Radial wave function and angular wave functions

It is simpler to solve the wave equation if the Cartesian coordinates x, y and z are converted into
polar coordinates r, θ and Ø. The coordinates of the point A measured from the origin are x, y, a.rid
z in cartesian coordinates, and r, θ and Ø in polar coordinates. It can be seen that the two sets of
coordinates are related by the following expressions:
z = r cos θ
y = r sin θ sin Ø
x = r sin θ cos Ø

Fig 1 relationship between Cartesian and polar coordinates

The Schrodinger equation is usually written:
8𝜋 2 𝑚
∇2 𝜓 + 2
(𝐸 − 𝑉)𝜓 = 0
ℎ
𝑑2 𝜓 𝑑2 𝜓 𝑑2 𝜓
Where, ∇2 𝜓 = 𝑑𝑥 2 + 𝑑𝑦 2 + 𝑑𝑧 2

Changing to polar coordinates,

𝑑 𝑑𝜓 1 𝑑2 𝜓 1 𝑑 𝑑𝜓
(𝑟 2 𝑑𝑟 ) + sin2 𝜃 𝑑Ø2 + (sin 𝜃 𝑑𝜃 ) = 0
𝑑𝑟 𝑠𝑖𝑛 𝜃 𝑑𝜃

The solution of this is of the form

Ψ = R(r) Θ(θ) Ø(Ø)
R(r) is a function that depends on the distance from the nucleus, which in turn depends on the
quantum numbers n and I
Θ(θ) is a function of θ; which depends on the quantum numbers I and m
Ø(Ø) is a function of Ø, which depends only on the quantum number m

Above equation may be rewritten as

Ψ = R(r)nl . Aml
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/.
2. Aml the total angular wave function, which depends on the quantum numbers m and I.

Radial Wave Function

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 4πr2, so the probability of the electron being at a distance r from ·the nucleus is
4πr2R2. This is called the radial distribution function.

Fig 2 Radial distribution functions for various orbitals in hydrogen atom

• These diagrams show that probability is zero at the nucleus and the most probable distance
increases markedly as the principal quantum number increases.

• 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 (ls) have a shell-like structure, rather like an onion or a
hailstone, consisting of concentric layers of electron density.

• Similarly, all except the first p orbitals (2p) and the first d orbitals (3d) have a shell
structure.
Angular wave function
The angular 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 θ, Ø at any
distance from the nucleus to infinity.
These diagrams do not represent the total wave function u, 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.
Ψ = R(r) A (θ, Ø)
Thus, the overall probability of finding an electron is given as
Ψ2 = R2(r) A2 (θ, Ø)
Polar diagrams are used for the combination of both the types (radial and angular) wave functions

The value of angular wave function can be + or – and since it is difficult to have pictorial
representations of angular wave function, thus the boundry surface diagrams are made to visualize
the solid shape of the orbital containing 90% of electron density.

Also inside a particular orbital, the sign of wave function may get change which can be represented
by the presence of a node.
PAULl EXCLUSION PRINCIPLE

Three quantum numbers n, I and m are needed to define an orbital. Each orbital may hold up to
two electrons, provided they have opposite spins. An extra ·quantum number is required to
define the spin of an electron in an orbital. Thus four quantum numbers are needed to define the
energy of an electron in an atom. The Pauli exclusion principle states that no two electrons in
one atom can have all four quantum numbers the same. By permutating the quantum numbers,
the maximum number of electrons which can be contained in each main energy level can be
calculated.

BUILD-UP OF THE ELEMENTS, HUND'S RULE

When atoms are in their ground state, the electrons occupy the lowest possible energy levels. The
simplest element, hydrogen, has one electron, which occupies the 1s level; this level has the
principal quantum number n = 1, and the subsidiary quantum number I = 0. Helium has two
electrons. The second electron also occupies the 1s level. This is possible because the two
electrons have opposite spins. This level is now full. The next atom lithium has three electrons.
The third electron occupies the next lowest level. This is the 2s level, which has the principal
quantum number n = 2 and subsidiary quantum number I = 0.

The fourth electron in beryllium also occupies the 2s level. Boron must have its fifth electron in
the 2p level as the 2s level is full. The sixth electron in carbon is also in the 2p level. Hund's rule
states that the number of unpaired electrons in a given energy level is a maximum. Thus in the
ground state the two p electrons in carbon are unpaired. They occupy separate p orbitals and
have parallel spins. Similarly in nitrogen the three p electrons are unpaired and have parallel
spins. To show the positions of the
electrons in an atom, the symbols Is, 2s, 2p, etc. are used to denote the main energy level and
sub-level. A superscript indicates the number of electrons in each set of orbitals. Thus for
hydrogen, the 1s orbital contains one electron, and this is shown as 1s1. For helium the 1s orbital
contains two electrons, denoted 1s2. The electronic structures of the first few 'atoms in the
periodic table may be written:

An alternative way of showing the electronic structure of an atom is to draw boxes for orbitals,
and arrows for the electrons.
Atoms Are Built Up by Adding Electrons

Although the nucleus of an atom is very dense, the electrons around it can take on a variety of
positions which can be summarized as an electron configuration. An element’s electron
configuration can be represented using energy level diagrams, or Aufbau diagrams. The Aufbau
principle (from the German Aufbau meaning “building up, construction”) describes a model-
building method in which an atom is “built up” by progressively adding electrons. As electrons
are added, they assume the most stable shells with respect to the nucleus and the electrons
already present.

Filling in an Aufbau Diagram

The order in which orbitals are filled is given by the Madelung rule. The rule is based on the total
number of nodes in the atomic orbital, n + ℓ, which is related to the energy. In this context, n
represents the principal quantum number and ℓ represents the azimuthal quantum number. The values
ℓ = 0, 1, 2, 3 correspond to the s, p, d, and f labels, respectively. According to the principle,
electrons fill orbitals starting at the lowest available energy states before filling higher states
(e.g., 1s before 2s).

SEQUENCE OF ENERGY LEVELS

It is important to know the sequence in which the energy levels are filled. From this it can be
seen that the order of filling of energy levels is: 1s, 2s, 2p, 3s, 3p, 4s, 3d, 4p, 5s, 4d, 5p, 6s, 4f,
5d, 6p, 7s, etc. After the 1s, 2s, 2p, 3s and 3p levels have been filled at argon, the next two
electrons go into the 4s level. This gives the elements potassium and calcium. Once the 4s level
is full the 3d level is the next lowest in
 energy, not the 3p level. Thus the 3d starts to fill at scandium. The elements from scandium
to copper have two electrons in the 4s level and an incomplete 3d level, and all behave in a
similar manner chemically. Such a series of atoms is known as a transition series.

A second transition series starts after the 5s orbital has been tilled, at strontium, because in
the next element, yttrium, the 4d level begins to fill up. A third transition series starts at-
lanthanum where the electrons start to fill the 5d level after the 6d level has been filled with
two electrons. A further complication arises here because after lanthanum, which has one
electron in the 5d level, the 4f level begins to fill, giving the elements from cerium to
lutetium with from one to 14f electrons. These are sometimes called the inner transition
elements, but are usually known as the lanthanides or rare earth metals.

For example, let us calculate the n+l values for 2s, 3p, 4s, 3d orbitals
2s 2 + 0 =2
3p 3 + 1 = 4
4s 4 + 0 = 4
3d 3 + 2 = 5

Based on the n+l values of the above mentioned orbitals, 2s has lowest energy and 3d has
highest among themselves. But since 3p and 4s have same n+l values, therefore, the orbitals
having lower n value will be filled first and the orbital with higher n value shall be filled
later. So, 3p will be filled before 4s.