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For most realistic potentials, the Schrdinger equation in Cartesian coordinates is not soluble by using the
separation of the wave function in three independent wave functions. For example, for the electromagnetic
interaction between an electron and a proton, the potential
is:
2
2
V( x, y, z ) =
ke
x 2 + y2 + z 2
ke
= V( r )
r
Separation of variables
Separation of variables
1.
The Schrdinger equation for the hydrogen atom involves Coulomb potential ke2/r. Since this is a central
potential (it has spherical symmetry) the equation can be separated in different independent equations
when it is expressed in spherical coordinates.
RADIAL
ANGULAR
RADIAL
= -L2
ANGULAR
1 d 2 F( ) L2
sin d
+ 2 sin 2
2
h
F( ) d
P( ) d
= -L2
dP( )
sin
=0
( r , , ) = R( r ) P( ) F ( )
SS 06 - 20 102: Introduction to atomic and molecular physics
The solution of every independent equation gives rise to a different quantum number.
2
1 d F( )
=C
F( ) d 2
General solution
F( ) = Ae
Azimuth solution
F( ) = Aeiml
ml = int eger
F( ) = F( + 2 )
c = ml
General solution
2
ml +
L
sin d
2
sin
h2
P( ) d
dP( )
sin
=0
L2
= l( l + 1 )
h2
L2
2
ml 0 ; l > ml
2
h
Pml ( x )
x = cos
The solution of the angular part of the electronic wave
function for the hydrogen atom are Spheric Harmonic
Yl ,m l ( , ) = P( ) F ( ) = Pml (cos )e
SS 06 - 20 102: Introduction to atomic and molecular physics
im
Positive integers
ml < l
Spherical Harmonics
= l ( l + 1 ) h 2
General solution
R( r ) = e r / na0 g ( x ) = e r / na0 r l Ln ,l
En =
2 mc 2
2n 2
13,6 eV
=
n2
( r , , ) = R( r ) P( ) F ( )
SS 06 - 20 102: Introduction to atomic and molecular physics
n=2
l=0
ml=0
l=0
l=1
ml=-1
ml=0
ml=1
ml=-1
ml=1
ml=-2
ml=2
l=0
l=1
l=2
= l( l +1) h
The equation represent the one dimensional equation
of a particle under an effective potential given by:
ke 2
l (l + 1)h 2
Veff ( r ) =
+
r
2mr 2
The potential represents the electrostatic attraction of
opposite charges plus a centrifugal potential L2/2mr2.
Thus, the separation constant is the orbital angular
momentum. The electron, in spite of not having a well
defined orbit, has an orbital degree of freedom which
is represented by a vector L .
The magnitude of L is:
L =
L2
sin d
ml + 2 sin 2
h
P( ) d
2
dP( )
sin
=0
h,
L cos = ml h
l (l + 1)h
L2 = l ( l + 1 ) h 2
L = l( l + 1 ) h
2 The squared angular momentum is
discrete in integer values of l .
l = 1
Lz = ml h
ml=+1
ml=0
ml=-1