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    L16 PDF

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    Umar Jutt
    1. Selection rules dictate which electronic transitions are allowed in coordination complexes. The Laporte selection rule forbids transitions between states of the same parity, while the spin selection rule forbids transitions between states of different spin multiplicities. 2. Vibronic coupling and spin-orbit coupling can relax the selection rules by temporarily changing the symmetry or mixing spin states. 3. Tanabe-Sugano diagrams correlate the electronic states of octahedral complexes and are used to determine spectroscopic splitting parameter Δo and Racah parameter B from absorption spectra.

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    L16 PDF

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    Umar Jutt
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    1. Selection rules dictate which electronic transitions are allowed in coordination complexes. The Laporte selection rule forbids transitions between states of the same parity, while the spin selection rule forbids transitions between states of different spin multiplicities. 2. Vibronic coupling and spin-orbit coupling can relax the selection rules by temporarily changing the symmetry or mixing spin states. 3. Tanabe-Sugano diagrams correlate the electronic states of octahedral complexes and are used to determine spectroscopic splitting parameter Δo and Racah parameter B from absorption spectra.

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    1. Selection rules dictate which electronic transitions are allowed in coordination complexes. The Laporte selection rule forbids transitions between states of the same parity, while the spin selection rule forbids transitions between states of different spin multiplicities. 2. Vibronic coupling and spin-orbit coupling can relax the selection rules by temporarily changing the symmetry or mixing spin states. 3. Tanabe-Sugano diagrams correlate the electronic states of octahedral complexes and are used to determine spectroscopic splitting parameter Δo and Racah parameter B from absorption spectra.

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    259 views14 pages

    L16 PDF

    Uploaded by

    Umar Jutt
    1. Selection rules dictate which electronic transitions are allowed in coordination complexes. The Laporte selection rule forbids transitions between states of the same parity, while the spin selection rule forbids transitions between states of different spin multiplicities. 2. Vibronic coupling and spin-orbit coupling can relax the selection rules by temporarily changing the symmetry or mixing spin states. 3. Tanabe-Sugano diagrams correlate the electronic states of octahedral complexes and are used to determine spectroscopic splitting parameter Δo and Racah parameter B from absorption spectra.

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    Selection rules

    1. Laporte selection rule


    Transition between states of the same parity are
    forbidden. e.g., g  u allowed; g  g forbidden
    Relaxation mechanism:
    a. Vibronic coupling – vibration may temporarily change
    the symmetry to relax the first selection rule.
    d-d transitions, having molar absorptivity in the range
    of 5-50 L mol–1 cm–1, occurs exhibiting the colors.
    b. mixing of p-orbital character with d-orbital character

    1
    Selection rules
    2. Spin selection rule
    Transition between states of different spin multiplicities
    are forbidden. e.g., 4A2  4T1 spin-allowed; 4A2  2A2
    spin-forbidden
    Relaxation: spin-orbit coupling may relax the second
    selection rule as allowing transitions between different
    spin multiplicity. For the 1st row transition metals, very
    weak (<1 L mol–1 cm–1), more important for 2nd , 3rd
    transition metals.

    2
    Correlation diagrams

    3
    Tanabe-Sugano diagrams
    The ground
    electronic state is
    always plotted
    along the horizontal
    axis. This makes it
    easy to determine
    values of E/B above
    the ground state.
    Example [V(H2O)6]3+ (d2)
    Three spin-allowed transitions
    for d2 configuration:
    Tanabe-Sugano diagrams for d2, d3, d8
    Tanabe-Sugano diagrams for d4 – d7
    Determining Δo from spectra using T-S diagram
    First approximations of Δo values, B by using the positions
    of the absorption from spectra (depends on d-electron
    configuration), sometimes directly deduced from spectrum
    Example [V(H2O)6]3+ (d2)
    Two absorption bands at
    17,800 and 25,700 cm–1.
    Estimate values of Δo, B
    Example [V(H2O)6]3+ (d2)
    Example Co(II) (d7) Two absorption bands at
    16,000 cm–1 for 4T1g  4A2g,
    20,000 cm–1 for 4T1g (4F)  4T1g
    (4P)
    Tetrahedral complexes
    More intense absorptions than octahedral complexes as a
    result of the first (Laporte) selection rule (lack of center of
    symmetry in Td).
    Hole formalism:

    In practical terms, we can use the correlation diagram for


    the d10-n configuration of Oh geometry to describe the dn
    configuration of Td geometry
    Charge transfer
    Very intense, responsible for the vivid colors of halogens in
    donor solvents. X2·donor → [donor+][X2–]
    Molar absorptivity (ε) > ~50,000 L mol–1 cm–1, much more
    intense than d-d transitions (ε < ~20 L mol–1 cm–1).
    Ligand to metal charge transfer (LMCT), resulting formal
    reduction of metal. e.g., IrBr63– (d6)
    Charge transfer
    Metal to ligand charge transfer (MLCT), resulting in
    oxidation of metal, found in coordination complexes
    having π-acceptor (empty π* orbital)ligands (CO, CN–,
    SCN–, bipyridine, dithiocarbamate)

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