Name: Chua Weijun Student No.

: U092451E Lab Group: We1

Email: U0902451@nus.edu.sg Date: 16/02/2011

CM2101 Laboratory Report

Experiment 4: Vibrational Spectroscopy

Aim

To obtain an infra-red spectrum of a liquid sample and to perform an energy optimization and vibrational frequency
calculation using Gaussian 03 software package.

Introduction

Spectroscopy methods are used in laboratory to determine the identity and structures of unknown compounds.
Due to the quantization of energy levels and the unique spectral patterns for different functional groups and bonds, the
structure of the compounds can be determined using pre-determined values obtained for specific groups. The source of
energy for the transitions is usually electromagnetic waves, which can cause transitions such as electronic and
rovibrational transitions.
Infrared radiation (750nm to 1mm) is used for this experiment in particular. The wavelength of radiation that
corresponds to the fundamental vibraitonal transitions in molecules occurs in the mid infrared range of 2.5µm to 25µm
(4000cm-1 to 400cm-1).

Compounds having covalent bonds are able to vibrate and rotate and the process of absorption of radiation is
quantized. As the sample is irradiated with infrared radiation, radiation that corresponds to the natural vibrational
frequency will be absorbed by the sample. The infrared radiation interacts with the molecule in the form of photons.
During the interaction, only photons with energy that corresponds to the transition energy between the energy levels
will be absorbed. The absorption of the photon will increase the ampliltude of the vibration of the molecule.
Similar bonds will absorb radiation that falls within a range of wavelength. However, similar molecular bonds in
different compounds will be in different chemical environment. The wavelength at which the bonds absorb will differ
slightly from each other. Thus, in addition to quantization of energy levels, each compound will have a unique
absorption spectrum under infrared radiation. This identity of the compounds can thus be deduced from the spectrum
obtained.

In the 3D space, each atom will be able to move in the three directions, namely, x, y and z-axis. This movement
of the atom, or particle, is known as translation. Thus, each independent atom will have degree of freedom of 3. The
degree of freedom of a polyatomic molecule and an atom is related such that the total degree of freedom of the
polyatomic is equivalent to the sum of the degree of freedom of the atoms (i.e. 3N, where N is the number of atoms in
the polyatomic molecule).
The degree of freedom of the polyatomic molecule, 3N, is further classified into translation, rotation and
vibration. Similar to an independent particle, the molecule will be able to translate in the three different directions, as
translation of the molecule is with respect to the centre of mass. A polyatomic molecule also has three rotational
degree of freedom (or two for linear polyatomic molecules). Therefore, each polyatomic molecule will have
vibrationall degree of freedom of 3N-6 (3N-5 for linear molecules).

The degree of freedom for vibration is observed using infrared radiation. However, not all vibrational modes are
infrared active. Vibrational modes which are able to cause a change in dipole moments of the molecules will be able
to absorb infrared radiation. Whereas for vibrational modes which are unable to cause a change in dipole moment will
not be able to absorb infrared radiation even if the frequency of the radiation matches the vibrational frequency of the
bond. Homonuclear diatomic molecules is an example of an molecule which will be infrared inactive due to the
existence of symmetric bonds.

The spectrum of the sample is obtained using a Fourier Transform Infrared (FTIR) spectrophotometer. In the
FTIR spectrometer, infrared radiation is passed through the sample. The amount of radiation absorbed at each
wavelength is recorded by the detector and a spectrum, of intensity against wavelength, is plotted. The lower the
intensity (or transmittance) would represent a larger amount of radiation absorbed at the wavelength. Therefore, the
low intensity at specific wavelength will indicate the presence of certain functional groups.
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Results and Calculations

1. Table of theoretical values and experimental values obtained from the Infra-red spectrum of CH 3OH

Peak Theoretical Freq /cm-1 Intensity Experimental Freq /cm-1 Peak Assignment
1 299.846 120.384 (Not observed) C-H bending
2 1036.9 121.074 1030 C-H bending, C-O stretching
3 1076.39 3.5589 1030 C-H bending, O-H bending
4 1170.24 0.3388 1120 C-H bending
5 1369.43 24.439 (not observed) C-H bending, O-H bending
6 1477.73 3.1618 1520 C-H bending
7 1496.75 3.4186 1520 C-H bending
8 1507.93 5.2969 1550 C-H bending
9 2993.56 62.4012 2950 C-H stretching (symmetric)
10 3041.16 55.5474 (Not observed) C-H stretching (asymmetric)
11 3111.03 24.669 (Not observed) C-H stretching (asymmetric)
12 3840.17 30.9477 3360 O-H stretching

2. Table of values obtained from the Raman Spectrum and Peak assignment

Peak Theoretical Freq /cm-1 Intensity Raman Activity Peak Assignment

1 299.846 120.384 No C-H bending
2 1036.9 121.074 1030 C-H bending, C-O stretching
3 1076.39 3.5589 No C-H bending, O-H bending
4 1170.24 0.3388 1120 C-H bending
5 1369.43 24.439 Yes C-H bending, O-H bending
6 1477.73 3.1618 Yes C-H bending
7 1496.75 3.4186 Yes C-H bending
8 1507.93 5.2969 Yes C-H bending
9 2993.56 62.4012 Yes C-H stretching (symmetric)
10 3041.16 55.5474 Yes C-H stretching (asymmetric)
11 3111.03 24.669 Yes C-H stretching (asymmetric)
12 3840.17 30.9477 Yes O-H stretching

Discussion

1. CH3OH, Methanol

The bonds present in methanol are 3 C-H, 1 O-H and 1 C-O bonds. As it is a non-linear polyatomic molecule, it
has vibrational degree of freedom of (3(6) – 6 =) 12, which is observed using the Gaussian software. However, as
mentioned, not all the vibrational modes are infrared active and thus was not observed in the spectrum obtained in the
experiment.

The C-H of the sp3 carbon of methyl is able to undergo the two modes of stretching and the four modes of
bending, as observed in the figures of the mode of vibration. Both theoretical peaks observed at 3111.03cm-1 and
3041.16cm-1 are peaks due to asymmetric stretching of C-H. As the asymmetric stretching does not cause any net
change in dipole moment, little or no infrared radiation will be absorbed at these wavelengths. Thus, the peaks are
absent in the experimental spectra.
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 In contrast, the symmetric stretching of the bond is IR active and can be observed at 2950cm -1, which is close to
the theoretical value given by Gaussian. Similarly, the series of C-H bending can be observed in the experimental
spectrum, at peaks centred at 1520, as compared to the position of C-H bending which occurs at a frequency of
1375cm-1 to 1450cm-1.

As observed from the table above, the experimental peak obtained for O-H stretching occurs at 3360cm -1, which
is well within the range for O-H stretching. However, the experimental value obtained is far lower than that of the
theoretical value obtained using Gaussian. This can be due to the extent of hydrogen bonding present in the alcohol,
which lowers value observed.
The peaks of both O-H stretching and C-O bending coincide with some bending modes of C-H bending. This
results in the observation of a single peak at 1030cm -1 in the experimental peak. This observation corresponds to the
literature values given to C-O-H bending (1220cm-1 to 1440cm-1) and C-O stretching (1000cm-1 to 1300cm-1).

2. Absorption Values

The absorption value of the vibration between two atoms is proportional to the square root of K, the force
constant, and inversely proportional to the square root of µ, the reduced mass.

As hydrogen is the smallest atom in the periodic table, any bonds which involve hydrogen will have a larger
absorption value. This can be verified by comparing the theoretical values given for both C-O stretching and C-H
stretching, which are approximately 1050cm-1 and 3000cm-1 respectively. In addition, the shorter bond length of C-H
as compared to C-O accounts for the higher force constant, due to the short atomic radius of the hydrogen atom.
However, an anomaly can be observed in this experiment as O-H stretching has higher absorption value as
compared to C-H even though O-H has a larger reduced mass than C-H. As a vibration mode must be able to cause a
change in dipole moments, the stretching of O-H will be able to cause a larger change in dipole moments as O is more
electronegative than C.

Force constant, K, is another factor which will affect the absorption value. A stronger bond will have a higher K
value. This can be observed by comparing the literature values for C=C (1600cm -1 to 1680cm-1) and C≡C (2210cm-1 to
2250cm-1). Another example can be between a sp2 and a sp3 carbon, of which a C-H bond of the former will give a
slightly larger absorption value.

Stretching vibrational modes will have a higher absorption value as compared to bending. This is due to the
extent of change in dipole moments. The bending mode will cause a smaller change in dipole moments as compared to
the stretching modes. During the molecular bending, the bond length remains the same, while the bond length changes
during stretching and thus accounting for the difference in change in dipole moments.
3. Raman vs IR Spectrum

A Raman spectrum is also obtained for the molecule using the Gaussian software. The main difference between
Raman spectrum and IR spectrum is such that a Raman active molecule experiences a change in polarisability, while
an IR active molecule experiences a change in dipole moments. As observed from the Raman spectrum, not all
vibration modes are Raman active. Similarly, not all vibration modes are IR active.
The point group of the molecule can be determined and the activity of the vibration mode can be determined
using the point group symmetry table. Vibration modes represented by irreducible that contains the normal modes
represented by single variable term, x, y and z are IR active. Whereas vibration modes represented by irreducible, that
contains the quadratic terms, eg. x2, are Raman active.

Conclusion

The prediction of the Gaussian software is accurate the

References

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