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General Idea
The lines in the spectrum (in either emission or absorption):
•the atom undergoes a transition with a change of energy |ΔE |,
and
•emits or absorbs a photon of frequency
the energies of electrons
in atoms
the actual energy levels:
• not solely the energies of the orbitals
• the energy interaction of the electrons with one another
Doppler broadening
radiation is shifted in frequency when the source is moving
towards or away from the observer.
Doppler
shifts
nonrelativistic speeds
to obtain spectra
of maximum
sharpness, it is
best to work with
cool samples.
Doppler
broadening
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Lifetime broadening
The residual broadening is due to quantum mechanical effects. Specifically,
when the Schrödinger equation is solved for a system that is changing with
time.
If on average a system survives in a state for a time τ (tau), the lifetime of
the state, then its energy levels are blurred to an extent of order δE
Rydberg states
some excited states that are so diffuse that δ →0 and the 1/n2 variation is
valid
Triplet
The state of two parallel spins
The angular momenta of two parallel spins add together to give a nonzero total spin,
for states arising from the same configuration, the triplet state generally
lies lower than the singlet state.
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SPIN–ORBIT COUPLING
The interaction of the spin
magnetic moment with the
magnetic field arising from the
orbital angular momentum
The total orbital angular momentum quantum number, L >>> the magnitude of
the angular momentum through {L(L + 1)}½ħ.
It has 2L + 1 orientations distinguished by the quantum number ML, which can
take the values L, L − 1, . . . , − L.
Term symbols only consider the electrons of the unfilled shell. In the case of a single
electron outside a closed shell, the value of L is the same as the value of l; so the
configuration [Ne]3s1 has only an S term.
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The multiplicity
Total spin angular momentum quantum number, S, for several electrons
two electrons: S = 1, 0
three electrons: S = 3/2 and S = ½
the total spin angular momentum is obtained by coupling the third spin to each of
the values of S for the first two spins
a doublet term,
A single electron, S= s = ½,
2S >>> [Ne]3s1
2P >>>[Ne]3p1
a triplet term
two unpaired electrons S = 1, so 2S + 1 = 3
3D
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The total angular momentum
the quantum number j : the relative orientation of the spin and orbital angular momenta
of a single electron.
The total angular momentum quantum number, J : does the same for several electrons (a
non-negative integer or half integer)
L≥S
the multiplicity is equal to the number of levels.
2P term has the two levels 2P
3/2 and P1/2, and
2
3D has the three levels 3D , 3D , and 3D .
3 2 1
L<S
the term 2S, for example, has only the one level 2S½
Selection rules
for atoms