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    Sarthak Singh
    This document discusses electronic spectra of transition metal complexes. It begins by providing examples of common complexes and their colors, which are due to electronic transitions in the visible light region. The spacing of these transitions depends on the geometry, ligands, and metal oxidation state. Later sections explain molecular orbital diagrams, the effect of electron-electron repulsion and ligand fields on term symbols and splitting. Correlation diagrams are used to illustrate relationships between terms under varying ligand field strengths. Selection rules for allowed transitions are also noted.

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    ElecSpectra 1 Upload

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    Sarthak Singh
    36 views20 pages
    This document discusses electronic spectra of transition metal complexes. It begins by providing examples of common complexes and their colors, which are due to electronic transitions in the visible light region. The spacing of these transitions depends on the geometry, ligands, and metal oxidation state. Later sections explain molecular orbital diagrams, the effect of electron-electron repulsion and ligand fields on term symbols and splitting. Correlation diagrams are used to illustrate relationships between terms under varying ligand field strengths. Selection rules for allowed transitions are also noted.

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    ElecSpectra

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    This document discusses electronic spectra of transition metal complexes. It begins by providing examples of common complexes and their colors, which are due to electronic transitions in the visible light region. The spacing of these transitions depends on the geometry, ligands, and metal oxidation state. Later sections explain molecular orbital diagrams, the effect of electron-electron repulsion and ligand fields on term symbols and splitting. Correlation diagrams are used to illustrate relationships between terms under varying ligand field strengths. Selection rules for allowed transitions are also noted.

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    © All Rights Reserved
    Download as PDF, TXT or read online from Scribd
    Download as pdf or txt
    36 views20 pages

    ElecSpectra 1 Upload

    Uploaded by

    Sarthak Singh
    This document discusses electronic spectra of transition metal complexes. It begins by providing examples of common complexes and their colors, which are due to electronic transitions in the visible light region. The spacing of these transitions depends on the geometry, ligands, and metal oxidation state. Later sections explain molecular orbital diagrams, the effect of electron-electron repulsion and ligand fields on term symbols and splitting. Correlation diagrams are used to illustrate relationships between terms under varying ligand field strengths. Selection rules for allowed transitions are also noted.

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    Electronic Spectra of Complexes

    [Co(H2O)6]2+
    Oh, Pink

    Many TM complexes show color, e.g.

    [CoCl4]2Td, Blue

    [Ni(H2O)6]2+ NH
    3
    Oh, Green

    [Ni(NH3)6]2+
    Oh, Blue

    [Cr(H2O)6]3+
    Oh, Violet

    [Cr(H2O)6]2+
    Oh, Bright Blue

    Color is due to electronic transition b/w levels whose SPACING corresponds to


    the wavelength of light available in visible region (complimentary color is
    observed).

    SPACING depends on:


    - geometry of complex
    - nature of ligands
    - oxidation state of metal

    Electronic Spectra: Examples

    Electronic Spectra

    MO diagram of octahedral
    complex discussed so far
    is based on one-electron
    model

    Configuration dn add effect of ee repulsion add effect of Ligand Field

    Effect of e-e repulsion: Term Symbols

    Splitting of Terms in Chemical Environment

    (Transformation matrix)

    (else 2l + 1)

    (General Transformation matrix)

    Construction of Correlation Diagram


    Configuration dn add effect of ee repulsion add effect of Ligand Field

    Correlation Diagram for a d2 system in Oh

    (a) Free ion terms


    (b) Weak field terms
    (c) Strong field ground
    and excited configuration
    (d) Strong field terms
    (e) Intermediate field

    Total degeneracy
    = (2l+1)*(2s+1)

    Splitting of dn and d10-n Terms in Oh and Td Field

    dn vs d10-n

    Oh vs Td

    Correlation Diagram for a d2 and d8 system

    t
    Octahedral d8 and
    tetrahedral d2 on Left

    O
    Octahedral d2 and
    tetrahedral d8 on Right

    Correlation Diagram for a d4 system

    Octahedral d10-n and tetrahedral dn on Left

    Correlation Diagram for a dn system

    (a) d2 and d8 (b) d3 and d7 (c) d4 and d6

    (d) d5

    Octahedral d10-n and tetrahedral dn on Left

    Interpretation of Electronic Spectrum


    Interpretation of Electronic Spectrum:
    1. No. (and position) of spectral lines
    2. Intensity of spectral lines
    3. Width of spectral band

    Selection Rules:
    Laporte allowed transition are those with a change in parity
    Spin allowed transition have same spin multiplicity

    Molar absorptivities for various types of electronic transition


    observed in complexes

    Ground & excited terms having the same spin for weak field

    Orgel Diagram
    d3 system Co2+ ion
    Td (right), Oh (left)

    Tanabe Sugano Diagrams

    Tanabe Sugano Diagrams

    Info. From Tanabe Sugano Diagrams


    d6 system

    e.g. Low spin [Co(en)3]+

    Info. From Tanabe Sugano Diagrams

    Ratio = 1.32;
    corresponds to D/B = 32.8
    Gives B = 657/cm and D = 21550/cm

    Info. from Tanabe Sugano Diagrams

    d3

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