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    Grupos Pontuais Irredutiveis

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    Eduardo Silva
    The document discusses the irreducible representations of point groups and how they relate to normal coordinates and vibrational modes of molecules. It provides the following key points: 1) Normal coordinates and vibrational wavefunctions can be categorized based on the point group of the molecule. This allows predictions from character tables about possible symmetries. 2) Every normal mode has a certain symmetry associated with the point group of the molecule. Identifying the point group is important for determining normal mode symmetries. 3) Water, with C2v symmetry, has 3 normal modes that can be grouped into the reducible representation 2A1 + B2 based on character table analysis of how each mode transforms under symmetry operations.

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    Grupos Pontuais Irredutiveis

    Uploaded by

    Eduardo Silva
    19 views2 pages
    The document discusses the irreducible representations of point groups and how they relate to normal coordinates and vibrational modes of molecules. It provides the following key points: 1) Normal coordinates and vibrational wavefunctions can be categorized based on the point group of the molecule. This allows predictions from character tables about possible symmetries. 2) Every normal mode has a certain symmetry associated with the point group of the molecule. Identifying the point group is important for determining normal mode symmetries. 3) Water, with C2v symmetry, has 3 normal modes that can be grouped into the reducible representation 2A1 + B2 based on character table analysis of how each mode transforms under symmetry operations.

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    Grupos pontuais irredutiveis

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    Grupos pontuais irredutiveis

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    The document discusses the irreducible representations of point groups and how they relate to normal coordinates and vibrational modes of molecules. It provides the following key points: 1) Normal coordinates and vibrational wavefunctions can be categorized based on the point group of the molecule. This allows predictions from character tables about possible symmetries. 2) Every normal mode has a certain symmetry associated with the point group of the molecule. Identifying the point group is important for determining normal mode symmetries. 3) Water, with C2v symmetry, has 3 normal modes that can be grouped into the reducible representation 2A1 + B2 based on character table analysis of how each mode transforms under symmetry operations.

    Copyright:

    © All Rights Reserved
    Download as PDF, TXT or read online from Scribd
    Download as pdf or txt
    19 views2 pages

    Grupos Pontuais Irredutiveis

    Uploaded by

    Eduardo Silva
    The document discusses the irreducible representations of point groups and how they relate to normal coordinates and vibrational modes of molecules. It provides the following key points: 1) Normal coordinates and vibrational wavefunctions can be categorized based on the point group of the molecule. This allows predictions from character tables about possible symmetries. 2) Every normal mode has a certain symmetry associated with the point group of the molecule. Identifying the point group is important for determining normal mode symmetries. 3) Water, with C2v symmetry, has 3 normal modes that can be grouped into the reducible representation 2A1 + B2 based on character table analysis of how each mode transforms under symmetry operations.

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    13.

    10: IRREDUCIBLE REPRESENTATION OF POINT GROUPS


    There exists an important fact about normal coordinates. Each of these coordinates belongs to an irreducible representation of the
    point the molecule under investigation. Vibrational wavefunctions associated with vibrational energy levels share this property as
    well. The normal coordinates and the vibration wavefunction can be categorized further according to the point group they belong
    to. From the character table predictions can be made for which symmetries can exist. The irreducible representation offers insight
    into the IR and/or Raman activity of the molecule in question.

    SYMMETRY OF NORMAL MODES


    It is important to realize that every normal mode has a certain type of symmetry associated with it. Identifying the point group of
    the molecule is therefore an important step. With this in mind it is not surprising that every normal mode forms a basis set for an
    irreducible representation of the point group the molecule belongs to. For a molecule such as water, having a structure of XY2,
    three normal coordinates can be determined. The two stretching modes are equivalent in symmetry and energy. The figure below
    shows the three normal modes for the water molecule:

    Figure 13.10.1: Three normal modes of water


    By convention, with nonlinear molecules, the symmetric stretch is denoted v1 whereas the asymmetric stretch is denoted v2.
    Bending motions are v3. With linear molecules, the bending motion is v2 whereas asymmetric stretch is v3.
    The water molecule has C2v symmetry and its symmetry elements are E, C2, σ(xz) and σ(yz). To determine the symmetries of the
    three vibrations and how they each transform, symmetry operations will be performed. As an example, performing C2 operations
    using the two normal mode v2 and v3 gives the following transformation:

    Figure 13.10.2: Symmetry operations on the symmetric and asymmetric stretches of water
    Once all the symmetry operations have been performed in a systematic manner for each modes the symmetry can be assigned to
    the normal mode using the character table for C2v:
    Table 13.10.2: Character table for the C2v point group
    C2v E C2 σ (xz) σ (yz)
    ν1 1 1 1 1 = a1

    ν2 1 1 1 1 = a1

    ν3 1 -1 -1 1 = b2

    Water has three normal modes that can be grouped together as the reducible representation

    Γv ib = 2 a1 + b2 . (13.10.1)

    Determination of normal modes becomes quite complex as the number of atoms in the molecule increases. Nowadays, computer
    programs that simulate molecular vibrations can be used to perform these calculations. The example of [PtCl4]2- shows the

    9/3/2019 13.10.1 https://chem.libretexts.org/link?13673


    increasing complexity (Figure 13.10.2). The molecule has five atoms and therefore 15 degrees of freedom, 9 of these are
    vibrational degrees of freedom. The nine normal modes are exemplified below along with the irreducible representation the
    normal mode belongs to (D4h point group).

    Figure 13.10.3: A1g, b1g and eu are stretching vibrations whereas b2g, a2u, b2u and eu are bending vibrations.

    CONTRIBUTORS
    Kristin Kowolik, University of California, Davis

    9/3/2019 13.10.2 https://chem.libretexts.org/link?13673

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