Coordination Chemistry III: Electronic Spectra
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=Ilc (define variables) In a common absorption spectrum, the A is plotted versus wavelength or cm-1 (1/P).
are not independent of each other. we need to understand in more detail how these electrons interact with each other.Quantum Numbers of Multielectron Atoms
In order to understand energy transitions between states with more than one electron. each of the 2p electrons could have one of six possible combinations. The two electrons. Independently. however. 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.
± Works well for 1st and 2nd row transition metals.
± Commonly. 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.
.Interaction between Electrons
In any microstate. a number of microstates will contribute to a single term (degeneracies).
This is an approximation using the one-electron wave mechanical mode.
L is related to the vectorial addition of vectors taken from the l quantum number.Term Designation (Free-Ion)
± 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). Carter). Discuss the permitted ways in which the l values can combine (Figure 20.
«.Overall Orbital Angular Momentum Quantum Number. the magnitude of the resultant angular momentum is fixed.
± A partial lift of degeneracy by the magnetic field. ± Allowed orientations for a given term are associated with the overall magnetic quantum number.
ML = L. The vector for the momentum can have a number of allowed orientations. For a given term. L-1. ML. L
The vectorial addition produces the possible terms for a given configuration. [L(L+1)]1/2(h/2T).-L
± An ML value can be assigned to each microstate. L
ML relates to the orbital multiplicity or orbital degeneracy (Each has projection equal in magnitude to ML(h/2T)). a given L value must arise from a complete set of microstates with the 2L+1 values. ML = §ml.Overall Orbital Angular Momentum Quantum Number.
± What are the allowed orientations for a D term?
In the Russell-Saunders scheme.
S can be obtained by vectorial addition of the spin angular momentum vectors (related to s or ms). 1.
± MS = S.
± S=0. S
Spin state of the term. 2S+1 ± spin multiplicity of the state. The produces the spin degeneracy in a spin state. 2
Like L. MS.
.«-S (2S+1 values) ± Indicates the µallowed¶ orientations of the vector relative to an applied magnetic field.Overall Spin Quantum Number. S-1.
± Magnitude [S(S+1)]1/2(h/2T)
S is related to an overall spin quantum number.
but its projections on a particular axis in the allowed orientation are given by MS(h/2T).Overall Spin Quantum Number. MS=§ms
Magnitude of the spin angular momentum is [S(S+1)]1/2(h/2T).
± Russell-Saunders scheme.
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. Value of the term
± L = largest possible value of ML
Let¶s do the d2 configuration.
What are the allowed ML and MS values?
± It is sufficient to designate the microstates by x (only the number is important). What are the allowed ML and MS values? Determine the number of microstates for a doublet D.
Number of microstates in a given free-ion term is equal to (2L + 1)(2S +1).
± Row multiplied by column
Determine the number of microstates for a triplet P.
± The spin multiplicity is same as the number of columns of microstates.
± This process is shown for a p2 configuration in Table 11-4.
(2L+1)(2S+1) Do the p2 and d2 configurations. ± The # of rows to include in the rectangular array is equal to +L p -L (number of values).
.Reducing a Microstate Table/Configuration into Its Free-Ion Terms
Notice that each term is composed of a rectangular array of microstates.
the ground term is the one having the highest L value. If two or more terms share the same maximum spin multiplicity. What is the term with the lowest energy for the d2 configuration?
.Term of the Lowest Energy
The ground term (lowest energy) has the highest spin multiplicity.
J = L+S. L+S-1.
There is also spin-orbit coupling wherein the spin and orbital angular momenta couple with each other. L+S-2.`L-S| (no negative values) J is a subscript on the right side of the L quantum # ± Determine the spin-orbit coupling in the 1S and 3P free-ion terms. Designate these with J.
the state having the lowest J value has the lowest energy. the state having the highest J value has the lowest energy.
.Lowest Energy Term Including Spin-Orbit Coupling
For subshells (such as p2) that are less than half-filled. For subshells that are more than half-filled.
± Determine the lowest energy state for the p2 configuration.
.and low-spin d6 configurations in octahedral symmetry. High. ± Determine the maximum possible value of ML (§ms) for the configuration. ± Combine steps.Electronic Spectra of Coordination Compounds
Absorption spectra in most cases involve the d orbitals of the metal. Identifying lowest energy term (quickly)
± Sketch the energy levels showing the d electrons. ± Spin multiplicity of lowest-energy state equal highest possible number of unpaired electrons +1.
D ± fivefold degeneracy (ML = ?) F ± ???
.Reducing the Symmetry of the Free Ion by a Ligand Field
The orbital term symbols for the free atom/ion are identical to the symbols for the appropriate symmetry species in the spherical group.
± There are no inherent symmetry restrictions on possible orbital degeneracies. R3 (show Table).
All term symbols will be redefined by the new symmetry. the maximum degeneracy is 3 (Ttype IR¶s. the free-ion term can be treated as a reducible representation composed of irreducible representations in the appropriate character table. however.
± In an octahedral complex. look at table). Orbital degeneracies present in the free ion must be split. Upon reducing the symmetry. there are restrictions placed on the maximum orbital degeneracy.
.Reducing the Symmetry of the Free Ion by a Ligand Field
When a ligand field is imposed.
Reducing the Symmetry of the Free Ion by a Ligand Field
The total number of microstates. Examine
. remains the same. Do the d1 configuration.
± What does this split into when an octahedral field is imposed? ± How many microstates are possible when imposing the ligand field? The new ligand-field terms will retain the original spin multiplicities found in the free-ion terms. Dt.
the ligand field has very little influence.
± Far left (absence of ligand field) ± the free-ion terms.
Examine the previous table. the situation is somewhere in the middle.Correlation Diagrams ± Relating Electron Spectra to Ligand Field Splitting
Examine the correlation diagram for a d2 configuration in an octahedral ligand field.
Observed before in the crystal field and ligand field discussion. On this side.
± Far right (strong ligand field) ± the states are largely determined by the ligand field.
In real compounds.
± Each state has symmetric characteristics of that IR.
The IRs on the right and left sides must µcorrelate¶. ± IRs are also obtained from the strong-field limit configurations (right side of table).Splitting of Free-Ion Terms
Irreducible representations are produced.
± Examine the correlation diagram and the Oh table.
± Laporte Selection Rule
Transitions between states of different spin multiplicities are forbidden.
± 4A2 p 4T1 and 4A2 p 2A2 Discuss how the rules are relaxed on the expected absorption intensities.Selection Rules for Transitions
Transitions between states of the same parity are forbidden.
± Lowest energy state is plotted along the horizontal axis.
(o/B (field strength)
± Vertical axis is the measure of the energy above the ground state
E/B B = Racah parameter.
Special correlation diagrams useful in the interpretation of electronic spectra. a measure of the repulsion between terms of the same multiplicity.
± Lines connecting states of the same symmetry cannot cross.
The diagrams of d2-d8 are illustrated in Figure 11-7. the absorption bands are off-scale (x-axis) or obscured by the charge-transfer bands (discussed later).
. Discuss the terms for the configurations. They are not the same as observed for the orbital terms. What does the vertical line represent? What happens once the line is crossed? In some cases. There is a vertical line near the center of d4-d7 diagrams.
± The complex has a d1 configuration (Fig.
Jahn-Teller distortion is usually only significant for asymmetrically occupied eg orbitals. 11-8). ± Why are there two overlapping bands?
If degenerate orbitals are asymmetrically occupied a distortion will occur to remove the degeneracy. ± The most common distortion is along the z-axis (elongation).Jahn-Teller Distortions
Spectrum of the [Ti(H2O)6]3+ complex. ± Go over terms for the configurations.
± The others cannot be resolved.
Symmetry Labels for Configurations
Symmetry labels for electron configurations match their degeneracies.
Effect of a D4h field.
± T = triply degenerate asymmetrical state ± E = doubly degenerate asymmetrical state ± A or B = nondegenerate Do a few without Jahn Teller splitting/distortion.