Jordan Mahoney

Partner: Ryan Anderson

Chem 334

Date Performed: 10-03-2017

Date Turned in: 10-17-2017

Raman Spectroscopy of Carbon Tetrachloride

Purpose:

A plot of intensity of scattered light versus energy difference is a Raman spectrum, this is

what is to be studied in this particular lab. The purpose of this lab was to understand and use the

Raman spectrometer and how using it to measure the polarization of molecule is done by

inducing a dipole moment from the generation of a magnetic field.

Procedure:

The samples of cyclohexane and carbon tetrachloride were prepared and Since the Raman

Spectrometer had already been turned on it did not need the 5-minute warm up before use. Once

in the program COM4 was selected as the spectrometer port. The sample of cyclohexane was

placed inside the sample holder. At first, 1s for integration time was selected 10 acquired spectra

with polarization turned off, and then continuous was clicked, there was noticeable noise.

Integration time was bumped up to 25s and 10 spectra to acquire was set. The best was chosen.

This was done under the same parameters for the carbon tetrachloride. The integration time was

then set to 40s and 6 spectra to acquire was set. These parameters were done for both non-

polarized and polarized and the best data set was selected for calculations.
Data:

The original spectrum of cyclohexane was taken to get the parameter readings needed for the

Raman.

Figure 1: Raman Vibrational Spectrum of Cyclohexane

Using the graph below generated by the NuSpec, the wavenumber for each peak could be found.

These wavenumbers correspond to v1, v2, v3, and v4. Using this graph v1 was found to be 456cm-1

with v2, v3, and v4 being 216, 787, and 311 cm-1 respectively.

Figure 2: Raman Spectrum of Nonpolar CCl4

The polarized spectrum of carbon tetrachloride was also taken shown below. In this graph the

wave numbers of each peak are about the same, however the intensity and width of the peak

changes between the two graphs. The polarized spectrum also has a much noisier baseline

compared to the peaks.

Figure 3: Raman Spectrum of Polarized CCl4

Calculations:

Using the two equations below, v1 and v2 could be found theoretically.

k
4 π 2 v 21= (Equation 1)
mcl

k delta
4 π 2 v 22=
( m3 )(
cl l2
) (Equation 2)

k delta
These equations can also be used to determine the values of K and . For this case K was
l2

calculated to be 4.806*10-16 N/m and 3.581*10-16 N/m respectfully. Using these values Equations

3 and 4 were calculated as seen in Table 1.

4 mCl 8 mCl 2 kδ
(
4 π 2 ( ν 23 + ν 24 ) = 1+
3 mC )( ) (
k
2 mCl
+ 1+
3 mC mCl )( )( )
l2
(Equation 3)
 8 mCl kδ
(
16 π 2 ( ν 23 ν 24 ) = 1+
3 mC )( )( )( )
k
mCl
2
mCl l
2 (Equation 4)

Value Comparison from Different Equations

Equation 2 3.581*10-16 N/m
Equation 3 2.106*10-16 N/m
Equation 4 3.81*10-18 N/m
Standard Deviation 1.77923*10-16 N/m
Table 1: Value Comparisons

The values of v1, v2, v3, and v4 for carbon tetrachloride can also be calculated theoretically using

GaussView. Below is a table with the theoretical wavenumbers for v1 through v4 using the

Hartree-Fock Method and the MP2 Method.

GaussView Calculated Results

Hartree-Fock Method Frequency (cm-1)
ν1 436
ν2 220
ν3 815
ν4 311
MP2 Method
ν1 515
ν2 227
ν3 880
ν4 328
Table 2: Gaussview Calculated Results

The numbers between the two methods vary slightly for all of the values of v with the MP2

values all being higher than the H-F method. These theoretical values can also be compared with

the values obtained using the experimental results and the literature values show below.

Experimental Raman Band Frequencies

Band Value Wavenumber (cm-1)
ν1 456
ν2 216
ν3 787
ν4 311
Literature
ν1 456.6
ν2 218.0
ν3 791.0
 ν4 314.0
Table 3: Experimental Raman Band Frequencies

Error Analysis:

The numbers found from using the peaks in Figure 2, were compared the literature values, the

Hartree-Fock Method, and the MP2 methods calculated frequencies, a percent error was

calculated to understand the difference.

Experiment Literatur Literature % MP2 % H-F %

al e MP2 H-F Error Error Error
11.456310
456 456.6 515 436 0.131406045 7 4.587156
4.8458149
216 218 227 220 0.917431193 8 1.8181818
10.568181
787 791 880 815 0.505689001 8 3.4355828
5.1829268 0.3205128
311 314 328 312 0.955414013 3 2
Table 4: Percent Errors Calculations

As seen in Table 4, the method that was the most different from the other values were the MP2

values, they gave not only the largest percent error for the experimental results but were also the

most different from all the results.

Discussion:

Compared to the literature values, our experimental data was very close with v1 only

being 0.13%, v2 being 0.91%, v3 being 0.50% and v4 being 0.955% off. With all the values being

less than 1% off of the literature values, the experimental values are considered nearly equivalent

to the literature values. This not only showed accuracy but also precision. When comparing the

experimental values with the H-F method values v1 through v4 are 4.58%, 1.82%, 3.43%, and

0.32% different. Once again, the experimental values are within the 5% margin of error, showing
once again the experimental results are accurate. When the values are compared to the MP2

method values the percent difference between the results were 11.5%, 4.8%, 10.57% and 5.2%

off. When these values are compared the experimental data is not statistically accurate due to

being above 5% margin of error. This is not unexpected however when looking at the data on a

whole. All of the values for MP2 are higher than the values calculated using the H-F method. In

turn the experimental values of v2, v3, and v4 for less than the values for v2, v3, and v4 for the H-F

method, with the experimental v1 only being slightly above the value calculated by the H-F

method. When comparing the experimental and H-F methods the increase is slight enough that

the experimental results still fall in the experimental error range of 5%. However, when the

values increase again when compared to the MP2 method, they increase too much for the percent

difference to stay within the accepted 5% margin.

To conclude the experimental values for v1, v2, v3, and v4 were all within the 5% margin

of error when compared to the provided literature values and the H-F method of theoretical

calculation. Even though the experimental values were not within the 5% margin when compared

to the MP2 method for theoretical calculation, the experimental values are shown to be accurate

results.

References:

A. Tokmakoff,* M. J. Lang, D. S. Larsen, and G. R. Fleming*, V. Chernyak and S. Mukamel,

Phys. Rev. Lett.79, 2702, (1997).

Garland, Carl. Experiments in Physical Chemistry. 7th Edition. (McGraw-Hill Publishing

Company, 2003)

Howell G. M. Edwards, John M. Chalmers, Raman Spectroscopy in Archaeology and Art

 History, Royal Society of Chemistry, 2005

Scudiero, Louis. “Raman Spectroscopy: vibrational spectrum of Carbon Tetrachloride (CCl4)”

September 20, 2016.

Hartree-Fock Method:

Figure 1. ν1 Figure 5. V2

Figure 2. V3 Figure 7. V4
MP2 Method:

Figure 8. V1 Figure 9. V2

Figure 10. V3 Figure 11. V4