Hydrogen atom

Masatsugu Sei Suzuki

Department of Physics, SUNY at Binghamton
(Date: January 13, 2012)

Bohr model
Schrödinger equation
Hydrogen atom

Niels Henrik David Bohr (7 October 1885 – 18 November 1962) was a Danish physicist
who made fundamental contributions to understanding atomic structure and quantum
mechanics, for which he received the Nobel Prize in Physics in 1922. Bohr mentored and
collaborated with many of the top physicists of the century at his institute in Copenhagen.
He was part of a team of physicists working on the Manhattan Project. Bohr married
Margrethe Nørlund in 1912, and one of their sons, Aage Bohr, grew up to be an
important physicist who in 1975 also received the Nobel prize. Bohr has been described
as one of the most influential scientists of the 20th century.

http://en.wikipedia.org/wiki/Niels_Bohr

_______________________________________________________________________
Erwin Rudolf Josef Alexander Schrödinger (12 August 1887– 4 January 1961) was an
Austrian theoretical physicist who was one of the fathers of quantum mechanics, and is
famed for a number of important contributions to physics, especially the Schrödinger
equation, for which he received the Nobel Prize in Physics in 1933. In 1935, after
extensive correspondence with personal friend Albert Einstein, he proposed the
Schrödinger's cat thought experiment.

1
http://en.wikipedia.org/wiki/Erwin_Schr%C3%B6dinger

1. Orbital angular momentum in quantum mechanics

The orbital angular momentum is defined as

ex ey ez
ˆ
L  rˆ  pˆ  xˆ yˆ zˆ
pˆ x pˆ y pˆ z

Lˆ x  yˆ pˆ z  zˆpˆ y

Lˆ y  zˆpˆ x  xˆpˆ z

Lˆ z  xˆpˆ y  yˆ pˆ x

[ Lˆ x , Lˆ y ]  [ yˆ pˆ z  zˆpˆ y , zˆpˆ x  xˆpˆ z ]

 [ yˆ pˆ z , zˆpˆ x ]  [ zˆpˆ y , xˆpˆ z ]
 yˆ[ pˆ z , zˆ ] pˆ x  pˆ y [ zˆ, pˆ z ]xˆ

  ( yˆ pˆ x  xˆpˆ y )  iLˆ z
i

or

[ Lˆ x , Lˆ y ]  iLˆ z ,

2
Similarly,

[ Lˆ y , Lˆ z ]  iLˆ x , [ Lˆ z , Lˆ x ]  iLˆ y

L̂2 is defined by

Lˆ2  Lˆ x  Lˆ y  Lˆ z
2 2 2

We have

[ Lˆ2 , Lˆ z ]  [ Lˆ x  Lˆ y  Lˆ z , Lˆ z ]  [ Lˆ x , Lˆ z ]  [ Lˆ y , Lˆ z ]
2 2 2 2 2

 [ Lˆ z , Lˆ x ]  [ Lˆ z , Lˆ y ]  0̂
2 2

using the relations

[ Lˆ z , Lˆ x ]  [ Lˆ z , Lˆ x ]Lˆ x  Lˆ x [ Lˆ z , Lˆ x ]  i ( Lˆ y Lˆ x  Lˆ x Lˆ y )
2

[ Lˆ z , Lˆ y ]  [ Lˆ z , Lˆ y ]Lˆ y  Lˆ y [ Lˆ z , Lˆ y ]  i ( Lˆ y Lˆ x  Lˆ x Lˆ y )
2

Similarly

[ Lˆ2 , Lˆ x ]  0̂ , [ Lˆ2 , Lˆ y ]  0̂ [ Lˆ2 , Lˆ z ]  0̂

2. Quantum mechanical orbital angular momentum: spherical coordinates

3
 z

e` r

dr e` f
r cosq
rdq
q r
e` q
dq

f df
r sinq

r sinq df

x
The orbital angular momentum in the quantum mechanics is defined by

L  r  p  i ( r   )

using the expression

 1  1 
  er  e  e
r r  r sin  

in the spherical coordinate. Then we have

 1  1 
L  i(r  )  ie r r  (e r  e  e )
r r  r sin  
 1 
 i (e  e )
 sin  

.
The angular momentum Lx, Ly, and Lz (Cartesian components) can be described by

4
  1 
L  i[( sin e x  cos e y )  (cos  cos e x  cos  sin e y  sin e z ) ]
 sin   .

or

 
Lx  i (sin   cot  cos  )
 

 
L y  i ( cos   cot  sin  )
 


Lz  i


We define L+ and L- as

 
L  Lx  iLy  iei (i  cot  )
 

and

 
L  Lx  iLy  ie  i (i  cot  )
 

We note that the operator  can be expressed using the operator L as

 i rL
  er 
r  r 2

The proof of this equation is given as follows.

(r  L)  1   1 
 re r  (e  e )  r (e  e )
i  sin    sin  

or

(r  L) 1  1  
 e  er    er
ir 2
r  r sin   r

or

5
  i (r  L)
  er 
r r 2

2 2 2
From L2  Lx  Ly  Lz , we have

1 2 1  
L2   2 [  (sin  )]
sin  
2 2
sin   

Using

L2  
 r 2 2  (r 2 )
 2
r r

we can also prove that

 i
r 2  (1  r )  L
r 

((Note))

1 2 1  2 
2   L  2 (r )
 r 2 2
r r r
1 1  2 
  2 2 L2  2 (r )
 r r r r
1 1 2
  2 2 L2  (r )
 r r r 2
2
1 p
  2 2 L2  r2
 r 

where the definition of pr is given below. This expression can be rewritten as

2
 2 2 pr L2
   
2 2  2 r 2

______________________________________________________________________
3. Radial momentum operator pr in the quantum mechanics
(a) In classical mechanics, the radial momentum of the radius r is defined by

1
prc  (r  p)
r

6
(b) In quantum mechanics, this definition becomes ambiguous since the component
of p and r do not commute. Since pr should be Hermitian operator, we need to
define as the radial momentum of the radius r is defined by

1 r r
prq  ( p  p  )
2 r r

This symmetric expression is indeed the canonical conjugate of r.


prq r  rprq 
i

Note that

 1 1 
prq  (i )(  )  (  i ) r
r r r r

This can be proved as follows.

1
prq ( r , ,  )  ( i ){e r . ( r , , )    [e r ( r , ,  )]}
2
1  1 
 ( i )[  2 ( r 2 )]
2 r r r
1  2 
 ( i )(2  )
2 r r r
 1 
 i  (  )
r r r
1 
 ( i  r )
r r

where

 1  1 
  e r  e  e
r r  r sin  

1  2 1  1 
A  (r Ar )  (sin A )  A
r r
2
r sin   r sin  

For convenience we use

peq  pr

then we have

7
 2 1  1  1 2
pr  (i r )(i r )   2 r
r r r r r r 2

________________________________________________________________________
4. Central field problem
Free particle wave function  satisfies the Schrödinger equation

2 2
[   V (r )]  E ,
2

where  is the reduced mass of particle, E is the energy eigenvalue of the system. The
wavefunction can be expressed by

   km (r , ,  )

1 L2
[ pr  2  V (r )] nm (r , , )  E nm (r , , )
2

2 r

(separation variables),

 nm (r , , )  Rn (r )Ym ( , )

with

L2Ym ( ,  )   2(  1)Ym ( ,  )

LzYm ( , )  mYm ( , )

Note that Ym ( ,  ) is the spherical harmonics.

1 2  2l (l  1)
[ pr  ]Rn (r )  V (r ) Rn (r )  ERn (r )
2 r2

1 
Since pr  r , we have
i r r

2 1  1  1 2
pr Rn (r )  r( r ) Rn (r )   2 [rRn (r )]
i r r i r r r r 2

or

8
 1 2 2 1 2
 [rRn (r )]  [ 2 V (r )  2 (  1)]Rn (r )  2 ERn (r )
r r 2
 r 

or

1 2 2 1
[rRn (r )]  [ 2 ( E  V (r ))  2 (  1)]Rn (r )  0 .
r r 2
 r

Note that for a fixed l, the energy eigenvalue is independent of m, and is at least (2l+1)-
fold degenerate.

We assume that

u (r )
Rnl (r )  ,  = -1
r

l(l  1) 2 ( 1  V (r)

u"(r)  [ 2  2 ]u(r)  0
 r 

We further assume a Coulomb potential given by

Ze 2
V (r )  k
r

with

1
k
4 0

Then

Ze 2
2 (1  k )
l (l  1) r ]u (r )  0
u" ( r )  [ 2 
r 2

We now introduce a new variable

   2 n an 
r    
81 Z 2 e 4 2kZe 2
2Z 2
8k 2
2 2 n 2

where

9
 Z 2 e 4 ke 2 Z 2
1  k 2  , En  1
2 2 n 2 2a n 2

2
a (a = a0: Bohr radius when  = m (electron mass))
ke 2

ke 2
(Rydberg energy when a = a0)
2a

Z

na

Since

2rZ
  2r
na

we get

d d d d
  2
dr dr d d

d2 d d 2 d
2
 2 (2 )  4
dr 2 d d d 2

l(l  1) 4n
4 2 u"(  )  [4 2   2 (1  )]u( )  0
 2


where

2 Ze 2 4n
(  k )   2 (1  )
 2 1
r 

Then we have

l(l  1) 1 n
u"(  )  [  (  )]u(  )  0
 2
4 
or

d 2 l(l  1) n 1
[ 2    ]u( )  0 (1)
d 2  4

10
5. Series expansion method

Solution of radial part of the hydrogen atom (we need to show that  = n; positive
integer)

d 2 l (l  1)  1
[    ]u(  )  0 (1)
d 2 2  4

with

kZe 2 
 , which corresponds to the eigenvalue.
 21

Note that according to the Bohr model,  = n (positive integer) since

Z 2 e 4 ke 2 Z 2
1  k 2 
2 2 n 2 2a n 2

We solve the differential equation to determine the eigenvalue and eigenfunction. In the
limit of   0 , we assume that it behaves at the origin like

u
s

1 s
[s(s  1)  l(l  1)] s 2   s 1   0
4

Note that the s-2 term dominates for small .

s(s  1)  l(l  1)  0 ,

or

(s    1)(s  l)  0


s  l  1 or s = - l.

We must discard those solutions that behave as  l . So we get the form around  = 0:

u (  )   l 1

In the limit of    ,

11
 d2 1
( 2  )u(  )  0
d 4

The solution for this equation is

u(  )  Ae  / 2  Be / 2

The constant B should be equal to zero (    ):

u(  )  e   / 2

Thus we can attempt to find a solution of the form

l 1   / 2
u(  )   e F ( )

With this substitution, the differential equation (1) becomes

d 2 F( ) 2l  2 dF(  )  l  1
(  1) (  )F( )  0
d 2
 d  

We assume that

F(  )   Ck 
k

k0

with C0 ≠ 0.

  

 k(k  1)C } k
k 2
  (2l  2)kCk 
k 2
 [ k    (l  1)]Ck}
k 1
0
k 2 k 1 k0

or


{k(k  1)  (2l  2)(k  1)]C k 1  [ k    (l  1)]Ck}

k 1
0
k 0

leading to

Ck  1 k  l 1  

Ck (k  1)(k  2l  2)

((Note))

12
Coefficient of 0

(1  l   )C0  (2  2l )C1  0

Coefficient of 1

(2  l   )C1  2(3  2l )C2  0

Coefficient of 2

(3  l   )C2  3(4  2l )C3  0

Coefficient of 3

(4  l   )C3  4(5  2l )C4  0

Coefficient of 4

(5  l   )C4  5(6  2l )C5  0

Coefficient of 5

(6  l   )C5  6(7  2l )C6  0

............................................................................................

Note that

Ck 1 1

Ck k

which is the same asymptotic behavior as e. Thus, unless the series terminate, u() will
grow exponentially like e.

To avoid this, we must have

For k = nr,

nr  l  1    0

or

13
   nr  l  1

Then we have

Cn r 1  Cnr  2  ...  0

For nr = 0,   l  1

F(  )  C0

For nr = 1,   l  2

F(  )  C0  C1 

For nr = 2,   l  3

F(  )  C0  C1   C2  2

The function F will thus be a polynomial of degree of nr, known as an associated

Laguerre polynomial.

Ze 2 
k  l  1  nr
 2E

or

k 2 Z 2 e 4
E
2 2 (l  1  nr ) 2

Since l = 0, 1, 2, 3,..., nr = 0, 1, 2,..., we introduced a principal quantum number n,

defined by

n = l + 1 + nr

with n = 1, 2, 3, .... Thus, in terms of n,

k 2 Z 2 e 4 ke 2 Z 2
En   
2 2 n 2 2an 2

_____________________________________________________________________
n = 1, nr = 0, l = 0 (1s)
______________________________________________________________________
n = 2, nr = 0, l = 1 (2p)
14
 n = 2, nr = 1, l = 0 (2s)
______________________________________________________________________
n = 3, nr = 0, l = 2 (3d)

n = 3, nr = 1, l = 1 (3p)

n = 3, nr = 2, l = 0 (3s)
______________________________________________________________________
n = 4, nr = 0, l = 3 (4f)

n = 4, nr = 1, l = 2 (4d)

n = 4, nr = 2, l = 1 (4p)

n = 4, nr = 3, l = 0 (4s)

______________________________________________________________________
n = 5, nr = 0, l = 4 (5g)

n = 5, nr = 1, l = 3 (5f)

n = 5, nr = 2, l = 2 (5d)

n = 5, nr = 3, l = 1 (5p)

n = 5, nr = 4, l = 0 (5s)
_______________________________________________________________________

These nlm states have the same energy which is only dependent on n.

6. Spherical harmonics Ylm ( ,  )

 
LzYlm ( , )  Ylm ( , )  mYlm ( , ) (1)
i 

The  and  dependence of Yl m ( , ) is given by

1 2 1  
L2Yl m ( ,  )   2 [  (sin  )]Yl m ( ,  )
sin  
2 2
sin    (2)
  l (l  1)Yl ( ,  )
2 m

Equation (1) shows that

15
 Yl m ( , )  lm ( )eim

where Yl m ( , ) is normalized as

* *
 l ,l ' m,m '   dYl m' ' ( ,  )Yl m ( ,  )   sin ddYl 'm ' ( ,  )Yl m ( ,  )

where  is a solid angle and d  sin dd . We must require that the eigenfunction be
single valued
im im ( 2  )
e e

which means that m = 0, ±1, ±2, (integers). Equation (2) can be rewritten as

1 d d m2
[ (sin  )  l (l  1)]lm ( )  0
sin  d d sin 
2

The result for m≥0 is

(1)l (2l  1) (l  m)! im 1 d l m

Yl m ( ,  )  e (sin  ) 2l
2l l! 4 (l  m)! sin  d (cos )
m l m

and we define Yl  m ( ,  ) by

Yl  m ( ,  )  (1)m [Yl m ( , )]*

or

[Yl m ( ,  )]*  (1) m Yl  m ( ,  )

7. Quantum numbers

n: the principal quantum number.

l: the azimuthal quantum number
m: the magnetic quantum number

For the fixed n (=1, 2, 3, 4, ...),

l = n-1, n-2,......., 1, and 0.

l=0 sharp (s)

m=0

16
 l = 1 principal (p)
m = 1, 0, -1

l = 2 diffuse (d)
m = 2, 1, 0, -1, -2

l = 3 fundamental (f)
m = 3, 2, 1, 0, -1, -2, -3

l =4 (g)
m = 4, 3, 2, 1, 0, -1, -2, -3, -4

There are (2 l +1) solutions to the Schrodinger equation corresponding to the same energy
eigenvalue En.

n 1
n(n  1)
Degeneracy of En =  (2l  1)  2
l 0 2
 n  n2 .

((Note)) Including spin degeneracy of states is 2n2.

n l m ms
1s 1 0 0  1/ 2
2s 2 0 0  1/ 2
2p 2 1 0, ±1  1/ 2
3s 3 0 0  1/ 2
3p 3 1 0, ±1  1/ 2
3d 3 2 0, ±1, , ±2  1/ 2
4s 4 0 0  1/ 2
4p 4 1 0, ±1  1/ 2
4d 4 2 0, ±1, , ±2  1/ 2
4f 4 3 0, ±1, , ±2, ±3  1/ 2

8. Vector model of the orbital angular momentum

We consider a case which l is some fixed number (l = 1, 2, 3,...). Then the total
angular momentum may be represented by a vector of length

 l (l  1)

The component m in the z direction is

m = l, l - 1, l - 2, ........, -l+ 1, -l

The vector J should be thought of as covering a cone, with vector angle given by
17
 m
cos m 
l (l  1)

where m is the angle between the z axis and L.

(a)
l=1

1 1 + 1
m = 1, 0, -1

m=1

m=0

m=-1

(b)
l= 3
m = 3, 2, 1, 0, -1, -2, -3

18
 3 3 + 1

m=3

m=2

m=1

m=0

m=-1

m=-2

m=-3

(c)
l=6
m = 6, 5, 4, 3, 2, 1, 0, -1, -2, -3, -4, -5, -6

6 6 + 1

m=6
m=5
m=4
m=3
m=2
m=1
m=0
m=-1
m=-2
m=-3
m=-4
m=-5
m=-6

2
9. SphericalPlot3D of Yl m ( , )
We make a SphericalPlot3D of the spherical harmonics.
________________________________________________________________________
(i)
l=0 m=0 Yl 0 0 ( , )

19
 1
0 0
2 

l = 0, m = 0

_______________________________________________________________________
(ii) m = -1, 0, 1
l=1 m Yl m1 ( ,  )

1  1 1   3
Sin
2 2

1 0 1 3
Cos
2 

1 1  1   3
Sin
2 2

l = 1, m = ±1 l = 1, m = 0

________________________________________________________________________
(ii) m = -2, -1, 0, 1, 2
l=2 m Yl m 2 ( , )

20
 2  2 1 2   15
Sin2
4 2

2  1 1   15
Cos Sin
2 2

2 0 1 5
1  3 Cos2 
8 

2 1  1   15
Cos Sin
2 2

2 2 1
2   15
Sin2
4 2

l = 2, m = ±2 l = 2, m = ±1 l = 2, m = 0

_______________________________________________________________________
(iv) m = -3, -2, -1, 0, 1, 2, 3

l=3 m Yl m 3 ( , )

21
 3  3 1 3   35
Sin3
8 

3  2 1 2   105
Cos Sin2
4 2

3 1 1
  21
3  5 Cos2  Sin
16 

3 0 1 7
3 Cos  5 Cos3 
16 

3 1  1   21
3  5 Cos2  Sin
16 

3 2 1
2   105
Cos Sin2
4 2

3 3  1 3   35
Sin3
8 

l = 3, m = ±3 l = 3, m = ±2 l = 3, m = ±1 l = 3, m = 0

10. SphericalPlot of 2p orbitals

22
p-orbitals

- Y11 (q, f)+Y1-1 (q, f)]

1
ypx=
2

ypy=Â 1
Y11(q, f)+Y1-1(q, f)]
2

ypz=Y10(q,f)

px orbit

23
 py orbit

Out[53]=

pz orbit

11. SphericalPlot of 3d orbitals

24
de-orbitals

1
yxy=-Â [Y22(q, f)-Y2-2(q, f)]
2

1
yyz=-Â [Y22(q, f)+ Y2-2(q, f)]
2

1
yzx=- [Y21(q,f)- Y2-1(q, f)]
2

dg-orbitals

1
y x2- y2 = [Y22(q, f)+Y2-2(q, f)]
2

y3 z2-r2 =Y20(q,f)

d(xy) orbit

25
d (yz) orbit

d (zx) orbit

26
 d(x2-y2) orbit

d(3z2-r2) orbit

________________________________________________________________________
12. The form of radial wave function Rnl(r)
The radial wave function Rnl(r) is given by

rRnl (r)  unl (r)  Ae  / 2  l 1 L2nll11 ( ) ,

27
where

  2 r .

Then we have

unl (r) A  / 2 l 1 2 l 1  / 2 l 2 l 1
Rnl (r)   e  Ln l1 ( )  2A e  Ln l 1 ( )
r r

A is determined from the condition of normalization.

 
A 2   2 l 2 2 l 1
1   [Rnl (r)] r dr 2 2
 e  [L n l 1 (  )]2 d , (2)
0
2 0

Here we use the formula:


( p  q)!
e

 q 1 Lqp (  )Lqp (  )d  (2 p  q  1)
0
p!

Note that

p  n  l  1, q  2l  1, p  q  n  l , and 2 p  q  1  2n

Then we have

(n  l)!
e

 2 l 2 [L2nl1l 1 (  )]2 d  (2n)
0
(n  l  1)!

Using this formula, Eq.(2) can be rewritten as

A2 (n  l)!
1 (2n)
2 (n  l  1)!

or

Z 1/ 2 (n  l  1)!
A  1/ 2
na (n  l)!

Thus we get

Rnl (r)  Rnl (  )  Anl e  / 2  l L2ln l11 (  )

with

28
 2Z 3 / 2 (n  l  1)!
Anl 
n2a3 / 2 (n  l )!

((Note)) The final form of Rnl (r ) is as follows.

(n  l  1)!
l
2Z 3 / 2 Zr  2Z  2l 1 2Z
Rnl (r )  2 3 / 2 exp( ) r  Ln  l 1 (   r)
na (n  l )! na  na  na
(n  l  1)! l 1  l  3 / 2 l  3 / 2  l  2 l Zr 2Z
 2 a Z n r exp( ) L2nll11 (   r)
(n  l )! na na

since

2Z
 r
na

This function satisfies the differential equation

d2 2 d 1 n l(l  1)
[ 2  (   )]Rnl ( )  0 .
d  d 4  2

We also have

Z 1/ 2 (n  l  1)!   / 2 l 1 2l 1
unl (r )  unl (  )  e  Ln  l 1 (  )
na1 / 2 (n  l )!

13. Radial probability

The wave function  nlm (r ) is normalized as

1    nlm (r ) dr 2 dr

where  is the solid angle and d  sin dd

 nlm (r )  Rnl (r )Yl m ( , )

and

2 2 2
1   drr 2 Rnl (r )  d Y l
m
( , )   drr 2 Rnl (r )

where

29
 2
 d Yl ( , )  1
m

We define Prdr as

Pr dr  r 2 | Rnl (r ) |2 dr

Then the average r s is defined by

 
 r s   drr 2 [ Rnl (r )]2 r s   drr s 2 [ Rnl (r )]2
0 0

where

2
a
ke 2
kZe 2
En  
2n 2 a

The average r s is obtained as

Z 4 [3n 2  l (l  1)]
r 4 
n5 a 4l (l  1 / 2)(l  1)[2l (l  1)  3 / 2]
Z3
r 3 
n 4 al (l  1 / 2)(l  1)
Z2
r 2 
n 3a 2 (l  1 / 2)
Z
r 1  2
na
r0 1
a
r  [3n 2  l (l  1)]
2Z
a2 2 2
r2  n [5n  1  3l (l  1)]
2Z 2
a3
r3  3 n 2 [35n 4  3(l  1)l (l  1)(l  2)  5n 2 (6l (l  1)  5)]
8Z

14. Form of the wave function

We use the radial wave function as
30
 2Z 3 / 2 (n  l  1)!   / 2 l 2l 1
Rnl (r )  Rnl (  )  e  Ln  l 1 (  )
n2a3 / 2 (n  l )!

where

2 Zr
  2r 
na

________________________________________________________________________
(a) Expression of Rnl (r )
n =1

3/ 2
Z  Zr
R10 (r )  2  exp( )
a a

n=2

3/ 2
1 Z Zr Zr
R20 (r )    (1  ) exp( )
2a 2a 2a

3/ 2
1 Z Zr Zr
R21 (r )    exp( )
2 6a a 2a

n=3

3/ 2
2 Z  2 Zr 2 Z 2 r 2 Zr
R30 (r )    (1   2
) exp( )
3 3 a 3a 27a 3a

3/ 2
8 Z  Zr Zr Zr
R31 (r )    (1  ) exp( )
27 6  a  a 6a 3a

3/ 2
4 Z Z 2r 2 Zr
R32 (r )    2
exp( )
81 30  a  a 3a

(b) Expression of Rnl (  )

n =1

31
 3/ 2
Z  
R10 (  )  2  exp( )
a 2

n=2

3/ 2
1 Z  
R20 (  )    (2   ) exp( )
2 2a 2

3/ 2
1 Z 
R21 (r )     exp( )
2 6a 2

n=3

3/ 2
1 Z  
R30 (r )    (6  6    2 ) exp( )
9 3 a 2

3/ 2
1 Z  
R31 (r )     (4   ) exp( )
9 6a 2

3/ 2
1 Z  
R32 (r )     2 exp( )
9 30  a  2

________________________________________________________________________
15. Plot of the probability of the wave function and the average radius

(i) r 2 [ Rnl (r )]2 vs r/a, where a = 1 and Z =1.

a
(ii)  r  [3n 2  l (l  1)] , where a = 1 and Z = 1.
2Z

For the 1s state,

32
 Pr

0.5 <r>a

0.4 n =1

0.3 { =0

0.2

0.1

0.0 ra
0 1 2 3 4 5 6 7 

Fig. 1s (n = 1, l = 0). The straight line denotes the average value (<r>/a).

For the 2s, 2p states
Pr

0.20 n =2

0.15 { =0

0.10 { =1

0.05

0.00 ra
0 2 4 6 8 10 12 14

Fig. 2s (n = 2, l = 0). 2p (n = 2, l = 1). The straight lines denote the average value
(<r>/a).

For the 3s, sp, and 3d states,

33
 Pr

0.14
n =3
0.12

0.10

0.08
{ =0
0.06
{ =1
0.04

0.02 { =2
0.00 ra
0 5 10 15 20

Fig. 3s (n = 3, l = 0). 3p (n = 3, l = 1). 3d (n = 3, l = 2). The straight lines denote the

average value (<r>/a).

For the 4s, 4p, 4d, and 4f states,

Pr
0.10

0.08 n =4

0.06 { =0
{ =1
0.04 { =2

0.02 { =3

0.00 ra
0 5 10 15 20 25

Fig. 4s (n = 4, l = 0). 4p (n = 4, l = 1). 4d (n = 4, l = 2). 4f (n = 4, l = 3). The straight

lines denote the average value (<r>/a).

16. ContourPlot of the wavefunctions (Mathematica)

2
The probability function  nlm(r , , ) is expressed using the spherical co-ordinate (r,
, ).

34
 2 2
 nlm(r , , )  Rnl (r )Yl m ( , )

where

(n  l  1)! l 1  l  3 / 2 l  3 / 2  l  2 l Zr 2Z
Rnl (r )  2 a Z n r exp( ) L2nll11 (   r)
(n  l )! na na

Using the relations

 z  y
r  x2  y2  z 2 ,   arccos ,   arctan( )
 x2  y 2  z 2  x
 

the function can be expressed by the Cartesian co-ordinate. Here we assume that

Z = 1,  = m (mass of electron), and a = a0 (Bohr radius).

(a) d (zx) orbit

n Ø 3, l Ø 2, yzx,  x, 0, z
15

10

-5

- 10

- 15
- 15 - 10 -5 0 5 10 15

(b) d (3z2-r2) orbit

35
 n Ø 3, l Ø 2, y3z2 - r2 ,  x, y, 0
15

10

-5

- 10

- 15
- 15 - 10 -5 0 5 10 15

_______________________________________________________________________
APPENDIX

Vector analysis in the Spherical co-ordinates:

(a) 
The gradient is given by

 1  1 
  e r  e  e
r r  r sin  

where  is a scalar function of r, , and .

(b) A
The divergence is given by

1  2 1  1 
A  (r Ar )  (sin A )  A
r r
2
r sin   r sin  

(c) A

36
   A is given by

hr e r h e h e er re r sin e

1    1   
A   2
hr h h r   r sin  r  
hr Ar h A h A Ar rA r sin A

(d) Laplacian

1  h h   h hr   hr h 
 2  [ (   ) ( ) ( )]
hr h h r hr r  h   h 
1      1 
 [ (r 2 sin  ) (sin  ) ( )]
r sin  r
2
r    sin  

or

1  2  1   1  2
 2  ( r )  (sin  ) 
r 2 r r r 2 sin    r 2 sin 2   2

We can rewrite the first term of the right hand side as

1  2  1 
(r ) (r )
r r
2
r r r 2

which can be useful in shortening calculations.

Note that we also use the expression for the operator

1  2  1   1 2
  2 (r
2
) (sin  ) 2 2 
r r r r 2 sin    r sin   2
1  2  1 1   1 2
 ( r )  { (sin  )  }
r 2 r r r 2 sin    2
sin 2   2

37