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• define quantum numbers

• see the origin and significance of quantum numbers

• determine the separation of the energy levels in hydrogen

• looking at shell and sub-shells in hydrogen

• looking at the emission spectra of hydrogen

an orbital angular momentum (or azimuthal) quantum number l, and by a

magnetic quantum number ml. All of these three quantum numbers come out

of the solution of the SWE for the individual hydrogen atomic orbitals, and

together they give the ‘address’ of the electron in the atom (i.e. the orbital in

which the electron is located).

The principal quantum number, n is used to calculate the energy of the electron

in the atom, and is equal to “the total number of nodes in an orbital plus one”

and has values:

n = 1, 2, 3, …

angular nodes present in an orbital and has n possible values:

l = 0, 1, 2, 3, … (n –1)

i.e. for a specific value of n, l can have values from a minimum of zero

up to a maximum of (n – 1).

For a given value of l, there are 2l +1 values of the magnetic quantum number

ml in the range:

Shells

In the hydrogen atom, the energy of an orbital depends only on the value of n.

This means that all orbitals with the same value of n, regardless of the values of

l and ml, are degenerate (have the same energy). This is the reason that all

orbitals in hydrogen with the same value of n are said to belong to the same

shell. The values of n and the corresponding shell designations are:

1

n = 1 2 3 4…

K L M N…

Sub-Shells

Orbitals with the same value of n, but different values of l belong to different

sub-shells which are denoted as follows:

l = 0 1 2 3

s p d f

values of ml (all with the same value of l).

shell K L M

n 1 2 3

l 0 0 1 0 1 2

ml 0 0 1, 0, -1 0 1, 0, -1 2, 1, 0, -1, -2

type s s p s p d

sub-orbitals 1 1 3 1 3 5

# of orbitals/shell 1 4 9

It can be seen from the above table that for n = 1, there is only one value of l

(i.e. l = 0), and hence one value of ml and therefore only one orbital. Similarly

for n = 2, there are 4 orbitals and for n = 3 there are 9. In fact, the number of

orbitals for a shell of quantum number n is equal to n2. There is always one s-

orbital in a shell and (whenever they are present), three p-orbitals and five d-

orbitals.

Apart from splitting the nth level into individual sub-levels, ml describes how

each orbital is oriented relative to any arbitrary or preferred direction in space

(such as that of a magnetic field). The magnetic quantum number, ml, is used to

2

explain additional lines that appear in the emission line spectra when the atom is

subjected to an external magnetic field.

There is, in fact, a fourth quantum number which gives the absolute

configuration that the electron is allowed to have in an orbital. The spin

quantum number ms, is allowed the values of +½ and –½, signifying two

possible spin configurations, α and β. At this time, these can be viewed simply

as an up or down spin or a clockwise or anticlockwise spin. As you will see later

on in the chapter, for two electrons to occupy the same orbital they must have

opposite spins.

Therefore 2s and 2p correspond to states of the same energy, as shown in the

following diagram:

E

1S

For hydrogen, when the electron is in the 2s orbital the state is 2S, when the

electron is in the 2px orbital the state is 2Px, and so on.

atoms are able to absorb energy. In absorbing this energy, electrons are

promoted to higher levels. When the electrons fall back to states with lower

energy giving out energy in the form of radiation (photons), an emission

spectrum is observed. This spectrum is seen to consist of discrete sharp lines

which mean that the electrons are moving between specific energy levels and in

3

doing so are able to absorb or give out a discrete amount of energy. The energy

levels in hydrogen are given quantitatively by:

hcRH

En = − ,

n2

is the Rydberg constant for hydrogen.

In this definition, the ionized atom (H+ + e–) is taken as the zero of energy and

the energy levels lie at some negative value (more stable value) below this zero.

Therefore, the first three energy levels in hydrogen would be:

E1 = − 2

= − hcRH , E 2 = − 2 H = − , and E 3 = − 2 H = − ,

1 2 4 3 9

indicating how far below the zero each lies. As the value of n increases the

separation between successive energy levels decreases:

0 n=∞

– hcR/9 n=3

– hcR/4 n=2

– hcR n=1

When the H-atom absorbs or emits energy, the electron has to move between

these specific energy levels and therefore, absorbs or emits a specific amount of

electromagnetic energy. As a consequence, a line spectrum is observed. The

observed spectral emissions (lines) can be explained as follows:

4

Transition from n = 3 to n = 2 (in emission). The difference in energy, ∆E, is

∆E = E3 − E2 = −

hcRH hcRH 1 1 1 1

− − = hcRH − = hcRH 2 − 2

9 4 4 9 2 3

the electron falls from a higher level down to n = 2. The expression

corresponding to these lines is

∆E = hcRH

1 1

2

− 2 , where n = 3, 4, 5, 6.

2 n

This visible series of emission lines is known as the Balmer Series. Two other

series: Lyman (ultra-violet) and Paschen (infra-red) occur when emissions

terminate in the n = 1 and the n = 3 levels respectively.

6

5

4

3

Paschen (IR)

2

Balmer

(visible)

1

Lyman (UV)

n

5

It can be seen from the above figure that if the series are placed in order of

increasing energy the result is: Paschen (IR) < Balmer (vis) < Lyman (UV).

Exercise 6. Calculate the energy (in Joules) of the photon emitted when an electron

falls from the n = 4 level to the n = 2 level in the hydrogen atom. Convert the energy

of the photon from Joules to wavenumbers (cm-1).

Solution

1 1

Energy = hcRH 2 − 2

2 4

= (6.626 x 10 J s)(2.998 x 1010 cm s −1 )(109678 cm −1 )( 1 4 − 116)

− 34

= 4.085 x 10 −19 J

1 1

ν = RH 2 − 2 , where n and m are the quantum numbers of the levels.

n m

= (109678 cm −1 )( 1 4 − 116) = 20565 cm −1

The wavenumber of a radiation is the number of wavelengths that can fit in a length of

1 cm. In this example, 20565 wavelengths joined end-to-end would measure 1 cm.

atom, we can now turn to the next higher atom, Helium. This should be more

demanding since we now have to account for the repulsion experienced between

the two electrons and the separate attractions between both electrons and the

positive nucleus. In this section we will try to apply, what we have just learnt

about hydrogen, to see if it can be used to explain the behaviour of the electrons

in the Helium atom

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