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    What Happens When We Move To More Complicated Systems? Consider O - The Lewis Dot Structure Famously Predicts The Wrong Electronic Structure For O We Can Use LCAO-MO Theory To Get A Better Picture

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    LCAO-MO theory uses atomic orbitals to form molecular orbitals and predict the electronic structure of molecules more accurately than Lewis structures. It accounts for orbital mixing between similar atomic orbitals. Photoelectron spectroscopy provides data on relative atomic orbital energies that help determine orbital interactions. LCAO-MO theory successfully explains trends in bond orders, distances, and properties of homo- and heteronuclear diatomic molecules.

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    What Happens When We Move To More Complicated Systems? Consider O - The Lewis Dot Structure Famously Predicts The Wrong Electronic Structure For O We Can Use LCAO-MO Theory To Get A Better Picture

    Uploaded by

    Devi
    38 views11 pages
    LCAO-MO theory uses atomic orbitals to form molecular orbitals and predict the electronic structure of molecules more accurately than Lewis structures. It accounts for orbital mixing between similar atomic orbitals. Photoelectron spectroscopy provides data on relative atomic orbital energies that help determine orbital interactions. LCAO-MO theory successfully explains trends in bond orders, distances, and properties of homo- and heteronuclear diatomic molecules.

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    M-2

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    LCAO-MO theory uses atomic orbitals to form molecular orbitals and predict the electronic structure of molecules more accurately than Lewis structures. It accounts for orbital mixing between similar atomic orbitals. Photoelectron spectroscopy provides data on relative atomic orbital energies that help determine orbital interactions. LCAO-MO theory successfully explains trends in bond orders, distances, and properties of homo- and heteronuclear diatomic molecules.

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    © All Rights Reserved
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    Download as pdf or txt
    38 views11 pages

    What Happens When We Move To More Complicated Systems? Consider O - The Lewis Dot Structure Famously Predicts The Wrong Electronic Structure For O We Can Use LCAO-MO Theory To Get A Better Picture

    Uploaded by

    Devi
    LCAO-MO theory uses atomic orbitals to form molecular orbitals and predict the electronic structure of molecules more accurately than Lewis structures. It accounts for orbital mixing between similar atomic orbitals. Photoelectron spectroscopy provides data on relative atomic orbital energies that help determine orbital interactions. LCAO-MO theory successfully explains trends in bond orders, distances, and properties of homo- and heteronuclear diatomic molecules.

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    Homonuclear Diatomic Molecules

    What happens when we move to more complicated systems?


    Consider O2.
    • The Lewis dot structure famously predicts the wrong electronic
    structure for O2

    • We can use LCAO-MO theory to get a better picture:

    Notice that
    Eσ > Eπ, Eσ Eπ
    2pa 2pb
    because the
    σ bonds have
    more overlap
    than π bonds

    2sa 2sb
    Electron Configurations and Bond Orders
    Just as with atoms, we can write a
    molecular electron configuration for O2

    σ2σ*2σ2π4π*2

    We can also calculate the O–O bond order:


    1
    BO  # bonding e   # anti-bonding e 
    2
    1
     8  4   2
    2

    LCAO MO theory also predicts (correctly) that O2 has two unpaired


    electrons.
    Orbital Mixing
    Orbitals of similar but unequal energies can interact if they have the
    same symmetry
    The 2s and 2pz orbitals form MOs with the same symmetry (σg and σu).
    sp mixing causes the σg and σu MOs to be pushed apart in energy:

    The σ and
    π orbitals
    change order!
    Orbital Mixing
    The size of
    the effect
    depends on
    the 2s-2p
    energy
    difference.
    order changes

    small Zeff = large Zeff =


    small energy large energy
    difference = difference =
    large sp mixing small sp mixing
    MOs of Homonuclear Diatomic Molecules
    The MO picture of homonuclear diatomic molecules depends on the
    amount of sp mixing.

    Li2, Be2, B2, C2, N2 O2, F2, Ne2


    Bond Order and Bond Distance
    The MO bond order is the main factor controlling the internucelar
    distance.

    B2
    σ2σ*2π2
    BO = 1
    F2
    σ σ* σ2π4π*4
    2 2

    BO = 1

    O2–
    σ2σ*2σ2π4π*3
    BO = 1.5
    C2
    σ σ*2π4
    2 C22–
    BO = 2 σ2σ*2π4σ2
    O2
    BO = 3
    σ σ* σ2π4π*2
    2 2

    BO = 2

    N2+ O2+
    σ2σ*2π4σ1 σ2σ*2σ2π4π*1
    BO = 2.5 N2 BO = 2.5
    σ σ*2π4σ2
    2

    BO = 3
    Relative AO Energies for MO Diagrams
    Photoelectron spectroscopy gives us a pretty good idea of the relative
    energies for AOs.

    Al
    B Si
    Li Na P
    C Mg S
    Be N Cl
    H –13.6 eV Al 3p Ar
    O 3s
    B 2p F –18.6 eV Si
    1s
    C Ne P
    2s
    He S
    N Cl
    Ar
    O

    F –40.2 eV

    Ne
    MO Diagram for HF
    The AO energies suggest that the 1s orbital of hydrogen interacts
    mostly with a 2p orbital of fluorine. The F 2s is nonbonding.

    σ*

    –13.6 eV
    1s
    –18.6 eV
    nb 2p
    Energy

    σ
    So H–F has one σ bond
    and three lone electron
    pairs on fluorine

    –40.2 eV
    2s
    nb

    H H–F F
    Relative AO Energies for MO Diagrams
    Photoelectron spectroscopy gives us a pretty good idea of the relative
    energies for AOs.

    Al
    B Si
    Li Na P
    C –10.7 eV Mg S
    Be N Cl
    H Al 3p Ar
    O –15.8 eV
    3s
    B 2p F Si
    1s
    –19.4 eV C Ne P
    2s
    He S
    N Cl
    Ar
    –32.4 eV O

    Ne
    Heteronuclear Diatomic Molecules: CO
    In molecules with more than one type of atom, MOs are formed from
    AOs that have different energies. Consider CO:

    σ*
    LUMO is on carbon too!
    π*

    HOMO is on carbon
    Energy

    2pa
    σ 2pb

    σ*
    Anti-bonding orbitals
    2sa
    get polarized towards
    carbon

    2sb
    Bonding orbitals
    get polarized
    σ
    towards oxygen
    C C≡O O
    Summary
    MO Theory

    • LCAO-MO Theory is a simple method for predicting the


    approximate electronic structure of molecules.

    • Atomic orbitals must have the proper symmetry and energy to


    interact and form molecular orbitals.

    • Photoelectron spectroscopy provides useful information on the


    energies of atomic orbitals.

    • Next we’ll see that symmetry will help us treat larger molecules in
    the LCAO-MO theory framework.

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