = nn ' ll ' mm '

() ( )

since components Rnl r Yl m , are normalized and orthogonal.

Lowest few total H atom wavefunctions, for n = 1 and 2 (with = Zr a0 ):

5.61 Fall 2007

n=1
n=2

Lecture #21

l=0
l=0

m=0
m=0

page 4

3/ 2

100

1 Z
=

a0

3/ 2

200

Z
=

32 a0

3/ 2

210

Z
=

32 a0

e
= 1s

(2 ) e

/ 2

= 2s

e / 2 cos = 2 p

l =1

m=0

l =1

Z
/ 2
m = 1 211 =

sin e i
a
e
64 0

3/ 2

or the alternate linear combinations

2p
2p

Z
=

32 a0
1

Z
=

32 a0
1

3/ 2

e / 2 sin cos =

3/ 2

e / 2 sin sin =

1
2
1
2i

21+1

+ 211

21+1

211

The value of l is denoted by a letter: l = 0,1,2,3...

s,p,d,f orbitals

The value of m is denoted by a letter for l = 1: m = 0, 1 linear combinations

pz , px ,p y orbitals

HYDROGEN ATOM ENERGIES

Potential energy of two electrons separated by the Bohr radius:
U = e2 4 0 a0 _ one atomic unit (a.u.) of energy.
H atom energies:

E = Z 2 e2 8 0 a0 n2 = Z 2 2 n2 a.u.

n
1
2
3
4
5
!

En (a.u.)
-1/2
-1/8
-1/18
-1/32
-1/50
!

5.61 Fall 2007

Lecture #21

page 5

H atom energies &transitions

E
E/hc
(a.u.) (cm-1)

4
3

0
0
-1/32 -6,855
-1/18-12,187

-1/8

-1/2 -109,680

H atom emission spectra

Lyman series

Balmer

Paschen

(A)
(1012 Hz)

DEGENERACIES OF H ATOM ENERGY LEVELS

As n increases, the degeneracy of the level increases.
What is the degeneracy gn of each level as a function of n?
Does this help understand the periodic table?

5.61 Fall 2007

Lecture #21

page 6

SHAPES AND SYMMETRIES OF THE ORBITALS

S ORBITALS

( )

1s = a03

1 2

r / a0

)(

2s = 32 a03 2 r a0 e
l=0

r / 2a0

spherically symmetric

n - l -1 = 0

radial nodes

l=0

angular nodes

n -1 = 0

n - l - 1 = 1

l = 0

n - 1 = 1

total nodes

Electron probability density given by r, ,

Probability that a 1s electron lies between r and r + dr of the nucleus:

P ORBITALS:

) (

( )

d d sin 1s* r, , 1s r, , r 2 dr = 4 a03

0

1l=

2r / a0 2

r dr

wavefunctions

Not spherically symmetric: depend on ,

m = 0 case:

2 p independent of

210 = 2 p = 32 a03
z

) (r a ) e
1/ 2

r / 2a0

cos

symmetric about z axis

radial nodes

n - l -1 = 0

angular nodes

l = 1

total nodes

n - 1 = 1

()

(note difference from 2s: Rnl r

depends on l as well as n)

xy nodal plane zero amplitude at nucleus

m = 1 case: Linear combinations give

Equivalent probability distributions

( ) (r a ) e
= ( 32 a ) ( r a ) e

2 p = 32 a03
x

2p

3
0

1/ 2

1/ 2

r / 2a0

sin cos

r / 2a0

sin sin

5.61 Fall 2007

Lecture #21

page 7

H atom radial probability densities

0.6

0.5

()

0.4

r 2 Rnl2 r a0
220nlrRra

()

0.3
0.6

0.6

0.2
0.5

0.5

2s

0.1
0.4

0.4

1s

0.3

0.6

0.3

0.5

0.2

10

15

20

25

30

10
30

15

20

25

30

0.2

0.4

0.1

2p

0.1

0.6
0

0.3
0

10

15

0
20
0

25
5

0.5
0.2
0.4
0.1
0.6

3s

0.3
0
0.5 0

10

15

20

25

30

20

25

30

20

25

30

0.2
0.4
0.1

3p

0.3
0

10

15

0.2

3d

0.1

10

15

s = r/a0

5.61 Fall 2007

Lecture #21

page 8

MAGNETIC FIELD EFFECTS

Electron orbital angular momentum (circulating charge)
=

magnetic moment

e
L
2me

Magnetic field B applied along z axis interacts with :

Potential energy
U = = zz = eBz Lz
2me
Include in potential part of Hamiltonian operator:
eB
H = H 0 + z Lz
2me

H atom wavefunctions are eigenfunctions of both H 0 and Lz operators

eigenfunctions of new H operator.
Energy eigenvalues are the sums
eB
Z 2 e2
E=
+ z m
2
2me
8 0 a0 n

Energy depends on magnetic quantum number m when a magnetic field is applied.

2p orbitals: m = -1,0,+1 states have different energies
Splitting proportional to applied field B z.

5.61 Fall 2007

Lecture #21

page 9

Applied
magnetic field

No magnetic
field
2p

m = +1
m=0
m = -1

Energy

m=0

1s

2p
1s Emission spectra
One line

Three lines

Complex functions 211 and 21+1 are eigenfunctions of Lz with eigenvalues m! .

2 p and 2 p are eigenfunctions of H 0 but not of Lz no longer energy

x

eigenfunctions once magnetic field is applied.