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    Preparatory Problems PDF

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    Gerel Bayrmagnai
    The document discusses the harmonic oscillator and rigid rotor models used to describe vibrational and rotational motion in diatomic molecules. It provides the relevant equations and asks the student to calculate vibrational frequencies, rotational energies, bond lengths, and transition frequencies for various carbon monoxide isotopologues.

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

    Preparatory Problems PDF

    Uploaded by

    Gerel Bayrmagnai
    149 views2 pages
    The document discusses the harmonic oscillator and rigid rotor models used to describe vibrational and rotational motion in diatomic molecules. It provides the relevant equations and asks the student to calculate vibrational frequencies, rotational energies, bond lengths, and transition frequencies for various carbon monoxide isotopologues.

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    Preparatory-Problems (4).pdf

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    The document discusses the harmonic oscillator and rigid rotor models used to describe vibrational and rotational motion in diatomic molecules. It provides the relevant equations and asks the student to calculate vibrational frequencies, rotational energies, bond lengths, and transition frequencies for various carbon monoxide isotopologues.

    Copyright:

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

    Preparatory Problems PDF

    Uploaded by

    Gerel Bayrmagnai
    The document discusses the harmonic oscillator and rigid rotor models used to describe vibrational and rotational motion in diatomic molecules. It provides the relevant equations and asks the student to calculate vibrational frequencies, rotational energies, bond lengths, and transition frequencies for various carbon monoxide isotopologues.

    Copyright:

    © All Rights Reserved
    Download as PDF, TXT or read online from Scribd
    Download as pdf or txt
    of 2

    52nd International Chemistry Olympiad, Istanbul, TURKEY Preparatory problems: THEORETICAL

    Problem 19. Harmonic Oscillator and Rigid Rotor Models

    Vibration of a diatomic molecule is reminiscent of two masses on a spring with a potential


    energy that is a function of the displacement from equilibrium. Hence, the harmonic oscillator
    model is utilized to compute vibrational frequencies. These frequencies are called harmonic
    vibrational frequencies. The energy of a harmonic oscillator can be written as follows:

    1
    𝐸𝑛 = ℎ 𝜈 (𝑛 + )
    2

    where 𝜈 is the harmonic vibrational frequency, ℎ is the Planck constant, and 𝑛 is a nonnegative
    integer. The harmonic vibrational frequency can be calculated as follows:

    1 𝑘
    𝜈= √
    2𝜋 𝜇

    where 𝑘 is the force constant and 𝜇 is the reduced mass:

    𝑚1 𝑚2
    𝜇=
    𝑚1 + 𝑚2

    where 𝑚1 and 𝑚2 are the masses of the first and the second atoms, respectively.

    For the 12C16O molecule the value of the force constant is 1902.4 N/m. For this problem, the
    atomic masses of isotopes can be approximated by their mass numbers.

    19.1. Calculate the harmonic vibrational frequency of the 12C16O molecule in Hz.

    19.2. Express the harmonic vibrational frequency of the 12C16O molecule in cm–1.

    19.3. Calculate the zero-point vibrational energy (ZPVE) of the 12C16O molecule in kcal/mol.

    19.4. Calculate the harmonic vibrational frequency of the 13C16O molecule in cm–1.

    19.5. Calculate the harmonic vibrational frequency of the 12C17O molecule in cm–1.

    78
    52nd International Chemistry Olympiad, Istanbul, TURKEY Preparatory problems: THEORETICAL

    The harmonic oscillator model can readily be extended to polyatomic molecules. In this case,
    the total vibrational energy of a molecule with nfreq vibrational frequencies can be written as
    follows:

    𝑛𝑓𝑟𝑒𝑞
    1
    𝐸𝑛1 𝑛2 …𝑛𝑛 = ℎ ∑ 𝜈𝑖 (𝑛𝑖 + )
    𝑓𝑟𝑒𝑞 2
    𝑖=1

    where 𝜈𝑖 are the harmonic vibrational frequencies, ℎ is the Planck constant, and 𝑛𝑖 are
    nonnegative integers.

    For the water molecule the harmonic vibrational frequencies are 1649, 3832, and 3943 cm–1.
    Using the harmonic oscillator model, for the water molecule:

    19.6. Calculate the ZPVE value (in J and cm–1 units).

    19.7. Calculate the first 5 energy levels (in cm–1).

    To describe the rotational motion of a diatomic molecule, the rigid rotor model is used. In this
    model the bond length (𝑅) of the diatomic molecule is kept constant during the rotational
    motion. Using the rigid rotor model, the rotational energy of a diatomic molecule can be written
    as follows:
    ℎ2
    𝐸𝑙 = 𝑙(𝑙 + 1)
    8 𝜋2𝐼

    where 𝐼 is the moment of inertia and 𝑙 is a nonnegative integer. The moment of inertia can be
    written as follows:

    𝐼 = 𝜇 𝑅2

    where 𝜇 is the reduced mass and 𝑅 is the bond length of the diatomic molecule.

    In the microwave spectrum of the 12C16O molecule the value of frequency for the lowest energy
    transition is 115.270 GHz.

    19.8. Calculate the bond length of the 12C16O molecule in Å.

    19.9. For the 12C16O molecule predict the frequency of the next two absorptions (selection
    rule is ∆𝑙 = ±1).

    19.10. For the 12C17O molecule, calculate the frequency of the lowest energy absorption.
    79

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