What began it all...the matter wave equation, i.e.

,
the time-independent Schrodinger wave equation:

h
2
8
2
m

x
2
+

2

y
2
+

2

z
2

+ V (x, y, z) = E
where:
V = potential energy =
K Z e
2
r
for the hydrogenic atom.
and
= (x, y, z) = matter wave amplitude
and
E = energy =
Z
2
R
y
n
2
for the hydrogenic atom

n,,m

(r, , ) = R
n,
(r)Y
,m

(, ) = R
n,
(r)

()e
im

The time-independent Schrodinger equation again, using the

2
x
2
+

2
y
2
+

2
z
2
.
We now have the following:

h
2
8
2
m

2
+ V = E .
||
2
= matter wave intensity = probability density (Max Born).
1
The wave functions, , a.k.a. Atomic Orbitals (AO), are
functions of r, , and ...Spherical Polar coordinates NOT the
Cartesian coordinates (x, y, z) ! How are the two coordinate systems
related?. Below is a diagram from Zumdahl 6/e:
10
Figure 12.15: The spherical polar coordinate system:
0 r < " ; 0 # (180) ; 0 $ 2 (360)
x = rsin(#)cos($) ; y = rsin(#)sin($) ; z = rcos(#)
2
The pictures of these atomic orbitals are plots of pieces of the wave
function (r, , ) , either with respect to angles (, ) or with
respect to r. The wave function or atomic orbital can be
decomposed into a radial portion (denoted R(r)) and an angular
portion (denoted Y (, )). The portions are themselves dependent
upon the three quantum numbers: n, , m

. The division is as follows:

n,,m

(r, , ) = R
n,
(r)Y
,m

(, ) = R
n,
(r)

()e
im

.
Recall the rules for each of the three (3) quantum numbers:
n = 1, 2, 3, . . . principal quantum number ;
= 0, 1, 2, 3, . . . , (n 1) for each n angular momentum (or
azimuthal) quantum number ; and
m

= 0, 1, 2, 3, . . . , for each magnetic quantum

( + 1)
h
2
Lets take another look at this wave function and compare to what we
see in Table 12.1 of Zumdahl :

n,,m

(r, , ) = R
n,
(r)Y
,m

(, ).
The radial part = R
n,
(r) can be partitioned into 2 parts:
R
n,
(r) {Polynomial in r} e

Zr
na
0
.
The angular part contains various combinations of trigonometric
functions of cos(), sin(), cos(), and sin().
3
Hydrogen Wave Functions (!)
Adapted from Table 12.1 of Chemical Principles (6/e) S. Zumdahl:
Solutions of the Schrdinger Wave Equation for the Hydrogen Atom
n l m
l
Orbital !(r,",#) = (Constant)(Radial)(Angular)
!(r,",#) = R
nl
(r)Y
lml
(",#)
[Spherical Polar Coordinates]
1 0 0 1s
$
%
&
'
(
)
1
!a
0
3
e
-r/a0
2 0 0 2s
$
%
&
'
(
)
1
4 2!a
0
3

$
%
&
'
(
)
2 -
$
%
&
'
(
)
r
a
0
e
-r/2a0
2 1 0 2p
z
$
%
&
'
(
)
1
4 2!a
0
3

$
%
&
'
(
)
r
a
0
e
-r/2a0
(cos("))
2 1 1 2p
x
$
%
&
'
(
)
1
4 2!a
0
3

$
%
&
'
(
)
r
a
0
e
-r/2a0
(sin(")cos(#))
2 1 1 2p
y
$
%
&
'
(
)
1
4 2!a
0
3

$
%
&
'
(
)
r
a
0
e
-r/2a0
(sin(")sin(#))
3 0 0 3s
$
%
&
'
(
)
1
81 3!a
0
3

$
%
&
'
(
)
27 -
$
%
&
'
(
)
18r
a
0
+
$
%
&
'
(
)
2r
2
a
0
2 e
-r/3a0
3 1 0 3p
z
$
%
&
'
(
)
2
81 !a
0
3

$
%
&
'
(
)
$
%
&
'
(
)
6r
a
0
-
$
%
&
'
(
)
r
2
a
0
2 e
-r/3a0
(cos("))
3 1 1 3p
x
$
%
&
'
(
)
2
81 !a
0
3

$
%
&
'
(
)
$
%
&
'
(
)
6r
a
0
-
$
%
&
'
(
)
r
2
a
0
2 e
-r/3a0
(sin(")cos(#))
3 1 1 3p
y
$
%
&
'
(
)
2
81 !a
0
3

$
%
&
'
(
)
$
%
&
'
(
)
6r
a
0
-
$
%
&
'
(
)
r
2
a
0
2 e
-r/3a0
(sin(")sin(#))
a
0
= Bohr radius = 5.29 x 10
-11
m = 52.9 pm = 0.529
(continued)
1
4
n l m
l
Orbital !(r,",#) = (Constant)(Radial)(Angular)
!(r,",#) = R
nl
(r)Y
lml
(",#)
[Spherical Polar Coordinates]
3 2 0 3d
z2
$
%
&
'
(
)
1
81 6!a
0
3

$
%
&
'
(
)
r
2
a
0
2 e
-r/3a0
(3cos
2
(") 1)
3 2 1 3d
xz
$
%
&
'
(
)
2
81 !a
0
3

$
%
&
'
(
)
r
2
a
0
2 e
-r/3a0
(sin(")cos(")cos(#))
3 2 1 3d
yz
$
%
&
'
(
)
2
81 !a
0
3

$
%
&
'
(
)
r
2
a
0
2 e
-r/3a0
(sin(")cos(")sin(#))
3 2 2 3d
xy
$
%
&
'
(
)
1
81 2!a
0
3

$
%
&
'
(
)
r
2
a
0
2 e
-r/3a0
(sin
2
(")sin(2#))
3 2 2 3d
x2-y2
$
%
&
'
(
)
1
81 2!a
0
3

$
%
&
'
(
)
r
2
a
0
2 e
-r/3a0
(sin
2
(")cos(2#))
a
0
= Bohr radius = 5.29 x 10
-11
m = 52.9 pm = 0.529
2
5
Form 7A. 2000 Mathematics Help Central. All Rights Reserved. http://www.mathematicshelpcentral.com

Name:
Description:
Section/Page Numbers: Problems: Date: Page
/

2

0, 2
11
6

7
4

5
3

3
2

4
3

5
4

7
6

5
6

3
4

2
3

4
6
4
+z
+y
+x
+
Spherically symmetric
Centered on origin
+ phase throughout
No ANGULAR nodal
planes.
s
BSD for s orbital (l = 0) :
7
5
BSDs for p orbitals (l = 1) p
z
& p
y
:
p
y
+z
+y
+
-
Oriented along y-axis
+ phase along +y
- phase along -y
xz nodal plane
through y = 0
+x
p
z
+y
Oriented along z-axis
+ phase along +z
- phase along -z
xy nodal plane
through z = 0
+
- +x
+z
8
6
BSDs for p orbitals (l = 1) p
x
:
(extends in/out of plane of page)
+x
+z
+y
+
-
Oriented along x-axis
+ phase along +x
- phase along -x
yz nodal plane
through x = 0
p
x
9
7
BSDs for d orbitals (l = 2) d
xy
, d
xz
, d
yz
:
+
+
-
-
d
xy
or d
xz
or d
yz
IF d
xy
:
Lies in xy plane
2 nodal planes
yz plane through x = 0
xz plane through y = 0
Phases (+/-) shown.
IF d
xz
:
Lies in xz plane
2 nodal planes
xy plane through z = 0
yz plane through x = 0
Phases (+/-) shown.
IF d
yz
:
Lies in yz plane
2 nodal planes
xy plane through z = 0
xz plane through y = 0
Phases (+/-) shown.
10
8
BSDs for d orbitals (l = 2) d
x2-y2
:
+
+
- -
d
x2-y2
y
x
Lies in xy plane - lobes lie along x & y axes.
2 nodal planes
yz & xz planes - "rotated 45".
Phases (+/-) shown.
11
9
BSDs for d orbitals (l = 2) d
z2
:
+
+
-
-
-
z
y
d
z2
Lobe along +z & -z.
"Doughnut" in xy plane.
2 nodal CONES radiating
up from z = 0 and down
from z = 0.
Phases (+/-) shown.
x
12
10
Radial Distribution Function (RDF)
Plot of 4!r
2
R
nl
2
(r) (RDF) versus r.
ALWAYS POSITVIVE (+) or ZERO (0).
# of RADIAL NODES = n - l - 1 .
[where RDF is 0 BETWEEN 0 & " ].
# of PEAKS (MAXIMA) = n - l.
PEAKS INCREASE in HEIGHT as r INCREASES.
Radial extent is greater as n increases.
SAME SUBSHELL (n,l) - SAME RDF.
SEE PICTURES on Radial Distribution Functions
which follows NEXT.
13
1s RDF (n = 1 & l = 0 (s)) Thus: 1s RDF = 4 % r
2
R
2
1 0
(r)
# of radial nodes = n & l & 1 = 1 & 0 & 1 = 0
# of maxima = n & l = 1 & 0 = 1
Plot of 4 % r
2
R
2
1 0
(r) versus r is shown (not to scale):
Page 2 of 11
14
2s RDF (n = 2 & l = 0 (s)) Thus: 2s RDF = 4 % r
2
R
2
2 0
(r)
# of radial nodes = n & l & 1 = 2 & 0 & 1 = 1
# of maxima = n & l = 2 & 0 = 2
Maxima increase in height with increasing r.
Plot of 4 % r
2
R
2
2 0
(r) versus r is shown (not to scale):
Page 3 of 11
15
2p RDF (n = 2 & l = 1 (p)) Thus: 2p RDF = 4 % r
2
R
2
2 1
(r)
# of radial nodes = n & l & 1 = 2 & 1 & 1 = 0
# of maxima = n & l = 2 & 1 = 1
Plot of 4 % r
2
R
2
2 1
(r) versus r is shown (not to scale):
Page 4 of 11
16
3s RDF (n = 3 & l = 0 (s)) Thus: 3s RDF = 4 % r
2
R
2
3 0
(r)
# of radial nodes = n & l & 1 = 3 & 0 & 1 = 2
# of maxima = n & l = 3 & 0 = 3
Maxima increase in height with increasing r.
Plot of 4 % r
2
R
2
3 0
(r) versus r is shown (not to scale):
Page 5 of 11
17
3p RDF (n = 3 & l = 1 (p)) Thus: 3p RDF = 4 % r
2
R
2
3 1
(r)
# of radial nodes = n & l & 1 = 3 & 1 & 1 = 1
# of maxima = n & l = 3 & 1 = 2
Maxima increase in height with increasing r.
Plot of 4 % r
2
R
2
3 1
(r) versus r is shown (not to scale):
Page 6 of 11
18
3d RDF (n = 3 & l = 2 (d)) Thus: 3d RDF = 4 % r
2
R
2
3 2
(r)
# of radial nodes = n & l & 1 = 3 & 2 & 1 = 0
# of maxima = n & l = 3 & 2 = 1
Plot of 4 % r
2
R
2
3 2
(r) versus r is shown (not to scale):
Page 7 of 11
19
4s RDF (n = 4 & l = 0 (s)) Thus: 4s RDF = 4 % r
2
R
2
4 0
(r)
# of radial nodes = n & l & 1 = 4 & 0 & 1 = 3
# of maxima = n & l = 4 & 0 = 4
Maxima increase in height with increasing r.
Plot of 4 % r
2
R
2
4 0
(r) versus r is shown (not to scale):
10
20 30 40
Page 8 of 11
20
Combo of subshells of n = 2: 2s & 2p RDF's on same set of axes (not to scale):
Combo of subshells of n = 3: 3s, 3p, & 3d RDF's on same set of axes (not to scale):
Page 9 of 9
21