ABSTRACT:

The objective of this experiment is to demonstrate how computational chemistry can be utilized to calculate vibrational frequencies and intensities of alkenes. The accuracy of this technique is measured by comparing these results with data obtained experimentally, however, a scaling factor must be considered in order to adjust the computational values. An average scaling factor of 0.90 has been determined in our results, thus, demonstrating how the computer interface overestimates the values by approximately 10%. The computer interface, WebMO, does provide a list of all the possible absorptions of the molecules being analyzed, however, not all these absorption bands are observed in the simulated spectra.

INTRODUCTION:
Quantum mechanics is used to compute infrared spectral data which provides an alternative method to obtain chemical properties of compounds without using any expensive instruments or attending a laboratory for experimental processing. WebMO is the web-based interface used which performs the computational chemistry calculations for you from the comfort of using your home computer. All that is required from you is for you to build the three-dimensional molecular structure of the compound on the interface, and the program will do the rest of the work for you in simply a few seconds.

The C=C bond of ethene is analyzed by observing variational frequencies and intensities in computationally generated infrared spectra of various monosubstituted ethenes and how they relate to the experimental data. It is known, however, that there is an approximate 10% overestimate of computational wavenumbers calculated due to systematic errors. This overestimate in figures generally range between 0.8 and 1.0, depending on the compound and the quality of the calculation. This means that an empirical factor must be taken into account when converting computational frequencies to experimental data and vice versa. An advantage in using computational chemistry to calculate vibrational frequencies with the WebMO interface is that low intensity and even inactive vibrations can be animated, and located in the computed spectrum. This allows for a superior analysis of the molecule being studied with the determination of theoretical vibrational frequencies which may not be present in experimental spectral data.
3 2 1

RESULTS:
VIBRATIONAL DATA FOR ETHENE AND MONOSUBSTITUTED ALKENES

CALCULATED (C=C) COMPOUNDS Ethene H H H H

(cm-1)

INTENSITY

EXPERIMENTAL (C=C) BAND SCALING (cm-1) INTENSITY FACTOR 1620 Zero

1828.7779

Zero

0.89

Propene H H H H H H

1806.6002

Weak

1650

Weak

0.91

Vinyl Alcohol H H O H H Vinyl Amine H H N H H H

1830.6733

Strong

1660

Medium

0.91

1846.9062

Strong

1670

Medium

0.90

THEORETICALLY DETERMINED EXPERIMENTAL C=C BAND OF ISO-B UT E N EAND 2-B UT E N E C=C BAND (cm-1) Iso-Butene COMPOUNDS: H COMPUTATIONAL EXPERIMENTAL H 1880.39 1692.35 2-Butene H H 1890.22 1701.20

Average Scaling Factor Used = 0.90

INFRARED SPECTRA OF COMPOUNDS:

ETHENE:

PROPENE:

C=C
Weak

VINYL ALCOHOL:

C=C
Strong

VINYL AMINE:

C=C
Strong

DISCUSSION:
Ethene and its monosubstituted derivatives; propene, vinyl alcohol, and vinyl amine, are analyzed by determining vibrational frequencies and intensities of the C=C band by using computational chemistry and comparing these values with experimental data. Comparison with the experimental figures provided enabled the determination of the scaling factor to further have an indication of the accuracy of using computational chemistry to obtain spectral data. As mentioned previously, there is an approximate 10% overestimate when computationally calculating vibrational frequencies, therefore, a 10% discrepancy in results is expected between computational and experimental data. Using the average scaling factor obtained from the four ethenes, the theoretically determined experimental C=C band stretch of iso-butene and 2-butene is made possible. By observing the experimental data presented, a trend is observed where the addition of an alkyl group on ethene increases the vibrational frequency of the C=C stretch. The more substituted the alkene, the more stable it is. Ethene has a experimental

C=C stretch of 1620 cm . Substituting an H atom in ethene with a methyl, alcohol, and an amine group in propene, vinyl alcohol, and vinyl amine, increases the vibrational frequency to 1650, 1660, and 1670 cm , respectively. This can be hypothesized by the effect of having stronger C=C bonds due to electron delocalization and resonance effects by the presence of monosubstituted groups on ethene. Having a methyl group on ethene delocalizes electrons from the double bond by resonance effects resulting in a stronger bond. Vinyl alcohol and vinyl amine have -OH and -NH2 functional groups substituted on the ethene which further stabilizes this molecule by withdrawing electrons by resonance from the C=C bond. With the increasing electronegativity of the substituents, the wavenumber increases. As oxygen and nitrogen are both electronegative, they will both inductively withdraw electrons from the C=C bond further providing an increased stabilization of the molecule resulting in an increased vibrational frequency, therefore, requiring more energy to break the bonds. The resonance form of C=N in vinyl amine will have a higher wavenumber than the resonance form of C=O in vinyl alcohol since C=O has a higher reduced mass which lowers the frequency and the wavenumber of the molecule. In reality, the vinyl amine has a lower wavenumber than the vinyl alcohol, since the nitrogen has a greater tendency to share its lone pair of electrons, thus reducing
-1

-1

the double bond effect of the ethene and decreasing its absorption wavelength. This demonstrates how the computational method may not necessarily be ideal in calculating vibrational data. The theoretically determined experimental C=C stretch of iso-butene and 2-butene have been calculated to have wavenumbers of 1692.35 and 1701.20 cm , respectively. When comparing these values to the C=C stretch of 1650 cm of propene, the increase in frequencies are observed. This can be accounted by the fact that iso-butene and 2-butene both have an additional methyl group (disubstituted), when compared to propene, thus, providing even more stabilization by inductive and resonance effects. Additional cis-trans isomers delocalize the electrons even more strengthening the C=C bond and increasing the vibrational frequencies of the bond. Increased stabilization in 2-butene is resultant from the structural internal symmetry of the C=C bond, leading to decreased polarization and a higher energy required to break the bond (1701.20 cm . Isobutene contains germinal methyl groups increasing polarity requiring slightly less energy to break the C=C bond (1692.35 cm ). When ethene is substituted with a ethyl group, a band stretch is obtained at 1650 cm , however, when it is substituted with a vinyl group, a decreased band stretch at 1600
-1 -1 -1) -1 -1

cm is obtained. It is known that with additional alkyl groups the C=C bond is further stabilized resulting in an increase in vibrational frequency. However, in the case of ethene substituted with a vinyl group, a decreased frequency is observed. This is explained by the fact that conjugation present in the ethene substituted with a vinyl group will increase the single bond characteristic of the C=C bond, thus, weakening the bond and resulting in a decreased frequency. The vibrational frequency of the C=C stretch of ethene is computationally calculated to an overestimated value of 1828.7779 cm having a scaling factor of 0.89, when compared to the experimental stretch of 1620 cm . The vibrational frequency of the C=C stretch of propene is computationally calculated to an overestimated value of 1806.6002 cm having a scaling factor of 0.91, when compared to the experimental stretch of 1650 cm . The vibrational frequency of the C=C stretch of vinyl alcohol is computationally calculated to an overestimated value of 1830.6733 cm having a scaling factor of 0.91, when compared to the experimental stretch of 1660 cm . The vibrational frequency of the C=C stretch of vinyl amine is computationally calculated to an overestimated value of 1846.9062 cm having a scaling factor of 0.90, when compared to the experimental stretch of 1670 cm . The scaling factors between the experimental and
-1 -1 -1 -1 -1 -1 -1 -1

-1

computational data have averaged to a scaling factor of 0.90. This further confirms the fact that computational chemistry overestimates wavenumbers by approximately 10%. Computational chemistry accurately approximates band stretches, however, an empirical factor must be accounted to obtain corrected experimental band stretches. The absorption within 1000 and 800 cm are referred to as the fingerprint region where out of plane bending vibrations occur, such as twisting and wagging. For nonlinear molecules with N atoms, 3N-6 amount of vibrations are expected. For linear molecules with N atoms, 3N-5 amount of vibrations are expected. Ethene has 6 atoms, therefore, 3(6)-6 = 12 stretching vibrations are expected. In the simulated spectrum only 2 vibrations are observed. Vinyl alcohol has 7 atoms and (3(7)-6 = 15 amount of vibrations are expected, however, not all these absorptions are observed in the simulated spectrum. For ethene, the peak corresponding to -CH stretch is observed and for vinyl alcohol the peaks observed were the C=C, -C-H, -OH, and -C-O. As ethene is a symmetrical compound, only one absorptions id observed in the simulated IR spectrum. All the vibrations occurring in the symmetric molecule are cancelling each other out. Propene contains an additional methyl group as one of the substituents on ethene, which is not creating a large enough dipole moment for absorption to occur, and can be
4 -1

observed to have only one peak as well on the simulated spectrum. Due to the fact that vinyl alcohol and vinyl amine both contain electronegative atoms, oxygen and nitrogen, presence of polarization in the molecule causes it to have more absorption in the IR spectrum.

CONCLUSION:
Computational chemistry enabled the calculation estimations of vibrational frequencies and intensities, however, a 10% overestimation is present in the calculated values which are required to be adjusted in order to be comparable to the experimental absorptions. This method also does not consider interactions of the molecules at the molecular level, as oxygen and nitrogen are both electronegative atoms, but they also

have the ability to share their lone par of electrons inductively which also influence the absorption frequencies and are atomic characteristics that must be accounted when applying computational chemistry to obtain data. The IR spectra simulated do generate a list of all the absorptions possible within a molecule, however, not all the absorption bands are present in the simulated spectra, and we have seen how structural symmetry decreases the amount of absorption bands present in the simulated spectra due to the lack of polarization of the molecule. Computational chemistry may provide absorption estimations that must be scaled before accounting them as acceptable values, however, to obtain accurate analysis and data of absorptions frequencies, perhaps utilizing an IR instrument and performing experimental chemistry may be the best option available for spectral analysis.

REFERENCES:
1, 2, 3

Laboratory Manual, Chem 393 Spectroscopy and Structure of Organic Compounds,

Prepared by Dr. T.J. Adley and F. Nudo, Modified by Dr. H.M. Muchall, Department of Chemistry and Biochemistry, Concordia University. (pp.11-13)

Introduction to Spectroscopy, Pavia, Lampman, Kriz, Third Edition, Washington, 2001.

(p. 68-75)