RADIAL AND ANGULAR FUNCTIONS

The Schrodinger equation can be solved completely for the hydrogen atom, and for related ions which have
only one electron such as He+ and Li2+ . For other atoms only approximate solutions can be obtained. For most
calculations, it is simpler to solve the wave equation if the Cartesian coordinates x, y and z are converted into
polar coordinates r,
The coordinates of the point A measured from the origin are x, y, and z in Cartesian coordinates, and r,
coordinates. It can be seen that the two sets of coordinates are related by the following expressions:
z = r cos
y = r sin sin
x = r sin cos
The Schrodinger equation is usually written

=0

𝝏 𝟐𝝍 𝝏 𝟐𝝍 𝝏𝟐𝝍
𝜵 𝟐𝝍= + +
𝝏𝒙𝟐 𝝏𝒚 𝟐 𝝏 𝒛𝟐
Changing to polar coordinates , becomes

r2

R (r ) is a function that depends on the distance from the nucleus , which in turn depends on the quantum
numbers n and l .
of , which depends on the quantum numbers l and m.

( is a function of , which depends only on the quantum number m .

This splits the wave function into two parts which can be solved separately:
1. R (r) the radial function , which depends on the quantum numbers n and l .
2. Aml the total angular wave function , which depends on the quantum numbers ml and l .
 The radial function R has no physical meaning , but R2 gives the probability of finding the electron in a small
volume dv near the point at which R is measured. For a given value of r the number of small volumes is 4 r2, so
the probability of the electron being at a distance r from the nucleus is 4 r2R2. This is called the radial distribution
function.

Fig:1.12 Radial distribution functions for various orbitals in the hydrogen atom .

Graphs of the radial distribution function for hydrogen plotted against r

Furthermore, by comparing the plots for 2s and 2p, or 3s, 3p and 3d it can be seen that the most probable radius
decreases slightly as the subsidiary quantum number increases.

All the s orbitals except the first one (1s) have a shell-like structure, rather like an onion or a hailstone,
consisting of concentric layers of electron density. Similarly, all but the first p orbitals (2p) and the first d orbitals
(3d) have a shell structure.

The angular variation function A, depends only on the direction , and is independent of the distance
from the nucleus (r) . Thus A2 is the probability of finding an electron at a given direction at any distance
from the nucleus to infinity.

The angular functions A are plotted as polar diagrams. It must be emphasized that these polar diagrams do
not represent the total wave function v, but only the angular part of the wave function. ( The total wave function
is made up from contributions from both the radial and the angular functions.)
The probability of finding an electron simultaneously at a distance r and in a given direction is

Polar diagrams , i.e., drawings of the angular part of the wave function, are commonly used to illustrate the
overlap of orbitals giving bonding between atoms.
The signs (+) and (-) relating to the symmetry of the angular function.
For bonding like signs must overlap. These shapes are slightly different from the shapes of the total wave
function . There are several points about such diagrams:
 z y z
z

x - -
- + + + y
+ - x x
+ + - + -
y
3dxz
z
2s 3dxy 3dyz
z

y
+
x
z
- + x -
+
-- - x +
y -
+ x
y

z 2py
2px y
3dx2-y2 3dz2

+
x
- Fig: (1.13 )
Boundary surface for the angular part of the wave function A(

2pz
 z z
y

x x

2px 2py

y Fig:1.14 The angular part of the wave function squared

2pz

The angular part of the wave function squared A2 ( ) for the 2p orbitals for a hydrogen atom.
Fig: (1.15) Total wave function (orbitals) for hydrogen
1. It is difficult to picture an angular wave function as a mathematical equation. It is much easier to visualize a
boundary surface, i.e., a solid shape , which for example contains 90% of the electron density. To emphasize that
is a continuous function, the boundary surfaces have been extended up to the nucleus in Fig (1.13 ).
For p orbitals the electron density is zero at the nucleus , and some texts show a p orbital as two spheres which do
not touch.
2. These drawings show the symmetry for the 1s, 2p, 3d orbitals. However, in the others, 2s, 3s, 4s, …….., 3p, 4p,
5p, …….., 4d, 5d, …. the sign (symmetry) changes inside the boundary surface of the orbital. This is readily seen as
nodes in the graphs of the radial functions (Fig: 1.12).
3. The probability of finding an electron at a direction is the wave function squared,, or more precisely
. The diagrams in Fig (1.13) are of the angular part of the wave function A, not A2. Squaring does not change the
shape of a s orbital., but it elongates the lobes of p orbitals (Fig:1.14) .
4. A full representation of the probability of finding an electron requires the total wave function squared and
includes both the radial and angular probabilities squared. It really needs a three-dimensional model to display this
probability, and show the shapes of the orbitals. It is difficult to do this adequately on a two-dimensional piece of
paper, but a representation is shown in Fig: (1.15 ).