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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=εlc (define variables)
• In a common absorption spectrum, the A is plotted versus
wavelength or cm-1 (1/λ).
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)
• L
2S+1