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    Spectroscopy ExerciseCollection Unit 2

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    David Gorriz Badia
    1. The document discusses vibrational spectroscopy and infrared and Raman spectra of various molecules. It provides problems involving determining vibrational frequencies, force constants, dissociation energies, and symmetry analysis of normal modes of molecules like HI, CO, NO, HF, ethylene oxide, formaldehyde, and transition metal complexes. 2. Symmetry and coordination of ligands like chromate and sulfate are analyzed from their vibrational spectra in different complexes. IR and Raman spectra are interpreted to assign normal modes and deduce structural information. 3. Problems involve calculating vibrational levels, dissociation energies, identifying fundamental, overtone and combination bands, and relating spectra to molecular structures.

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    © All Rights Reserved
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    Spectroscopy ExerciseCollection Unit 2

    Uploaded by

    David Gorriz Badia
    84 views6 pages
    1. The document discusses vibrational spectroscopy and infrared and Raman spectra of various molecules. It provides problems involving determining vibrational frequencies, force constants, dissociation energies, and symmetry analysis of normal modes of molecules like HI, CO, NO, HF, ethylene oxide, formaldehyde, and transition metal complexes. 2. Symmetry and coordination of ligands like chromate and sulfate are analyzed from their vibrational spectra in different complexes. IR and Raman spectra are interpreted to assign normal modes and deduce structural information. 3. Problems involve calculating vibrational levels, dissociation energies, identifying fundamental, overtone and combination bands, and relating spectra to molecular structures.

    Original Description:

    Ejercicios de espectroscopia nivel de grado segundo año, en Química.

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    1. The document discusses vibrational spectroscopy and infrared and Raman spectra of various molecules. It provides problems involving determining vibrational frequencies, force constants, dissociation energies, and symmetry analysis of normal modes of molecules like HI, CO, NO, HF, ethylene oxide, formaldehyde, and transition metal complexes. 2. Symmetry and coordination of ligands like chromate and sulfate are analyzed from their vibrational spectra in different complexes. IR and Raman spectra are interpreted to assign normal modes and deduce structural information. 3. Problems involve calculating vibrational levels, dissociation energies, identifying fundamental, overtone and combination bands, and relating spectra to molecular structures.

    Copyright:

    © All Rights Reserved
    Download as PDF, TXT or read online from Scribd
    Download as pdf or txt
    84 views6 pages

    Spectroscopy ExerciseCollection Unit 2

    Uploaded by

    David Gorriz Badia
    1. The document discusses vibrational spectroscopy and infrared and Raman spectra of various molecules. It provides problems involving determining vibrational frequencies, force constants, dissociation energies, and symmetry analysis of normal modes of molecules like HI, CO, NO, HF, ethylene oxide, formaldehyde, and transition metal complexes. 2. Symmetry and coordination of ligands like chromate and sulfate are analyzed from their vibrational spectra in different complexes. IR and Raman spectra are interpreted to assign normal modes and deduce structural information. 3. Problems involve calculating vibrational levels, dissociation energies, identifying fundamental, overtone and combination bands, and relating spectra to molecular structures.

    Copyright:

    © All Rights Reserved
    Download as PDF, TXT or read online from Scribd
    Download as pdf or txt
    of 6

    Spectroscopy

    Code: 102531

    II. VIBRATIONAL SPECTROSCOPY

    1. The infrared spectrum of HI shows a fundamental vibrational band at 2230 cm-1.


    Determine: (a) the fundamental vibrational frequency, in s-1, (b) the bond force
    constant and (c) the zero-point energy, assuming that this molecule behaves like a
    harmonic oscillator.

    2. Determine the proportion of CO molecules present in the vibrational level = 1


    with respect to those in level = 0, supposing that there is thermal equilibrium, at
    temperatures of 500 K, 750 K and 1000 K. The fundamental vibrational frequency
    is 2143 cm-1.

    3. The 14N16O molecule has an intense absorption band at 1876.06 cm-1 and a weak
    one at 3724.20 cm-1 ascribed to the first overtone. Use this data to find out the bond
    force constant, the vibrational frequency and anharmonicity constant. How much is
    the zero-point energy? Using the formula for the vibrational levels, estimate the
    value of the dissociation energy of the molecule.

    4. The spectrum of 1H19F presents an intense line at 3961.64 cm-1, and the equilibrium
    vibrational frequency is 4138.52 cm-1. Determine the dissociation energy of 1H19F.

    5. The fundamental harmonic frequency of 12C16O has been obtained from quantum
    mechanical calculations and is 2202.6 cm-1. The anharmonicity constant obtained
    through the same procedure is 4.48x10-3. Answer the following questions:
    a) What is the value of the zero-point energy (ZPE)?
    b) Compute the frequencies at which the fundamental band and the first overtone
    will be seen.
    c) What values would the same absorption bands have for the isotopologue 12C18O?
    Data: Atomic masses: 12C = 12.000 amu, 16O = 15.995 amu.

    6. The harmonic frequencies ̅ of 12C16O and 1H35Cl are 2202 and 2939 cm-1,
    respectively. Their respective anharmonicity constants are 0.005 and 0.02. With
    these data, and whenever necessary using their atomic masses approximated to be
    integer, answer the following questions:
    a) Find the values of the force constants of both molecules.
    b) Estimate the vibrational level at which the dissociation will occur for both
    molecules (Hint: in the anharmonic oscillator model, energy levels get closer
    as the quantum number grows until they become degenerate. Thus, the
    dissociation level can be estimated as the level where two consecutive states
    have the same energy, or in other words, the transition diss + 1 ← diss has
    zero energy).
    c) Estimate now the chemical dissociation energy of both molecules, .
    d) Now, use your results concerning force constants, dissociative state number
    and dissociation energy to discuss which of the two molecules has the
    strongest bond. Do all results agree? Do you have any chemical information on
    the structure that agrees, or disagrees, with your conclusion?

    7. The vibrational frequency of the HF molecule is 4136 cm–1. At 25 ºC the most


    intense transition on the R band is the 3 ← 2 transition, and the least intense that is
    still observed is the transition 8 ← 7.

    a) Draw a schematic representation of the ro-vibrational spectrum of this


    molecule. Mark on the plot what lines correspond to the P and R branches,
    along with their frequencies.
    b) What is the most intense P line?
    Data: = 18.3 cm-1 , = 17.5 cm-1

    8. Find the symmetry elements of the following species and determine the point group
    to which they belong.

    1) WF5Cl 2) SF4
    3) SiH3(CN) 4) PF5
    5) 1-chloro-3,5-difluorobenzene 6) cis-[PtCl2(NH3)2]
    7) trans-[PtCl2(NH3)2]

    9. Find the symmetry elements and the point group of the main conformers of
    butadiene.

    10. Using ethylene oxide (C2H4O) as a test molecule, determine the multiplication table
    for group C2v:
    C2v E C2(z) σv(xz) σv’(yz) First operation

    E
    z
    C2(z) O
    x
    σv(xz) C C
    H H
    H H
    σv’(yz)

    Second operation
    a) Are all H atoms equivalent in C2H4O?
    b) According to the table, is this group commutative (Abelian)?
    11. Consider the character table for C4v (below, on the left). Check that the
    corresponding direct product table (on the right) is correct and fill in the missing
    representations:
    C4v E 2C4 C2 2σv 2σv’ C4v A1 A2 B1 B2 E

    A1 1 1 1 1 1 A1 A1 A2 ? ? ?

    A2 1 1 1 –1 –1 A2 A2 ? B2 ? E

    B1 1 –1 1 1 –1 B1 ? B2 A1 ? E

    B2 1 –1 1 –1 1 B2 B2 ? A2 ? ?

    E 2 0 –2 0 0 E ? E E ? A1+A2+B1+B2

    a) In terms of Γ x Γ direct products: what can be said about the first representation
    in all character tables (in this example A1)?
    b) What can be said about the diagonal elements of the direct product table? (e.g.
    B1xB1= A1)

    12. The formaldehyde molecule (H2CO) has a total of six normal modes of vibration
    with the following frequencies:

    , / cm-1 1215 1281 1547 1861 2909 2969


    Produce a list of all lines, irrespective of their intensities, that would be observed if
    strong IR radiation were used to analyze the vibrational spectrum of formaldehyde
    via absorption, and identify the transitions, classifying them as overtones,
    combination bands and fundamental bands. Assume that your radiation source
    spans the range between 100–3000 cm-1. Can you predict, based on what you know,
    what the fundamental frequencies would be for D2CO?

    13. Again for the formaldehyde molecule: do a symmetry analysis to find out the
    symmetry species of all the normal modes (hint: start off the Γ ). Find now the
    symmetry species of the C—H stretchings. Can you propose, based on the
    symmetry of the latter, what form might these stretchings take?

    14. The chromate anion can act as a counterion and as a mono- and bidentate ligand. In
    the two latter cases it forms, in fact, polynuclear complexes, for instance:

    K2CrO4 [Cr(CrO4)(NH3)5]NO3 [Cr(CrO4)(NH3)4]ClO4


    a) Determine, in each of the above cases,
    the number of allowed bands that are
    associated to the stretching vibrations
    (Cr—O).
    b) On the right, the spectra (a,
    ( b, c) of three
    species containing the chromate ion are
    represented (in particular, the region
    where the stretching Cr—O
    Cr vibrations
    appear is shown). Work out the
    behavior, as concerns coordination
    mode, of the chromate ion in each case.

    15. The IR spectrum of complex salt


    [NEt4][MnI2(CO)4] presents, in CH2Cl2
    solution, four bands in the region where
    the CO stretching vibrations do normally
    occur (roughly around 2000 cm-1). What
    can be deduced about the structure of the
    complex?x? (Hint: think of the possible
    environment variations of the manganese
    and work out the symmetry of the CO
    stretchings in the corresponding
    symmetry point group(s))

    16. The figure shows the region of the IR spectrum


    associated to the stretchings of the sulphate
    sul
    anion for three Co(III) complexes that contain it.
    The
    he frequencies of the vibrational modes of
    SO42- as a free ligand are: ν(A1)=983 cm-1, ν
    (E)=450 cm-1, ν (T T2)=1105 cm-1 and ν (T2)=611
    -1
    cm . Relate each of the spectra (solid line,
    dot-dashed
    dashed line and dotted line) with the
    structure of the corresponding complexes.
    17. The vibrational IR and Raman spectra of ethylene oxide present the following
    bands between 1000 cm-1 and 4000 cm-1:
    1120
    IR 3079 - 3019 3005 1490 1470 - 1270 1153 1143
    1120
    Raman 3080 3063
    63 3020 3005 1490 1470 1345 1266 1150 1140
    Indicate the frequencies and symmetries of the vibrational modes ν(C—H). Try to
    assign the bands at 3063 cm-1 and 3005 cm-1. (Hint: again, start working out the
    symmetry of the C—HC H stretches. You might have to make assumptions based on
    the likely value range
    nge of the C—H
    C stretching frequencies).

    18. Consider the following four out-of-plane


    out
    motions of XeF4 (square planar) represented by
    the vectors shown on the figure. Answer the
    following questions:

    a) Which symmetry species do these motions


    belong to?
    b) Two of thee motions shown are global
    rotations of the whole molecule. Identify
    them by means of their symmetry species
    and the character tables and comment briefly on their relative energy.
    c) Two of the shown motions are out-of-plane
    out bending vibrations. Identify them.
    d) Which of the two bending vibrations will be observed
    observed in the IR spectrum?
    e) Which of the two bending vibrations will be observed
    observed in the Raman spectrum?

    19. The IR spectrum of [Os(NH3)4(N2)2]2+, I,, is shown in Figure A, and those of dimers II
    and III are shown inn Figure B (see below).

    (I)

    (II) (III)
    Figure A (IR spectrum) Figure B (IR spectrum)

    Answer the following questions:


    a) Determine the point group of the four Os complexes depicted above.
    b) Based on the appearance of the N≡N stretching region (≈ 2000 cm-1) shown in the
    IR spectrum in Figure A: Is complex I cis or trans? How many bands would you
    expect in that region for the vibrational Raman spectrum of both cis and trans
    isomers of complex I? Reason your answers by means of group theory.
    c) Focus now on Figure B and assign each of the superimposed spectra (dashed and
    solid lines) to one of the dinuclear species II or III. In order to do that, consider
    the N≡N stretching region (≈ 2000 cm-1) in terms of local symmetry (local
    symmetry means just considering the whole surroundings of the N≡ N bond as a
    “superatom”, i.e. your molecule is now of the type X—NN—Y (with X and Y
    taken as structureless atoms). Reason your assignment by means of group theory.
    d) Would vibrational Raman spectroscopy based on the same N≡N stretching region
    also be a good tool to discern between complexes II and III? Reason your answer
    by means of group theory.
    e) Compare the stretching frequencies of N2 when acting as terminal and bridging
    ligand. Theorize about the origin of the differences.

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