Scribd Logo
Upload

Welcome to Scribd!

  • 8 views

    6 Molecular Structure 2024

    Uploaded by

    tebzanelly

    Copyright:

    © All Rights Reserved
    Download as PPTX, PDF, TXT or read online from Scribd

    6 Molecular Structure 2024

    Uploaded by

    tebzanelly
    8 views30 pages

    Copyright

    © © All Rights Reserved

    Available Formats

    PPTX, PDF, TXT or read online from Scribd

    Did you find this document useful?

    Is this content inappropriate?

    Copyright:

    © All Rights Reserved
    Download as PPTX, PDF, TXT or read online from Scribd
    Download as pptx, pdf, or txt
    8 views30 pages

    6 Molecular Structure 2024

    Uploaded by

    tebzanelly

    Copyright:

    © All Rights Reserved
    Download as PPTX, PDF, TXT or read online from Scribd
    Download as pptx, pdf, or txt
    of 30

    NCHE 221

    INORGANIC CHEMSITRY 1

    STUDY UNIT 3

    MOLECULAR STRUCTURE AND BONDING


    SS 3.3: Molecular orbital theory

    Molecular orbitals of H2:


    y + = CA1s(A) + CB1s(B)
    y - = CA1s(A) - CB1s(B)

    The relative sign of the coefficients determine


    whether the atomic orbital’s influence is constructive or destructive.
     Increase or decrease of electron density between nuclei
    SS 3.3: Molecular orbital theory

    Heteronuclear diatomic molecules:


    y = CA (A) + CB (B) + . . . . . .

     are atomic orbitals on atom A and atom B

    CA and CB are coefficients that indicate the size of contribution from atomic
    orbitals to molecular orbitals (CA  CB)
    SS 3.3: Molecular orbital theory

    Heteronuclear diatomic molecules:


    The contribution of atomic orbitals to molecular orbitals can be determined by
    C2.

    The larger C2 is, the larger the contribution of the atomic orbital to the molecular
    orbital. (C’ 2 > C’ 2)
    B A

    Example:
    CA2 > CB2
    The molecular orbital is mainly composed of
    A’s atomic orbital.

    An electron that occupies the molecular orbital


    is more likely to be found near atom A than
    atom B.
    (CA2 > CB2)
    SS 3.3: Molecular orbital theory

    Heteronuclear diatomic molecules:


    The greater contribution to a the bonding molecular orbital normally comes
    from the more electronegative atom .
    • The bonding e- are likely to be found near that atom
    (Energetically favourable location)

    The greater contribution to the antibonding orbital is from the less


    electronegative atom.

    Heteronuclear diatomic molecule is polar.

    Extreme case of polar covalent bonds are ionic bonds.


    (covalent bonds formed by an e- pair that is shared unequally)
    SS 3.3: Molecular orbital theory

    Heteronuclear diatomic molecules:


    There is an energy mismatch between the two sets of atomic orbitals.
    The relative positions of the two atomic orbitals reflect on the ionisation
    energy of the atoms.
    SS 3.3: Molecular orbital theory

    Heteronuclear diatomic molecules:


    The more their energies differ, the smaller the effect that two wavefunctions
    will have on each other.

    -

    B
    -
    Energy

    A A

    +

    +
    Due to interference
    of wavefunctions
    SS 3.3: Molecular orbital theory
    Heteronuclear diatomic molecules (HF):

    Valence orbitals available for molecular orbital formation:


    1s of H 1s1
    2s and 2p of F [He]2s22p5

    1 + 7 = 8 valence electrons to populate the MO

    H(1s) + F(2s + (3 x 2p)) = 5 AO => 5 MO


    SS 3.3: Molecular orbital theory

    Heteronuclear diatomic molecules:


    The 1s AO of hydrogen has a relatively high energy when compared to the 2p AO
    of fluorine. (Also note the relative difference between the 2p and 2s AO of
    fluorine)
    SS 3.3: Molecular orbital theory
    Heteronuclear diatomic molecules (HF):

    H 1s

    F 2p
    Energy

    F 2s
    SS 3.3: Molecular orbital theory
    Heteronuclear diatomic molecules (HF):

     orbitals of HF:
    Constructed by allowing 1s orbital of H to overlap the 2s and 2pz orbitals of F.

    Three atomic orbitals combine to form three  molecular orbitals:

     = C11s(H) + C22s(F) + C32p (F)


    z
    SS 3.3: Molecular orbital theory
    Heteronuclear diatomic molecules (HF):
    3
    2p*

    H 1s

    F 2p
    2p
    Energy

    2

    F 2s

    1
    SS 3.3: Molecular orbital theory
    Heteronuclear diatomic molecules (HF):

     orbitals of HF:
    2px and 2py of F are unaffected as they have  symmetry and there is no valence
    orbital of H of that symmetry.
    SS 3.3: Molecular orbital theory
    Heteronuclear diatomic molecules (HF):
    3

    H 1s
    1
    F 2p
    Energy

    2

    F 2s

    1
    SS 3.3: Molecular orbital theory
    Heteronuclear diatomic molecules (HF):

     orbitals of HF:
    2px and 2py are unaffected as they have  symmetry and there is no valence
    orbital of H with that symmetry.

    The  orbitals are therefore nonbonding orbitals.

    • Nonbonding orbitals are orbitals that have a nonbonding or antibonding


    character .
    • And can be confined to one atom in a diatomic molecule.
    SS 3.3: Molecular orbital theory
    Heteronuclear diatomic molecules (HF):
    122214
    3

    H 1s
    1
    F 2p
    Energy

    2

    F 2s

    1
    SS 3.3: Molecular orbital theory
    Heteronuclear diatomic molecules (HF):
    122214
    3 Mainly H

    H 1s
    1
    F 2p
    Mainly F
    Energy

    2

    F 2s

    Mainly F 1
    SS 3.3: Molecular orbital theory
    Heteronuclear diatomic molecules (HF):
    122214
    3 LUMO

    H 1s
    1
    HOMO F 2p
    Energy

    Nonbonding orbital
    2
    Bonding orbital

    F 2s

    1
    SS 3.3: Molecular orbital theory
    Heteronuclear diatomic molecules (HF):

    HF: 122214

    NB
    All electrons fill orbitals that are mainly on the F atom.

    HF polar
    Partial negative charge on the F atom (Dipole)

    Note that g (gerade) and u (ungerade) notations are no longer used, since there
    is no symmetry.
    SS 3.3: Molecular orbital theory
    Heteronuclear diatomic molecules (CO):

    Both C and O have 2s and 2p orbitals that can participate in the formation of 
    and  molecular orbitals.
    SS 3.3: Molecular orbital theory
    Heteronuclear diatomic molecules (CO):

    Valence orbitals available for the formation of molecular orbitals:


    2s and 2p of C [He]2s22p2
    2s and 2p of O [He]2s22p4

    4 + 6 = 10 valence electrons to occupy MO

    C(2s + (3 x 2p)) + O(2s + (3 x 2p)) = 8 AO => 8 MO


    SS 3.3: Molecular orbital theory

    Heteronuclear diatomic molecules (CO):


    Carbon’s 2p and 2s are higher in energy than oxygen’s 2p and 2s AO
    respectively. Note the energy difference between oxygen’s 2s and 2p in
    comparison with that of carbon.
    SS 3.3: Molecular orbital theory
    Heteronuclear diatomic molecules (CO):

    Valence orbitals available for the formation of molecular orbitals:


    2s and 2p of C [He]2s22p2
    2s and 2p of O [He]2s22p4

    4 + 6 = 10 valence electrons to occupy MO

    C(2s + (3 x 2p)) + O(2s + (3 x 2p)) = 8 AO => 8 MO


    SS 3.3: Molecular orbital theory
    Heteronuclear diatomic molecules (CO):

    C 2p

    O 2p
    Energy

    C 2s

    O 2s
    SS 3.3: Molecular orbital theory
    Heteronuclear diatomic molecules:

    s/pz

    p
    Energy

    s/pz

    Mixing of s and pz AO to form two new  MO.


    SS 3.3: Molecular orbital theory
    Heteronuclear diatomic molecules (CO):
    4
    12221432
    2
    LUMO
    C 2p

    O 2p
    3
    Energy

    HOMO
    C 2s
    1

    2
    O 2s

    1
    SS 3.3: Molecular orbital theory
    Heteronuclear diatomic molecules (CO):
    • 1 - localized mostly on the O atom
    - NBMO
    • 2 - BMO
    • 1 - mainly C2p character
    - -BMO
    • 3 - mainly C2pz character
    - located on the C atom
    - largely NBMO (HOMO)
    • 2 - mainly C2p character
    - -ABMO

    Frontier orbitals of CO – characteristic feature of transition metal carbonyls


    SS 3.3: Molecular orbital theory
    Heteronuclear diatomic molecules (CO):
    4
    CO: 12221432
    LUMO 2

    -11 C 2p

    3
    -13 HOMO O 2p

    -19 C 2s 1
    Energy (eV)

    2
    𝛿 +¿
    − 𝛿
    O: O 2s
    -34
    :C 1
    SS 3.3: Molecular orbital theory
    Heteronuclear diatomic molecules (CO):
    Both C and O have 2s and 2p orbitals that can participate in the formation of 
    and  molecular orbitals.

    Although the difference in electronegativity between C and O is large, the dipole


    moment of the CO molecule is small.

    Despite C being the less electronegative atom, the negative end of the dipole is
    on the C atom.

    Lone pairs and bonding pairs have a complex distribution.

    It is wrong to conclude that the polarity is only dependent on electronegativity


    when the antibonding orbitals are filled.
    SS 3.3: Molecular orbital theory
    Heteronuclear diatomic molecules (CO):

    Molecular orbitals of CO:

    The size of the atomic orbitals


    indicate the degree of contribution to
    the molecular orbital.

    You might also like