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    Introduction To Molecular Spectros

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    Introduction To Molecular Spectros

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    introduction to molecular spectroscopy

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    Introduction To Molecular Spectros

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    Rotational & Vibrational Spectroscopy, Formula Sheet

    1

    2F4Y: Molecular Structure & Energy Levels
    Fundamentals of Rotational & Vibrational Spectroscopy
    Revision Helpsheet
    Introduction to Molecular Spectroscopy










    Rotational & Vibrational Spectroscopy, Formula Sheet
    2

    Rotational Spectroscopy
    Diatomic and Linear Polyatomic Molecules




    (

    )

    (2J+1)
    Rotational & Vibrational Spectroscopy, Formula Sheet
    3

    Rotational spectrum requires permanent dipole moment

    The spacing between absorption lines in rotational spectra = 2B

    Non-Linear polyatomic molecules







    Rotational & Vibrational Spectroscopy, Formula Sheet
    4

    Vibrational Spectroscopy
    Diatomic Molecules
    Simple harmonic oscillator

    (

    )
    Classical frequency of vibration



    For the transition to be allowed, the dipole moment of the
    molecule must change during the vibration
    Rotational & Vibrational Spectroscopy, Formula Sheet
    5


    For the v = 0 1 transition


    The absorbed frequency of light equals the classical frequency of
    molecular vibration
    Anharmonic Oscillator

    Rotational & Vibrational Spectroscopy, Formula Sheet
    6


    01 Fundamental
    13, 02, 03 Overtones
    12, 23 Hotbands
    [(


    x
    e
    is the anharmonicity constant
    How to use this equation to calculate frequencies of transitions (ie v
    0

    1
    ):
    To simplify, divide both sides of the equation by h. Then you can
    express a vibrational energy level as a frequency
    [(


    Calculate v for the higher energy state (E.g. v=1) and then subtract v
    for the lower energy state (E.g. v=0)

    {[

    ] [

    ]}

    )
    Rotational & Vibrational Spectroscopy, Formula Sheet
    7











    Rotational & Vibrational Spectroscopy, Formula Sheet
    8

    Polyatomic Molecules
    Any polyatomic has 3N (n=co-ordinates) degrees of freedom
    For a linear molecule
    3 translational degrees of freedom
    2 rotational degrees of freedom

    Therefore 3N-5 vibrational degrees of freedom remaining
    (3x3)-5 = 4 vibrations remaining






    Rotational & Vibrational Spectroscopy, Formula Sheet
    9

    For a non-linear molecule
    3 translational degrees of freedom
    3 rotational degrees of freedom

    Therefore 3N-6 vibrational degrees of freedom remaining
    (3x3)-6 = 3 vibrations remaining








    Rotational & Vibrational Spectroscopy, Formula Sheet
    10


    If the dipole moment changes in the course of a given vibration, as
    the molecule passes through its equilibrium configuration, that
    vibration will be active in the infra-red spectrum



    Rotational & Vibrational Spectroscopy, Formula Sheet
    11

    Raman Spectroscopy
    Result of scattering rather than absorption
    Most of scattered light has the same frequency v as the incident
    light v: Rayleigh Scattering: v = v.

    Rayleigh Scattering responsible for blue sky and redness of the
    sun at dawn and sunset light at blue end of spectra more
    effectively scattered than red



    Rotational & Vibrational Spectroscopy, Formula Sheet
    12

    Raman Stokes:


    Raman Anti-Stokes:

    )|


    If the polarizability changes in the course of a given vibration, as
    the molecule passes through its equilibrium configuration, that
    vibration will be active in the Raman spectrum
    Rotational & Vibrational Spectroscopy, Formula Sheet
    13


    Mutual exclusion rule for centrosymmetric molecules
    Vibrations allowed in the spectrum are Raman-forbidden and vice
    versa
    IR RAMAN RAMAN IR
    Raman-active modes must be of gerade (g) character
    IR-active modes must be of ungerade (u) character

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