CHEM101: Atoms and Molecules

Lecture 3
Further reading: Chemistry3, section 3.5

(1) Radial and Angular Parts of the Schrodinger Equation

It is more convenient to express the Schrodinger equation using spherical coordinates rather than in terms
of x, y and z. When we do this we see that quantum numbers n and l are related to the radial part of the
wavefunction and l and ml relate to the angular part.

Ψ ( r ,θ , φ)=R n ,l (r )• Y l ,m (θ ,φ)
l

(2) The Radial Wavefunction

We can plot the radial wavefunction, R(r), with changing r (distance from nucleus). The values of R(r) are
not something you need to know how to calculate. They arise from the Schrodinger equation.

Radial Wavefunction for n = 1

1s orbital (l and ml must both be 0). What happens to 𝛹 with changing r? 𝛹 is at a maximum when r = 0 and
reaches 0 when r = ∞.

Radial Wavefunctions for n = 2

Radial Wavefunctions for n = 3

When n > 1, 𝛹 can be both positive and negative. The points where R(r) = 0 are called radial nodes. For a
given l value, as n increases, the number of radial nodes increases. For a given n value, as l increases, the
number of radial nodes decreases. The number of radial nodes for r > 0 = n – l – 1.

Notice that R(r) is negative for certain values of r. This is the phase of the wavefunction (it is not to do with
charge or an electron’s position. As we will see later in course this is very important in BONDING when
electrons occupy orbitals in molecules not atoms – the orbitals which overlap must have the same phases
or they cancel out (like sine waves).

(3) The Radial Distribution

Ψ is physically meaningless but Ψ2 is probability of finding an electron at a point (the Born Interpretation).
So we can say that R(r)2 is the radial distribution – this is the probability of finding an electron at a given
point. However, we know that we cannot know the exact position of an electron due to its wave behaviour,
so we need to think in terms of electron density. A radial distribution therefore tells us the probability of
finding electron density at a given point at r distance from the nucleus for an orbital.

The effect of squaring R(r) is that the plots have no negative regions. Any point that was 0 for R(r) is still 0.

These plots do not take into account the 3 dimensional nature of orbitals; the most useful is a radial
distribution function (RDF).

(4) Radial Distribution Functions

To consider the distribution of electrons in an orbital, we need to consider the Radial Distribution Function
(RDF). This is better than considering Ψ 2, since the RDF considers the number of points available at a given
radius r.
  At r = 0: high probability, but only 1 point that the electron can occupy
 At r = small: few points each with high probability
 At r = large: many points with lower probability

Overall probability of x = probability of x × number of ways of getting x. For example, consider a die, where
there is equal probability of getting any number. Now consider a die with sides 1,1,1,2,3,4. The probability
of getting a 1 is now 0.5, i.e. 1/6 (prob of any side of die being up) × 3 (there are 3 ‘1’s).

So, probability of finding electron density at distance r from the nucleus =

Ψ 2 (probability of finding electron at 1 point) × 4πr2 (surface of sphere)

 The area of maximum probability (density) increases with increasing n but is independent of l. n
determines the orbital size
 There is a small (but > 0) probability of finding the electron a very long way from the nucleus – hard
to define the orbital size. So we use a boundary surface. A surface that captures 90% of
probability.
 There are distances from the nucleus (i.e. r>0) with zero probability, called nodes. In this case,
radial nodes (we are looking at radial wavefunction). Number of radial nodes = n – l – 1

Maximum shows the most probable distance from the nucleus that electron density will be found.

(5) Angular Wavefunction

Once we fix the boundary surface we can consider how the electron probability changes as we go around
the orbital in 3D, i.e. the shape of the orbital which is determined by l and ml and described by the angular
wavefunction, Y. Remember that there is still some probability of finding an electron at ∞, lines show 90%
probability limit. This is called a boundary surface.

Boundary surfaces show the phase of the wavefunction at the surface (+ or -). s orbitals have the same
phase over the whole boundary surface, whilst p and d orbitals contain both positive and negative phases,
usually indicated by shading the appropriate lobes.

The s Orbital
l = 0, s orbital. The s orbital is spherical in shape as it is independent of both θ and φ.
The p Orbitals
l = 1, p orbital, for l = 1 there are 3 value of ml: -1, 0, 1, meaning there are 3 p orbitals

The p orbitals are shaped like a dumbbell, with lobes pointing along the 3 axes. They are denoted np x, npy,
npz according to which axis they are aligned with.

 SHAPE is determined by l (s p d etc)

 ORIENTATION is determined by ml (px py pz)
 PHASE indicates the sign of Ψ (usually indicated by shading). This is important for bonding.

The d Orbitals
l = 2, d orbital, for l = 2 there are 5 value of ml: -2, -1, 0, 1, 2, meaning there are 5 d orbitals. There are 3
orbitals with 4 lobes (xy, xz, yz), the lobes point between the axes in a 2D plane. We define that the orbital
in the xy plane (drawn) is the dxy etc.

There is one orbital that looks the same as dxy etc but with lobes pointing along the x and y axes. This is
called the dx2-y2

There is one orbital looks different, like a p-orbital with a doughnut around it, its lobe points along z-axis.
This is the dz2 orbital, (the favourite orbital of every self-respecting chemist!)
Angular nodes are present in p, d and f orbitals: Number of angular nodes = l

For s orbitals, l = 0, so no angular nodes; for p orbitals, l = 1, 1 angular node etc.