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    Vibrational Spectros

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    Debanshu Agasti
    Vibrational (IR) spectroscopy analyzes the vibrational modes of molecules. For nonlinear molecules with N atoms, there are 3N-6 fundamental vibrations. For linear molecules, there are 3N-5 fundamental vibrations. The IR spectrum is divided into four regions: the fingerprint region from 400-1600 cm-1 which shows skeletal vibrations, the functional group region from 1600-4000 cm-1 which identifies functional groups, and higher energy regions above 4000 cm-1 that show overtones and combinations bands. The frequency of vibrational bands depends on factors like bond strength, reduced mass, hybridization, and conjugation.

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    Vibrational Spectros

    Uploaded by

    Debanshu Agasti
    21 views15 pages
    Vibrational (IR) spectroscopy analyzes the vibrational modes of molecules. For nonlinear molecules with N atoms, there are 3N-6 fundamental vibrations. For linear molecules, there are 3N-5 fundamental vibrations. The IR spectrum is divided into four regions: the fingerprint region from 400-1600 cm-1 which shows skeletal vibrations, the functional group region from 1600-4000 cm-1 which identifies functional groups, and higher energy regions above 4000 cm-1 that show overtones and combinations bands. The frequency of vibrational bands depends on factors like bond strength, reduced mass, hybridization, and conjugation.

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    Vibrational Spectroscopy (2)

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    Vibrational (IR) spectroscopy analyzes the vibrational modes of molecules. For nonlinear molecules with N atoms, there are 3N-6 fundamental vibrations. For linear molecules, there are 3N-5 fundamental vibrations. The IR spectrum is divided into four regions: the fingerprint region from 400-1600 cm-1 which shows skeletal vibrations, the functional group region from 1600-4000 cm-1 which identifies functional groups, and higher energy regions above 4000 cm-1 that show overtones and combinations bands. The frequency of vibrational bands depends on factors like bond strength, reduced mass, hybridization, and conjugation.

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    © All Rights Reserved
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    Download as pptx, pdf, or txt
    21 views15 pages

    Vibrational Spectros

    Uploaded by

    Debanshu Agasti
    Vibrational (IR) spectroscopy analyzes the vibrational modes of molecules. For nonlinear molecules with N atoms, there are 3N-6 fundamental vibrations. For linear molecules, there are 3N-5 fundamental vibrations. The IR spectrum is divided into four regions: the fingerprint region from 400-1600 cm-1 which shows skeletal vibrations, the functional group region from 1600-4000 cm-1 which identifies functional groups, and higher energy regions above 4000 cm-1 that show overtones and combinations bands. The frequency of vibrational bands depends on factors like bond strength, reduced mass, hybridization, and conjugation.

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    Vibrational (IR) spectroscopy

    Part-2
    Vibrations of Polyatomic Molecules
    Normal vibrational modes of a molecule containing N atoms is

    • Total degrees of freedom: 3N (N = No. of atoms in a molecule)


    Number of parameters Each atom can be specified using three coordinates (e.g. x, y, and z)
    of a system that may
    vary independently.

    • Translational motion uses 3 degrees of freedom.

    • Rotation of nonlinear molecule can occur along three axial direction,


    which counts 3 degrees of freedom.

    • For nonlinear molecule the remaining degrees of freedom, 3N−6, is


    due to internal vibration.

    For nonlinear N atomic molecule: 3N – 6 fundamental vibrations.


    Vibrations of Polyatomic Molecules

    • A linear molecule there is no rotation about the bond axis.

    • So, only 2 rotational degrees of freedom (and 3


    translational degrees of freedom).
    • Hence there are 3N – 5 degrees of vibrational freedom for
    linear molecule.

    All fundamental vibrations are not necessarily


    give vibrational spectrum or active in IR region.
    Fundamental modes of vibration in water molecule
    O
    O symmetric stretching O
    H H
    H H
    ν1 = 3652 cm-1 H H

    anti-symmetric
    stretching O O
    O
    H H
    H H
    ν3 = 3756 cm-1
    H H

    Bending O
    O (symmetric) O
    H H
    H H H H
    ν2 = 1595 cm-1
    Fundamental modes of vibration in CO2 molecule

    O CH O O CH O O CH O

    Symmetric stretch
    ν1 = 1330 cm-1

    O CH O O CH O O CH O

    Assymmetric stretch
    ν3 = 2349 cm-1

    O CH O

    Two degenerate bending modes


    ν2 = 667 cm-1
    • Occasionally more absorption bands than would be predicted are
    found.
    The number of observed absorption bands may be increased by the
    presence of bands which are not fundamentals but combination
    bands, overtones, or difference bands.

    More often fewer absorption bands are identified.


    • It may happen to have frequencies of some vibrations so nearly
    alike that they are not separated by the spectrometer
    • Some fundamental bands may be so weak that they are not
    observed or are overlooked.
    IR Spectrum of Complex Organic Molecules
    Two types of vibrational modes are possible:
    1. Skeletal vibrations where all the atoms in the molecule move about to some
    extent.
    These vibrations give rise to absorption peaks in the range 400 – 1600 cm -1
    which is called the fingerprint region.

    1600 cm-1  400 cm-1: “fingerprint” region.


    Many bands of mixed origin. Some prominent bands are reliable.

    2. Functional group vibrations in which only the atoms in that functional group
    vibrate appreciably.
    Each functional group gives rise to an absorption peak at a characteristic
    frequency, no matter what the rest of the molecule contains. These peaks can be
    used to identify the functional groups present in the molecules.

    4000 cm-1 1600 cm-1: “functional group” region.


    Most of the stretching bands, specific functional groups
    (specific atom pairs).
    Characteristic Stretching Frequencies of some Molecular Groups
    Four Primary Regions of IR Spectrum

      osc = 1  k cm-1
    spectroscopic 2 c
    Larger k  higher frequency
    Larger  (large atomic mass)
     lower frequency
    The x-axis of the IR spectrum is in units of wavenumbers (cm-1):
    directly proportional to the energy of transition being
    observed
    The y-axis on an IR spectrum is in % transmittance
    Few specific examples
    Predicting the trend of stretching frequency
     Effect of bond order (directly proportional)
    k

    C C C C C C

     (cm-1) = 1200 1650 2150

     Effect of reduced mass (inversly proportional)

    C H C C C O C Cl C Br C I

     (cm-1) = 3000 1200 1100 750 600 500

     Effect of Hybridisation

    s character

    C C C C C C H

    H H

     (cm-1) = 2900 3100 3300


    Predicting the trend of stretching frequency
     Effect of resonance O
    O

    C C

     (cm-1) = 1715 1675-1680

     Intensity of the bands depends upon the magnitude of dipole moment associated
    with the concerned bond
    R

    C O R C N R C CH R C C R
    Strong Medium Weak No
    R

     Bending vibrations involve lower energy than stretching vibrations


    Streching Vibration: 3000 cm-1
    C H Bending Vibration: 1340 cm-1

     Asymmetric stretching involves a larger dipole moment, hence absorbs strongly at


    higher frequency than symmetric stretching
    Ring strain
    p-character of the C=C bond

     (cm-1) [C=Cstr] 1656 1566 1611 1646 1650

    C
    C
    C
    combination combination
    band band

    sp: 180 oC, sp2: 120 oC, sp3: 109 oC, sp>3: <109 oC
    Effect of ring size: Smaller the ring, higher is the absorption frequency

    O O O O O C O

    C=O str. (cm-1) 1705 1715 1745 1780 1815 2140

    Conjugation lowers the absorption frequency:

    O
    O O O H
    O O
    O O

    C=O str. (cm-1) 1715 1715 1695 1685 1680 1665 1640
    Bo

    H
    O O O O
    tautomerisation

    C=O str. (cm-1) 1723 1622


    1706 O-H str. 3200 - 2400 cm-1

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