8.

1 The hydrogen atom solutions

Slides: Video 8.1.1 Separating for the

radial equation
Text reference: Quantum Mechanics
for Scientists and Engineers
Section 10.4 (up to “Solution of
the hydrogen radial
wavefunction”).
 The hydrogen atom solutions

Separating for the radial equation

Quantum mechanics for scientists and engineers David Miller

Internal states of the hydrogen atom

We start with the equation for

the relative motion of electron and proton
 2 2 
  2   r  V  r   U  r   EH U  r 
 
We use the spherical symmetry of this
equation
and change to spherical polar coordinates
From now on, we drop the subscript r in the
operator  2
Internal states of the hydrogen atom

In spherical polar coordinates, we have

1  2  1  1     1 2 
  2 r  2  sin    sin     sin 2   2 
2

r r r r    
where the term in square brackets
is the operator 2 ,   Lˆ2 /  2 we introduced
in discussing angular momentum
Knowing the solutions to the angular momentum problem
we propose the separation
U  r   R  r  Y  ,  
Internal states of the hydrogen atom

The mathematics is simpler using the form

1
U  r     r  Y  ,  
r
where, obviously
  r   rR  r 
This choice gives a convenient simplification of the
radial derivatives
1  2   r  1   r 
2

r 
r r r r
2
r r 2
Internal states of the hydrogen atom

Hence the Schrödinger equation becomes

1   r    r  1 ˆ2
  r 
2
 2
 Y  ,    3 L Y  ,    Y  , V  r 
2 r r 2
r 2 r
1
 EH   r  Y  ,  
r
Dividing by   2   r  Y  ,   / 2  r 3
and rearranging, we have
r 2    r  2 2
2

  r  r 2
 r
2
 E H  V  r   
1 1
 2 Y  ,  
ˆ2Y  ,  
L
Internal states of the hydrogen atom

In
2
 2
  r  2 2
r
  r  r 2
 r
2
 E H  V  r   
1 1
 2 Y  ,  
ˆ2Y  ,    l  l  1
L

in the usual manner for a separation argument

the left hand side depends only on r
and the right hand side depends only on  and 
so both sides must be equal to a constant
We already know what that constant is explicitly
i.e., we already know that Lˆ2Ylm  ,     2l  l  1 Ylm  ,  
so that the constant is l  l  1
Internal states of the hydrogen atom

Hence, in addition to the L̂2 eigenequation

which we had already solved
from our separation above, we also have
r 2    r  2 2
2

 r 2  EH  V  r    l  l  1
  r  r 2

or, rearranging
2 d   r    2 l  l  1 
2

  V  r      r   EH   r 
2  dr 2
 2 r 2

which we can write as an ordinary differential equation
All the functions and derivatives are in one variable, r
Internal states of the hydrogen atom

Hence we have mathematical equation

2 d   r    2 l  l  1 
2

  V  r      r   EH   r 
2  dr 2
 2 r 2

for this radial part of the wavefunction
which looks like a Schrödinger wave equation
with an additional effective potential energy
term of the form
 2 l  l  1
2 r2
Central potentials

Note incidentally that

though here we have a specific form for V  r 
in our assumed Coulomb potential

 
V re  rp  
e2
4 o re  rp
the above separation works for any potential
that is only a function of r
sometimes known as a central potential
Central potentials

The precise form of the equation

 2
d 2
 r    2 l  l  1 
  V  r      r   EH   r 
2  dr 2
 2 r 2

will be different for different central potentials
but the separation remains
We can still separate out the L̂2 angular
momentum eigenequation
with the spherical harmonic solutions
Central potentials

Since a reasonable first approximation for more

complicated atoms
is to say that the potential is still approximately
“central”
approximately independent of angle
we can continue to use the spherical harmonics
as the first approximation to the angular form of
the orbitals
and use the “hydrogen atom” labels for them
e.g., s, p, d, f, etc.
 8.1 The hydrogen atom solutions

Slides: Video 8.1.3 – 8.1.4 Radial equation solutions

Text reference: Quantum Mechanics for Scientists
and Engineers
Sections 10.4 starting with “Solution of the
hydrogen radial wavefunction”, and 10.5
Note: The section Text reference: Quantum Mechanics for Scientists and Engineers
Section 10.4 contains the complete mathematical details for solving the radial
equation in the hydrogen atom problem. For this course, not all those details are
required and they are consequently not all covered in the online lectures, so the
additional detail, in particular on power series solutions in section Text reference:
Quantum Mechanics for Scientists and Engineers Section 10.4, is optional for the
student.
 The hydrogen atom solutions

Radial equation solutions

Quantum mechanics for scientists and engineers David Miller

Radial equation solutions

Using a separation of the hydrogen atom wavefunction

solutions into radial and angular parts
U  r   R  r  Y  ,  
and rewriting the radial part using
  r   rR  r 
we obtained the radial equation
2 d   r   e2  2 l  l  1 
2

      r   EH   r 
2  dr 2
 4 o r 2  r
2

where we know l is 0 or any positive integer
Radial equation solutions

We now choose to write our energies in the form

Ry
EH   2
n
where n for now is just an arbitrary real number
We define a new distance unit
s  r
where the parameter  is
2 2
  2  2 EH
nao 
Radial equation solutions

We therefore obtain an equation

d 2   l  l  1 n 1 
2
 2    0
ds  s s 4
Then we write
  s   s l 1 L  s  exp   s / 2 
so we get
d 2L dL
s 2   s  2  l  1    n   l  1  L  0
ds ds
Radial equation solutions

The technique to solve this equation

d 2L dL
s 2   s  2  l  1    n   l  1  L  0
ds ds
is to propose a power series in s
The power series will go on forever
and hence the function will grow arbitrarily
unless it “terminates” at some finite power
which requires that
n is an integer, and
n  l 1
Radial equation solutions

The normalizable solutions of

d 2L dL
s 2   s  2  l  1    n   l  1  L  0
ds ds
then become the finite power series
known as the associated Laguerre polynomials
n l 1
Lnl 1  s     1
2 l 1 q  n  l !
sq
q 0  n  l  q  1! q  2l  1!
or equivalently
p
L p  s     1
j q  p  j !
sq
q 0  p  q ! j  q !q !
Radial equation solutions

Now we can work back to construct the whole solution

In our definition   s   s l 1 L  s  exp   s / 2 
we now insert the associated Laguerre polynomials
  s   s l 1 L2nll11  s  exp   s / 2 
where s  (2 / nao )r
Since our radial solution was   r   rR  r 
we now have
1
R  r  nao s / 2   s l 1 L2nll11  s  exp   s / 2 
r
 s l L2nll11  s  exp   s / 2 
Radial equation solutions - normalization

We formally introduce a normalization coefficient A so

1 l 2l 1
R  r  nao s / 2   s Lnl 1  s  exp   s / 2 
A
The full normalization integral of the wavefunction
U  r   R  r  Y  ,  
would be   2
1     R  r  Y  ,   r sin  d d dr
2 2

r 0  0  0

but we have already normalized the spherical harmonics

so we are left with the radial normalization
Radial equation solutions - normalization


Radial normalization would be 1   R 2  r  r 2 dr

0

2n  n  l !
s  s  exp   s  s ds 
2
We could show 2l
 L
2 l 1 2

0
n l 1
 n  l  1!
so the normalized radial wavefunction becomes
3 1/2
  n  l  1!  2    2r l
2 l 1  2 r   r 
Rr         Lnl 1   exp   
 
2n n  l !  nao    nao   nao   nao 

Hydrogen atom radial wavefunctions

We write the wavefunctions

using the Bohr radius ao as the unit of radial distance
so we have a dimensionless radial distance
  r / ao
and we introduce the subscripts
n - the principal quantum number, and
l - the angular momentum quantum number
to index the various functions Rn,l
Radial wavefunctions - n = 1

Principal quantum number 2

n=1
1.5

Angular momentum
R R1,0   
1
quantum number
l=0 0.5

R1,0     2exp    
0 5 10 15
Radius 
 Radial wavefunctions - n = 2

l=0 0.8
2
R2,0      2    exp    / 2  R 0.6
4
0.4 R2,0   
l=1 0.2 R2,1   
6
R2,1      exp    / 2  0 5 10 15
12
 0.2

Radius 
 Radial wavefunctions - n = 3

l=0 0.4
R3,0     0.3 R   
3,0
R
2 3 2 2
 3  2     exp    / 3
0.2
27  9  R3,1    R 
0.1 3,2  
l=1
6  2 
R3,1       4    exp    / 3 0 5 10 15
81  3   0.1

l=2
2 30 2 Radius 
R3,2      exp    / 3
1215
 Hydrogen orbital probability density

1s
z n=1
x l=0
x-z m=0
cross-section
at y = 0
0.3 MMZ
 Hydrogen orbital probability density

1s

z n=1
x l=0
x-z m=0
cross-section
at y = 0
logarithmic
1.2 MMZl intensity scale
 Hydrogen orbital probability density

2s
z n=2
x l=0
x-z m=0
cross-section
at y = 0
0.3 MMZ
 Hydrogen orbital probability density

2s
z n=2
x l=0
x-z m=0
cross-section
at y = 0
logarithmic
1.2 MMZl intensity scale
 Hydrogen orbital probability density

2p
z n=2
x l=1
x-z m=0
cross-section
at y = 0
2 MMZ
 Hydrogen orbital probability density

3s
z n=3
x l=0
x-z m=0
cross-section
at y = 0
.3 MMZ
 Hydrogen orbital probability density

3s
z n=3
x l=0
x-z m=0
cross-section
at y = 0
logarithmic
1.2 MMZl intensity scale
 Hydrogen orbital probability density

3p
z n=3
x l=1
x-z m=0
cross-section
at y = 0
2 MMZ
 Hydrogen orbital probability density

3p
z n=3
x l=1
x-z m=0
cross-section
at y = 0
logarithmic
1.5 MMZl intensity scale
 Hydrogen orbital probability density

3d
z n=3
x l=2
x-z m=0
cross-section
at y = 0
4 MMZ
 Hydrogen orbital probability density

3d
z n=3
x l=2
x-z m=1
cross-section
at y = 0
 10 MMZ
Behavior of the complete hydrogen solutions

(i) The overall “size” of the wavefunctions becomes

larger with larger n
(ii) The number of zeros in the wavefunction is n – 1
The radial wavefunctions have n – l – 1 zeros
and the spherical harmonics have l nodal “circles”
The radial wavefunctions appear to have an additional
zero at r = 0 for all l  1 , but this is already counted
because the spherical harmonics have at least one
nodal “circle” for all l  1
which already gives a zero as r  0 in these cases
Behavior of the complete hydrogen solutions

In summary of the quantum numbers

for the so-called principal quantum number
n  1, 2,3,
and l  n 1
We already deduced that l is a positive or zero integer
We also now know the eigenenergies
Given the possible values for n
Ry
EH   2
n
Note the energy does not depend on l (or m)