Chapter 6

Quantum Theory of the Hydrogen Atom

1
6.1 Schrodinger’s Equation for the Hydrogen Atom

Symmetry suggests spherical polar coordinates

2
Fig. 6.1
(a) Spherical polar coordinates.
(b) A line of constant zenith angle q on a sphere is a circle whose plane is perpendicular
to the z axis.
(c) A line of circle constant azimuth angle f is a circle whose plane include the z axis.
3
 Cartesian Coordinates
Cartesian coordinates. A differential volume in Cartesian coordinates.

4
Cylindrical coordinates

5
 Spherical coordinates
Spherical coordinates. A differential volume element in spherical
coordinates.

6
 Schrödinger’s equation for H-atom

1) Cartesian coordinates (x , y , z)

 Spherical polar coordinates ( r ,  ,  )

 2  2  2 2m
   E  U   0 (6.1)
x 2
y 2
z 2
 2

e2
Electric potenti
U  
al energy 4  0 r (6.2)

7
r x2  y2  z2 x  r sin  cos 
  cos 1
z y  r sin  sin 
x2  y2  z2 z  r cos 
y
  tan 1
x 8
1   2 ψ    ψ  1  2ψ 2 m
 2 E  U ψ  0
1
r  2  sin θ  2 (6.3)
r r  r  r sin θ θ 
2
θ  r sin θ  2


          2mr sin 
2 2 2
 e2 
sin   r 2
2
  sin   sin   2    E   0 (6.4)
r  r       2  4 0 r 

9
Laplacian operator
1    h2 h3 f    h1 h3 f    h1 h2 f 
 2 f    f          
h1 h2 h3  u1  h1 u1  u 2 h
 2 u 2  u 3 h
 3 u 3 

2 f 2 f 2 f
   (Cartesian coordinates)
x 2
y 2
x 2
1 f  2 f 1 2 f 2 f (Cylindrical coordinates)
   
r r r 2 r 2  2 z 2
1   2 f  1   f  1 2 f
 2 R  2  sin   2 (Spherical coordinates)
R R  R  R sin      R sin 2   2
10
6.2 Separation of variables

A differential equation for each variable

11
Hydrogen-atom
ψ(r,θ,φ) = R(r) Θ(θ) Φ(φ) = R Θ Φ (6.5)
Wave function

ψ R dR
= ΘΦ = ΘΦ
r r dr
ψ Θ dΘ
= RΦ = RΦ
θ θ dθ

ψ Φ dΦ
= RΘ = RΘ
φ φ dφ

The partial derivatives become full derivatives because R, , and

 depend on r, , and  only.

12
To separate variables, plug  = R into Schrödinger's equation and divide
by R. The result is

sin2θ d  2 dR  sinθ d  dΘ 
 r  +  sinθ 
R dr  dr  Θ dθ  dθ 
1 d 2Φ 2mr 2 sin2θ  e 2 
+ + 2  + E = 0 . (6.6)
Φ dφ   4πε 0r 

We have separated out the  variable! The term

1 d 2Φ
Φ dφ

is a function of  only. Let's put it over on the right hand side of the equation.
This gives us…

13
 sin2θ d  2 dR  sinθ d  dΘ 
r +  sinθ 
R dr  dr  Θ dθ  dθ 
2mr 2 sin2θ  e 2  1 d 2Φ
+ 2  + E = - . (6.7)
  4πε 0r  Φ dφ

This equation has the form

f(r,θ) = g(φ)
f is a function of r and  only, and g is a function of  only.

“How can this be? The RHS has only  in it (but no r and ), and the LHS has
only r and  in it (but no ).”

Yup, you heard right!

“And yet you’re telling me LHS = RHS. I repeat, how can this be?”
14
Only one way!

f(r,θ) = a constant, independent or r,θ, and φ  = g(φ)

“Are you telling me everything is just a constant?”

Absolutely not! It’s just that the particular combination of terms on the LHS
happens to add up to a constant, which is the same as the constant given by the
particular combination of terms on the RHS.

sin2θ d  2 dR  sinθ d  dΘ 
r +  sinθ 
R dr  dr  Θ dθ  dθ 
2mr 2 sin2θ  e 2  1 d 2Φ
+ 2  + E  = constant = - .
  4πε 0r  Φ dφ
This is really good. We've taken the one nasty equation in r, and separated
it into two equations, one in r, and the other in  only. Maybe we can
separate the r part? 15
 sin2θ d  2 dR  sinθ d  dΘ 
 r  +  sinθ 
R dr  dr  Θ dθ  dθ 
2mr 2 sin2θ  e 2  1 d 2Φ
+ 2  + E  = constant = - . (6.7)
  4πε 0r  Φ dφ

It turns out (although we won't do the math in this course) that the “constant”
must be the square of an integer.

If not, our differential equations have no solution.

Thus, we can write the RHS of this equation as

1 d  2
  m 2
l (6.8)
 d 2

Where did this mℓ come from? It’s an integer. We just “happened” to give it
that “name.” 16
The LHS of our big Schrödinger equation also must equal mℓ2. If we set the
LHS equal to mℓ2, divide by sin2, and rearrange, we get

1 d  2 dR  2mr 2  e2  m 2 1 d  dΘ 
r  + 2  + E  = 2
-  sinθ . (6.9)
R dr  dr    4πε 0r  sin θ Θ sinθ dθ  dθ 

= constant = l(l+1)

ml2 1 d  d 
  sin    l (l  1) (6.10)
sin   sin  d 
2
d 

1 d  2 dR  2mr 2  e2 
r  2   E   l (l  1) (6.11)
R dr  dr    4 0 r 

17
 Equations (6.8), (6.10), and 96.11) are usually written

d 2
Equation for   m 2
l 0 (6.12)
d 2

m i
2
+
1
-
1 d  dΘ   
 +    

s
n
sinθ 
Θ = 0

2
Equation for   (6.13)
sinθ dθ  dθ   θ 

+
1
1 d  2 dR   2m  e 2     R = 0
Equation for R 2 r  + 2  + E   (6.14)
r dr  dr     4πε 0r  r2 

18
 6.3 Quantum Numbers

Three dimensions, three quantum numbers

19
We find the first quantum number by solving the differential equation for .

d2Φ 2
2
+ m Φ = 0
dφ
That equation should look familiar to you; you've seen it a number of times
before. It has solutions which are sines and cosines, or complex exponentials.
We write the general solution

Φ  φ  = A e j mφ . (6.15)
We will get the constant A by normalization.

Now, because  and +2 represent a single point in space, we must have

j m φ j m  φ + 2 π 
Ae = Ae .
This happens only for mℓ = 0, 1, 2, 3, ... 20
 

Fig. 6.2 The angle  and +2 both indentify the same meridian plane

21
ℓ is another quantum number, called the orbital quantum number, and the
requirement on ℓ can be restated as

mℓ = 0, 1, 2, 3, ..., ℓ. I’ll summarize OSE’s

in a bit.

Finally, the radial differential equation is

+
1
1 d  2 dR   2m  e 2     R = 0
2 r  + 2  + E  2 
r dr  dr     4πε 0r  r 

It can be solved only for energies E which satisfy the same condition as we
found on the energies for the Bohr atom:

me 4 1 E1
En = - 2 2 2
= 2 , n = 1, 2, 3... (6.16)
32π ε0  n n
n is called the principal quantum number.
22
Here’s the differential equation for r again:

+
1
1 d  2 dR   2m  e 2     R = 0
2 r  + 2  + E  2 
r dr  dr     4πε 0r  r 
Note that the product ℓ(ℓ+1) shows up in the equation for R, and n comes out
of solving this equation. Another math requirement for valid solutions is that
n(ℓ+1).

We can express the requirement that n=1,2,3,… and n(ℓ+1) as a condition on

ℓ:

ℓ = 0, 1, 2, ..., (n-1).

Summarizing our quantum numbers:

n = 1, 2, 3, ...
(6.17)
ℓ = 0, 1, 2, ..., (n-1)

mℓ = 0, 1, 2, 3, ..., ℓ 23

  Rnl  lm  m
l l

24
Ex. 6.1 Can you get a0 and E1 from the ground state wave
function for hydrogen??

 2   r a0
Table 6.1 R   3 2 e
 a0 

put E=E1 , l=0 in Eq. (6.14)

 2 4mE1   me2 4  1 r a0
 7 2  2 3 2     5 2  e 0
 a  a0   0a032
a0  r 

402 E1  
2 me4
 2 2 2
a0 
me2 2ma0 32 0 

25
6.4 Principal Quantum Number

Quantization of energy

26
 E1
En  (n  1 , 2 , 3 ,  )
n2
How about solar system (e.g. earth and sun)
or planetary motion?
Is it quantized?
Yes, but the separation of permitted energy levels
too small to be detected.

classical physics planetary motion, not atomic motion!!

27
28
 6.5 Orbital Quantum Number

Quantization of angular-momentum magnitude

29
•Radial part of Schrödinger’s Eq.
 2m
(6.14)
1 d  2 dR   e2  l ( l  1) 
r    2   E   R  0
r dr  dr   4  0 r r
2 2
  
KE orbital e2
U   (6.2)
KE radial 4  0 r
E  KE radial  KE orbital  U

1  d  2 dR   2m   2 l ( l  1) 
 r    2  KE radial  KE orbital  R  0 (6.19)
r2  dr  dr    2 mr 2 

radial part should be zero

1 (m vr )2 L2
KE orbital  m v orbital
2
  (6.20)
2 2 mr 2
2 mr 2

30
 L2  2 l ( l  1)
   L l ( l  1) 
2 mr 2
2 mr 2

Electron angular momentum L  l (l  1) (6.21)

for l =2, L  2(3)  2.6 10 34 J  s

for earth l  very large L  2.7 1040 J  s

• Designation of angular momentum states

l =0 12 3 4 5 6 •••
sp d f g h i
(sharp) (principal)(diffused)(fundamental):depending on spectrum

31
6.6 Magnetic Quantum Number

Quantization of angular-momentum direction

32
Question:
What possible significance can a direction in space have for a hydrogen atom?
Answer:
The answer becomes clear when we reflect that an electron revolving about a
nucleus is a minute current loop and has a magnetic field like that of a magnetic
dipole. Hence an atomic electron that possesses angular momentum interacts
with an external magnetic field B.

The magnetic quantum number ml specifies the direction of L by determining

the component of L in the field direction. This phenomenon is often referred
to as space quantization.
33
 •If there is a magnetic field in Z-axis,
L  r  mv
LZ
angular momentum orientation is quantized

2 ml  2
 ml  1 space quantization
LZ  ml  (6.22)
ml  0
ml  0 ,1 ,2   l
 ml  1 (magnetic quantum number)
 2
ml  2
LZ  ml   L
l l  1
L 
?

 6 l  2
34
 Right-hand rule:
When the fingers of the right hand point in the
direction of the motion, the thumb is in the
direction of L.

Fingers of right hand in direction

of rotational motion

Fig. 6.3 The right-hand rule for angular momentum

35
Fig. 6.4 Space quantization of orbit angular momentum.

Here the orbital quantum number is l=2 and th

ere are accordingly 2l+1=5 possible values of
the magnetic quantum number ml, with each v
alue corresponding to a different orientation re
lative to the z axis.

36
Fig. 6.5 The uncertainty principle prohibits the angular momentum
vector L from having a definite direction in space.
37
• Uncertainty principle and space quantization
Z

i) LZ  L
L
Z  0
v p   Not
r L   right!

Z
ml  ii) LZ  L
L
L l (l  1) Z  0 OK within uncertainty

principle
Z

38
Fig. 6.6
The angular momentum vector L precesses constantly about the z axis.
39
6.7 Electron Probability Density

No define orbits

40
 In Bohr theory , angular momentum only one value
(not considering its orientation)

p r ,  ,   has a meaning in quantum mechanics.

The probability of density to find an electron:


2
 R
2

2

2
(6.23)

  Aeiml   is symmetrical for 

2

Radial part of probability

 2
P r dr  r R dr   sin  d    d   r R dr
2 2 2 2 2 2
(6.25)
0 0
 dV  r sin ddrdr

41
Figure 6.7
The Bohr model of the hydrogen atom in a spherical polar coordinate
system.

42
 Radial part

Figure 6.8 The variation with distance from the nucleus of the radial part of the
electron wave function in hydrogen for various quantum states.
The quantity a 0  4 0  / me = 0.053 nm is the radius of the first Bohr orbit.
2 2 43
 Probability of Finding the Electron
The probability density of the electron at the point r, ,  is proportional to  ,
2

But the actual probability of finding it in the infinitesimal volume element dV

there is  2 dV .
In spherical polar coordinates (Fig. 6.9)
Volume element dV  (dr )(rd )(r sin d )  r 2 sin drd (6.24)

44
Figure 6.9 Volume element dV in spherical polar coordinates.
Figure 6.10
The probability of finding the electron in a hydrogen atom in the spherical
shell between r and r+dr from the nucleus is P(r)dr.
45
 Not symmetric

Probability

a0

Figure 6.11
The probability of finding the electron in a hydrogen atom at a distance
between r and r+dr from the nucleus for the quantum states of Fig. 6.8. 46
Equation (6.25) is plotted in Fig. 6.11 for the same states whose radial functions
R were shown in Fig. 6.8.
The curves are quite different as a rule. We note immediately that P is not a
maximum at the nucleus for s states, as R itself is, but has its maximum a
definite distance from it.

(1) The most probable value of r for a 1s electron turns out to be exactly a0, the
orbital radius of a ground-state electron in the Bohr model.

(1) However, the average value of r for a 1s electron is 1.5a0, which is puzzling at
first sight because the energy levels are the same in both the quantum-mechanical
and Bohr atomic models. This apparent discrepancy is removed when we recall
that the electron energy depends upon 1/r rather than upon r directly, and the
average value of 1/r for a 1s electron is exactly 1/a0. 47
Hydrogen 1s Radial Probability

48
Hydrogen 2s Radial Probability

49
Hydrogen 3s Radial Probability

50
Hydrogen 3p Radial Probability

51
Hydrogen 3d Radial Probability

52
 6.8 Radiative Transitions

What happens when an electron goes from one state to another

53
The time-dependent wave function n of an electron in a state of quantum number
n and energy En is the product of a time-independent wave function n and a time-
varying function whose frequency is
En En
i t i t
n   n e 
,   e
*
n
*
n
 (6.26)

1) electron in a state
 
x   x n dx   x n* n dx 
*

n
 does not radiate (6.27)

2) electron transition from m n

  a n  b m (6.28)
a *a : probability in n-state
b *b : probability in m-state
 a * a  b *b  1
54
x 

  x a 
* *

n  b * *

m a n  b m dx



  x a 
2 *

n n  b *
a  *

m n  a *
b  *

n m  b m m dx
2 *
 (6.29)
1
2   i  E m  E n t
 a   x  n* n dx  b * a   x  m*  n e  dx
(1)
1
 i  E n  E m t 
 a *b   x  n* m e dx  b 2   x  m*  m dx (6.30)
(2)
 Em  En   Em  En 
real part of (1)+(2) cos   t  cos 2   t  cos 2  t (6.30)
    h 
E  En
where  m (6.33)
h
during transition : electron oscillation with frequency of
  radiation energy : h

55
When the electron is in state n or state m the expectation value of the electron’s
position is constant.
When the electron is undergoing a transition between these states, its position
oscillates with the frequency. Such an electron, of course, is like an electric
dipole and radiates electromagnetic waves of the same frequency. This result
is the same as that postulated by Bohr and verified by experiment. As we have
seen, quantum mechanics gives Eq. (6.33) without the need for any special
assumptions.

56
 6.9 Selection Rules

Some transitions are more likely to occur than others

57
The general condition necessary for an atom in an excited state to radiate is
that the integral
 
 
(6.34)
x n m* dx or x n* m dx
 - Exception value <x> of the position
of such an electron

not be zero, since the intensity of the radiation is proportional to it. Transitions
for which this integral is finite are called allowed transitions, while those for
which it is zero are called forbidden transitions.

Allowed transitions 

u n ,l ,ml n*',l ',ml ' dV  0 (6.35)

l  1 (6.36)
Selection rules ml  0,  1 (6.37)
58
The change in total quantum number n is not restricted.
Equations (6.36) and (6.37) are known as the selection rules for allowed trans
itions (Fig. 6.13).

59
Figure 6.13
Energy-level diagram for hydrogen showing transitions all
owed by the selection rule l  1.
In the diagram the vertical axis represents excitation energy
above the ground state.
60
 6.10 Zeeman effect
How atoms interact with a magnetic field

61
 Zeeman Effect

• First reported by Zeeman in 1896. Interpreted by Lorentz.

• Interaction between atoms and field can be classified into

two regimes:

– Weak fields: Zeeman effect, either normal or anomalous.

– Strong fields: Paschen-Back effect.

• Normal Zeeman effect agrees with the classical theory of Lorentz.

Anomalous effect depends on electron spin, and is purely quantum mechanical.

62
63
64
If you “shoot” an electron through a region of space with no magnetic field, the
electron will experience no deflection (assuming no gravitational forces).

If you “shoot” an electron through a region of space with a nonzero magnetic field,
you know that the electron will experience a deflection.

   
   
-
   

    65
In an external magnetic field B, a magnetic dipole has an amount of potential energy Um
that depends upon both the magnitude  of its magnetic moment and the orientation of this
moment with respect to the field (Figure 6.15).
The torque  on a magnetic dipole in a
magnetic field of flux density B is

    B  B sin
 B

Figure 6.15 A magnetic

dipole of moment 
0 0 at the angle  relative to
Um    d   B  sin  d  a magnetic field B.
2 2

U m   B cos
0


  B  // B  U m : minimum 
2 (6.38)

66
The magnetic moment of a current loop has the magnitude

=IA
where I is the current and A the area it encloses.

The charge circulating a loop constitutes a current of magnitude

e
I  ef
T

where T is the orbital period of the electron

67
  e 
= IA    L
 2m 

Figure 6.16
(a) Magnetic moment of a current loop enclosing area A.
(b) Magnetic moment of an orbiting electron of angular momentum I.
68
1)magnetic moment , of a current loop B
  I A   efr 2 e
I
2) electron magnetic moments

L  mvr  2mfr 2  e 
   L
   efr 2  2m  (6.39)

gyromagnetic ratio
 e  (6.40)
Um    LB cos 
 2 m 
ml
cos   , L  l l  1 
l l  1 

 e 
U m  ml  B 5
Bohr magneton:  B  5.788  10 eV/T
 2m 
(6.41)

69
 U m depends upon ml

B  0 : energy depends on n and degenerate by l

B  0 : energy depends on n and m l splitting

Em  En
0 
h

Zeeman effect l  2  l  1
B e
1  0  B  0  B
h 4m
 2  0 (6.43)
B e
3  0  B  0  B
h 4m

70
1
No magnetic field Magnetic field present

Spectrum without magnetic field Spectrum with magnetic field present

Figure 6.17 In the normal Zeeman effect a special line of frequency 0 is split into three
components when the radiating atoms are in a magnetic field B. One component
is 0 and the others are less than and greater than 0 by eB/4m. There are only
three components because of the selection rule ml = 0, ±1. 71
72