Symmetric Stretching Frequencies and Force Constants From Raman Spectroscopy and Ab Initio Calculation

Symmetric stretching frequencies and force constants
from Raman spectroscopy and ab initio calculation
References:
Physical Chemistry, Silbey, Alberty & Bawendi 4th edition 2005 Chapter 10, & 13
Introduction
When light is incident on a sample, a small proportion of the light may be scattered as
depicted in Figure 1:
Scattered light
Incident light Transmitted light

Sample
Figure 1: When light is incident on a molecular sample, a small portion may be scattered.
Of the light that is scattered, most has the same frequency as the incident light. This is
Rayleigh scattering (and is the mechanism which gives the sky its blue colour), however
a small proportion of the scattered light has a frequency which is lower than that of the
incident light (Stokes shift), and a still smaller proportion is scattered to higher
frequency (anti-Stokes shift). The difference in energy between the incident and
Stokes/anti-Stokes light corresponds to vibrational energy level spacing in the sample
molecules as shown in Figure 2.
Excited electronic state
Incident light Scattered light
Ground electronic state Vibrational states Δv

Δv
Rayleigh scattering Stokes scattering anti-Stokes scattering
Figure 2: Changes in vibrational state associated with Stokes and ant-Stokes scattering
An early observer of the frequency shift in the scattered light was Sir Chandrasekhara
Venkata Raman. Modern-day Raman spectroscopy is a powerful vibrational
spectroscopy tool which can be used to probe chemical bonding. As a form of
vibrational spectroscopy, Raman spectroscopy can give similar information to infra-red
spectroscopy. Crucially however the selection rules for infra-red and Raman
spectroscopies are different: In infra-red spectroscopy a transition between vibration
levels is only allowed if that transition causes a change in the molecular dipole; in
Raman spectroscopy the frequency shift is only observed if the resulting change in
vibrational level causes a change in the molecular polarizability. Thus vibrational
modes occur at the same energies in infra-red and Raman spectra, but often with very
different intensities: bands that are strong in the infra-red spectrum may be weak in the
corresponding Raman spectrum and vice versa.
In this experiment Raman spectroscopy is used to investigate the symmetric stretch in

a selected series of tetrahedral oxyanions:
X
O O
O
Figure 3: Symmetric stretching mode of a tetrahedral oxyanion
As seen in Figure 3 (and better visualized by software used in the experiment), for a
tetrahedral molecule changing the vibrational state of the symmetric stretching mode
does not change the molecular dipole but does change the molecular polarizability.
Therefore, for such a molecule, the symmetric stretching mode does not appear in the
infra-red spectrum but appears as a strong band in the Raman spectrum. Further, since
the central atom does not move during this motion, the vibrational frequency (υ)
depends only on the mass of the oxygen atom (mO) and the X-O bond strength (force
constant, k). The appropriate equation is given by Equation 1:
Equation 1
1
2
Equation 1 can be readily rearranged to give Equation 2:
Equation 2
Finally, switching from SI units and using mO = 15.995 amu, and υ in units of cm-1,
gives Equation 3 which enables the force constant to be calculated from the measured
frequency
Equation 3
5.829 10 where k will have units Nm

Force constants may also be conveniently predicted from ab initio quantum mechanical
calculations which then allow vibrational spectra to be simulated. For the anions
investigated here, the Hartree-Fock level of theory, with a suitable basis set, provide
sufficient accuracy at low computational cost.
Method
Using the handout ab initio frequency calculations of oxyanions as a guide, create a
Gaussian input file to perform an optimization + frequency calculation for a perchlorate
ion at the HF/DGDZVP level of theory. Ensure that the model has been symmetrized
to tetrahedral, Td, symmetry and that the option to calculate the Raman spectrum has
been selected. Submit the calculation to Gaussian. When the calculation is finished
open the output file with GaussView and use the software to display the simulated ir
and Raman spectra. Record the frequency of the symmetric stretching mode. Use the
software’s animation feature to confirm your assignment of the correct mode. Open
the output file with a text viewer such as notepad, find the details of the symmetric
stretching mode and record the calculated force constant (in units of mDyne/A).
Repeat these procedures for perbromate and periodate ions, each time record the
frequency and force constant predicted for the symmetric stretching mode.
Saturated solutions of NaClO4 (aq) and NaIO4 (aq) have been provided. Record the
Raman spectra of each and using the simulated spectra as a guide identify the symmetric
stretching modes and record their frequencies. Using the observed frequencies,
calculate the force constant in each case.
Compare frequencies and force constants obtained from the spectra with those from the
Hartree-Fock calculations. Compare values for perchlorate, perbromate and periodate
ions and comment on any trend noticed. The synthesis of perbromate compounds is
much more difficult than for perchlorate or periodate compounds and so the perbromate
Raman spectrum was not recorded as part of this experiment. Based on the other values
you have, do you expected your calculated values for the perbromate ion to be reliable?

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Symmetric Stretching Frequencies and Force Constants From Raman Spectroscopy and Ab Initio Calculation

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Symmetric stretching frequencies and force constants

from Raman spectroscopy and ab initio calculation

Incident light Transmitted light

Excited electronic state

Incident light Scattered light

Ground electronic state Vibrational states Δv

In this experiment Raman spectroscopy is used to investigate the symmetric stretch in

Figure 3: Symmetric stretching mode of a tetrahedral oxyanion

5.829 10 where k will have units Nm

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