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    Scott Kirkby - Molecular Orbital Theory

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    Nuansak3
    1) The document discusses molecular orbital theory for diatomic molecules, describing how molecular orbitals are constructed by combining atomic orbitals from each atom. 2) Atomic orbitals of similar energies are combined, with the symmetry and labeling of the resulting molecular orbitals depending on whether they are symmetric or antisymmetric with respect to inversion. 3) σ orbitals are symmetric about the internuclear axis while π orbitals have a nodal plane along the axis. The ordering of molecular orbital energies can vary depending on the molecule.

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    Scott Kirkby - Molecular Orbital Theory

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    Nuansak3
    72 views5 pages
    1) The document discusses molecular orbital theory for diatomic molecules, describing how molecular orbitals are constructed by combining atomic orbitals from each atom. 2) Atomic orbitals of similar energies are combined, with the symmetry and labeling of the resulting molecular orbitals depending on whether they are symmetric or antisymmetric with respect to inversion. 3) σ orbitals are symmetric about the internuclear axis while π orbitals have a nodal plane along the axis. The ordering of molecular orbital energies can vary depending on the molecule.

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    Scott Kirkby- Molecular Orbital Theory

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    1) The document discusses molecular orbital theory for diatomic molecules, describing how molecular orbitals are constructed by combining atomic orbitals from each atom. 2) Atomic orbitals of similar energies are combined, with the symmetry and labeling of the resulting molecular orbitals depending on whether they are symmetric or antisymmetric with respect to inversion. 3) σ orbitals are symmetric about the internuclear axis while π orbitals have a nodal plane along the axis. The ordering of molecular orbital energies can vary depending on the molecule.

    Copyright:

    Attribution Non-Commercial (BY-NC)
    Download as PDF, TXT or read online from Scribd
    Download as pdf or txt
    72 views5 pages

    Scott Kirkby - Molecular Orbital Theory

    Uploaded by

    Nuansak3
    1) The document discusses molecular orbital theory for diatomic molecules, describing how molecular orbitals are constructed by combining atomic orbitals from each atom. 2) Atomic orbitals of similar energies are combined, with the symmetry and labeling of the resulting molecular orbitals depending on whether they are symmetric or antisymmetric with respect to inversion. 3) σ orbitals are symmetric about the internuclear axis while π orbitals have a nodal plane along the axis. The ordering of molecular orbital energies can vary depending on the molecule.

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    of 5

    Page 1 of 5

    27. Molecular Orbital Theory


    Date: 4 November 2001 Suggested Reading: Chapters 9-7 to 9-16 of the text.

    Introduction
    We will construct sets of molecular orbitals for diatomic molecules by combining pairs of atomic orbitals, one from each atom.

    Labelling of the Molecular Orbitals


    If the resulting molecular orbital is symmetric about the internuclear axis, then the MO s called a (sigma) orbital. For example,

    Figure 27-1: Sketch of two 1s atomic orbitals forming a molecular orbital.


    Scott Kirkby Last revised: 04 November 2002

    Introduction to Quantum Chemistry

    Lecture # 27

    Page 2 of 5

    There are many combinations of atomic orbitals that will lead to orbitals. thus we add on the label for the originating atomic orbital, that is
    1s A + 1s B 1s

    (27-1)

    An antibonding orbital is designated with a * superscript.


    1s A 1s B 1s

    (27-2)

    orbitals may be alternately designated by their symmetry with respect to a center of inversion at the center of the molecule. If the orbital does not change sign with inversion, it is labelled with a g for the German word for even (gerade). If it changes sign, it is labelled u for ungerade. (not even, that is odd).
    1 1s = ------------------------ ( 1s A + 1s B ) 2(1 + S) = g 1s 1 1s = ----------------------- ( 1s A 1s B ) 2(1 S) = u 1s
    (27-4) (27-3)

    Note: It is possible for an orbital to be g and antibonding and u and bonding as we shall see. Only atomic orbitals of similar energies are combined in this fashion to give molecular orbitals. (Large differences in energy lead to little overlap.)

    Scott Kirkby

    Last revised: 04 November 2002

    Introduction to Quantum Chemistry

    Lecture # 27

    Page 3 of 5

    2s A + 2s B g 2s 2s A 2s B u 2s 2p zA + 2p zB g 2p z 2p zA 2p zB u 2p z
    (27-5)

    What if we combine 2px and 2pz?


    2p xA + 2p zB No net overlap 2p xA 2p zB No net overlap
    (27-6)

    Figure 27-2: Pictorial representation of the combination of the 2px and 2pz orbitals.

    Scott Kirkby

    Last revised: 04 November 2002

    Introduction to Quantum Chemistry

    Lecture # 27

    Page 4 of 5

    Symmetry plays a role in combining orbitals in useful ways.

    Figure 27-3: Pictorial representation of the combination of the 2pxA and 2pxB orbitals.

    The 2pxA + 2pxB molecular orbital has a nodal plane in the yz plane (by convention, the z direction is the line joining the two nuclei) running through the internuclear axis. Molecular orbitals that have a nodal plane colinear with the internuclear axis are called orbitals.
    2p xA + 2p xB u 2p x 2p xA 2p xB g 2p x
    (27-7)

    Here the gerade molecular orbital is antibonding. The same happens for 2py
    2p yA + 2p yB u 2p y 2p yA 2p yB g 2p y
    (27-8)

    Scott Kirkby

    Last revised: 04 November 2002

    Introduction to Quantum Chemistry

    Lecture # 27

    Page 5 of 5

    Ordering of Energies

    Figure 27-4: Ordering of the molecular orbitals for diatomic molecules. Note figure is not to scale. For molecules N2 and lighter g2pz is higher in energy that u2px and u2py. For O2 and heavier, the ordering is reversed.

    Suggested Reading for Next Lecture: Chapter 10 of the text.

    Scott Kirkby

    Last revised: 04 November 2002

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