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Electronic Spectra
Chapter 11
Coordination Complexes
• Unlike most organic compounds, many
coordination compounds have vivid colors.
– These vivid colors are due to the electronic
transitions between the d-orbitals of the metal.
• The energy levels of d electron
configurations, however, are usually more
complicated than might be expected since
the electrons in the atomic orbitals interact
with each other.
Absorption of Light
• Complementary colors – if a compound
absorbed light of one color, the complement of
that color is observed.
– [Cu(H2O)6]2+ has a blue color. What is absorbed?
• Beer-Lambert Absorption Law
• log(Io/I)=A=lc (define variables)
• In a common absorption spectrum, the A is plotted versus
wavelength or cm-1 (1/).
Quantum Numbers of
Multielectron Atoms
• In order to understand energy transitions between states
with more than one electron, we need to understand in
more detail how these electrons interact with each other.
• Each conceivable set of individual ml and ms values
constitutes a microstate of the configuration.
– How many microstates in a d1 configuration?
– Examine the carbon atom (p2 configuration)
• Determine the electron configuration and quantum numbers.
• Independently, each of the 2p electrons could have one of six possible
combinations. The two electrons, however, are not independent of each
other.
Interaction between Electrons
• In any microstate, the individual orbital magnetic
moments (related to ml) and the spin magnetic moments
(related to ms) will interact resulting in an energy state or
term for the configuration.
– Commonly, a number of microstates will contribute to a single
term (degeneracies).
• This is an approximation using the one-electron wave
mechanical mode.
– Works well for 1st and 2nd row transition metals.
Term Designation (Free-Ion)
• 2S+1 L
– L and S relate to the overall orbital and spin angular
momenta for the system (or state).
– L = overall orbital angular momentum quantum
number.
• Discuss possible values (analogous to the l quantum
number).
• L is related to the vectorial addition of vectors taken from
the l quantum number.
• Discuss the permitted ways in which the l values can
combine (Figure 20, Carter).
Overall Orbital Angular
Momentum Quantum Number, L
• The vectorial addition produces the possible terms for a
given configuration.
• For a given term, the magnitude of the resultant
angular momentum is fixed, [L(L+1)]1/2(h/2).
• The vector for the momentum can have a number of
allowed orientations.
– A partial lift of degeneracy by the magnetic field.
– Allowed orientations for a given term are associated with the
overall magnetic quantum number, ML.
• ML = L, L-1,….-L
Overall Orbital Angular
Momentum Quantum Number, L
• ML relates to the orbital multiplicity or orbital
degeneracy (Each has projection equal in magnitude
to ML(h/2)).
– What are the allowed orientations for a D term?
• In the Russell-Saunders scheme, ML = ml.
– An ML value can be assigned to each microstate.
• Therefore, a given L value must arise from a complete
set of microstates with the 2L+1 values.
– Examples
Overall Spin Quantum Number, S
• Spin state of the term.
• 2S+1 – spin multiplicity of the state.
– S=0, 1, 2
• Like L, S can be obtained by vectorial addition of the spin
angular momentum vectors (related to s or ms).
– Magnitude [S(S+1)]1/2(h/2)
• S is related to an overall spin quantum number, MS.
– MS = S, S-1,…-S (2S+1 values)
– Indicates the ‘allowed’ orientations of the vector relative to an applied
magnetic field. The produces the spin degeneracy in a spin state.
Overall Spin Quantum Number, S
• Magnitude of the spin angular momentum is
[S(S+1)]1/2(h/2), but its projections on a
particular axis in the allowed orientation are
given by MS(h/2).
– Russell-Saunders scheme, MS=ms
In Summary
• Any given term with L and S values arises from
a set of microstates that has the necessary 2L+1
values of ML and also the necessary 2S+1
values of MS.