PH2240 - Peter Stokes

Assignment 2
1. The two optically active or valence electrons in an atom have quantum numbers and a) What is their configuration? (i) The configuration of ( ) is: .

(ii) The configuration of ( * + ) is:

b) Using LS coupling, determine all possible fine structure levels. Order the levels according to energy, and label each one using spectroscopic notation. Below is the calculation of the possible valuees of the orbital angular momentum , the spin angular momentum and the total angular momentum : | | For | | | | | | | | | || | | | | ):

(singlet state due to multiplicity of | | | | || |

This state corresponds to the following term symbol:

For |

(triplet states due to multiplicity of | | | | | | |

):

This state corresponds to the following term symbols:

Spin-orbit coupling results in the following dipole potential energy:

PH2240 - Peter Stokes

(( where

))

is the spin-orbit constant. ( ( ) )

() ( ) ( ) ( )

The new energies depend on the various combinations of

( ) ( )

and which give particular values of :

where

is the unperturbed energy.

Therefore, in order of increasing energy: ( ( ( ) ) )

( ) ( ) ( )

( ) ( ) ( )

( ) ( ) ( )

c) Using the Land interval rule predict the ratio of the energy splitting in each fine structure multiplet. The Land interval rule is as follows: ( ) is the spin-orbit constant. and terms:

between successive states, where

Applying the Land interval rule to the ( ( ) ) ( ( ) )

The ratio of the energy splitting in each fine structure line of the triplet is:

Applying the Land interval rule cannot be performed on the other multiplet state.

as it is a singlet

PH2240 - Peter Stokes d) If this is an excited configuration of calcium, use the electric dipole selection rules to determine which transitions, if any, are allowed to the ground state. The electric dipole selection rules are as follows:

The excited states are:

The ground state of calcium is:

By applying the selection rules, it can be seen that no transitions are allowed:

2. a) Calculate, using only the spectroscopic information given above, the values of L, S and J for each of these fine-structure levels. Three fine structure levels with energies:

Where is the energy of the ground state of the carbon atom. These energies are expressed in units of , and can be expressed as units of energy by multiplying by the conversion factor . As these are energies of photons whose energy can be determined as:

PH2240 - Peter Stokes where photon. The Land interval rule is as follows: ( ) is the spin-orbit constant. is the energy of the photon, is Plancks constant equal to approximately , is the speed of light equal to and is the wavelength of the

between successive states, where

In this case, due to the units the energy is expressed in, the Land interval rule takes the following form: ( ) will not actually come into the solution when

It will be seen soon, that the constant determining the values of and . According to the Land interval rule: ( and ( ) )

where is the total angular momentum of which

specifically is a function of.

Solving the above set of simultaneous equations gives the following value for : ( ) ( ( | | | | | , which means that, taking into account the first ) | | ( | ) ( ) ( ) )

The latter equation is only possible for equation, the values of and are:

PH2240 - Peter Stokes b) The ground state term of carbon is ( ) is split into three fine structure levels,

i)

with . The levels with and are and respectively above the level. Which dipole transitions are allowed between the excited term considered in (a) and this ground state term? and .

The excited states considered in a) are The electric dipole selection rules are as follows:

By following these rules, we can see that transitions rely on satisfying transitions are allowed:

and

, this means that the allowed . Hence, the following

Transitions which are not allowed are:

ii)

What are the wavelengths of these transitions?

The Land interval rule is as follows: ( ) is the spin-orbit constant.

between successive states, where

From part a) the 3 energies of the excited state were written as:

PH2240 - Peter Stokes

where

is the energy of the ground state.

Doing the same for the energies at the ground state, we have: ( ) ( ) ( ) ( ) ( ) ( ) is the energy difference

where is the energy of the ground sate of the carbon atom, and between the ground state and the level. ( ) (( ) ( ) ( ))

( ) is the energy difference between the ground state and the level in units of where , is the spin orbit constant, is Plancks constant equal to approximately , is the speed of light equal to , is the orbital angular momentum, is the spin anuglar momentum and is the total angular momentum.

() ( ) As we know: ( )

( (

( )

Out of the allowed transitions, their wavelengths of the subsequently emitted photons are:

( )

PH2240 - Peter Stokes

( )

( ))

( )

( )

( )

( )

( )

PH2240 - Peter Stokes

( )

( )

( )

( )