3 Potential of bond stretching for the three ab initio levels of theory The graphs below confirm the DVZ is the best level of theory. Check if there is any leftover H2O/D2O mixture from a previous experiment. The different sections of the input file are explained in reference 6. and G.L. Through an understanding of quantum mechanics, information about the nature of a chemical can be deduced. Flush the cell for at least 10 min and then test whether the gas contains any acid by placing the end of the exhaust tube in a fresh indicator solution. The spectrum of HCl shows two separate peaks, one for the each of the two isomers of chlorine. Vibrational spectroscopy only works if the molecule being observed has dipole moments. ;  Freeman: New York, 2006; p. 36.1-36.14. Taking the diatomic molecule HCl, if the hydrogen is replaced by its isotope deuterium, µ is doubled and therefore νe will be decreased by √2. Hehre, W. J. in Engel, T. and Reid, P. Physical Chemistry; Benjamin Cummings: San Francisco, CA, 2006; p. 597-655. You will be prompted to obtain a background. VIBRATION-ROTATION SPECTROSCOPY OF HCl Remove the serum stopper from one end of the drying tube and connect it to the apparatus using a short piece of tubing. B.; Adamo, C.;  Jaramillo, J.; Gomperts, R.; Stratmann, R. E.; Yazyev, O.; Austin, A. J.; Cammi, R.; Pomelli, C.; Ochterski, J. W.; Ayala, P. Y.; Morokuma, K.; Voth, G. A.; Salvador, P.; Dannenberg, J. J.; Zakrzewski, V. G.; Dapprich, S.; Daniels, A. D.; Strain, M. C.; Farkas, O.; Malick, D. K.; Rabuck, A. D.; Raghavachari, K.; Foresman, J. momentum leads to selection rules for the change in vibrational and rotational quantum numbers. H 2 O. ONF. Energy transitions from the spectra were plotted vs. frequency, from which several physical constants were determined. HCN. O 2. There must also be a figure showing your fit of the wavenumber of each 1H-35Cl transition as a function of m.1  There must also be a representative figure showing the fit of the computational results as described in reference 6. CH 2 O. HCO 2 H. CH 4. Figure 2. Deuterium substitution leads to an isotopic ratio of 1.35-1.41 for the frequencies corresponding to the hydrogen/deuterium vibrations. B1 1.2694990. Cl 2 O. CH 2 Cl 2 (Details Available) C 2 H 2. Once the flow has been returned to a low level open the gas cell’s inlet stopcock and then open the stopcock leading to the indicator solution. Glossary . The experimental values were compared against literature values, the percent errors are shown below in Table 5: Table 5:  Percent Errors for the constants. It is modified slightly from a similar apparatus described in the literature.5 The whole apparatus will be flushed with nitrogen before and after use on a Schlenk line in the hood. The vibrational temperature is used commonly when finding the vibrational partition function. Vibrational Spectra of Diatomic Molecules ... HCl: 8.66: 480: HBr: 7.68: 384: HI: 6.69: 294: CO: 6.42: 1860: NO: 5.63: 1550 * From vibrational transition 4138.52 cm-1 in Herzberg's tabulation. It is advised that you not try to do the peak picking in Excel as it is extremely tedious. The gross selection rule for such transitions states that the molecule will exhibit a pure rotational absorption spectrum only if the molecule possesses a permanent dipole moment” [1]. SPARTAN ignores the corrections due to rotational motion, and so the values calculated for the vibrational frequency correspond roughly to the position of the Q-branch. When you make these changes be sure to pay close attention to spaces and blank lines; they are very important and a misplaced space can lead to very unexpected results. Discuss any relevant differences. Atkins, P. W. and de Paula, J. [2] University of South Carolina, Department of Chemistry and Biochemistry. You also do not need to be concerned with any statistical mechanical calculations. Do not get water anywhere near the IR cell windows! Carefully add small portions of water to destroy any remaining SOCl2. Close both of the cell’s stopcocks. Close the gas cell’s other stopcock and disconnect the cell from the drying tube. Mayer, S. G.; Bard, R. B. and Cantrell, K. J. Chem. If there is none, prepare it as described in reference 6. Br 2. Where a=v0, b=-2(αe–Be ), c=-αe and d=-4De. Click here to view instructions on Schlenk line operations. The spectra of HCl and DCl were used to create separate plots of the m transition with corresponding wavenumber. Born-Oppenheimer Approximation • Max Born (December 11, 1882 – January 5, 1970) was a German physicist and mathematician. Figure 3. 660-785-4000, http://www.webmo.net/download/WebMO_Users_Guide.pdf, Accommodations for Persons with Disabilities. 5. 2. In this exercise you will be evaluating whether the Morse potential is a sufficiently good model for the single vibration of the HCl molecule. e e e e e − − − − − α ~ Infrared absorption or emission can only occur at allowed transition levels • Vibrational: ν”= 0, ν’= 1 • Rotational: Δ. J = ± 1 • R and P branches • Spacing between peaks. This is not a problem, unless the flow is so high that mineral oil is splashed out of the bubbler. However, you must thoroughly rinse the syringe and the needle with distilled water and then with methanol within a few minutes of finishing the addition of the H2O/D2O mixture to the SOCl2. Note that you do not need to discuss the He results in the main body of the report, but the results and some analysis should be included in the supplemental material. Enhanced Intensity Distribution Analysis of the Rotational–Vibrational Spectrum of HCl. Each peak, differentiating between 35Cl and 37Cl, is assigned an m value and then plotted with wavenumber vs. m value. Shoemaker, D. P.; Garland, C. W. and Nibler, J. W. Experiments in Physical Chemistry, 7thEd. This method of describing a rotating molecule consists of two particles connected by a rigid bond. 2 and click OK. Isotope Effect: mass difference between atoms effects the vibrational and rotational energies • Splitting of peaks (35. HI. A.;  Vreven, T.; Kudin, K. N.; Burant, J. C.; Millam, J. M.; Iyengar, S. S.; Tomasi, J.; Barone, V.; Mennucci, B.; Cossi, M.; Scalmani, G.; Rega, N.; Petersson, G. A.; Nakatsuji, H.; Hada, M.; Ehara, M.; Toyota, K.; Fukuda, R.; Hasegawa, J.; Ishida, M.; Nakajima, T.; Honda, Y.; Kitao, O.; Nakai, H.; Klene, M.; Li, X.; Knox, J. E.; Hratchian, H. P.; Cross, J. ICN. CO 2. Increase the flow to about 10 bubbles of nitrogen per second passing through the Schlenk line’s input bubbler (there should be little if any nitrogen flow through the Schlenk line’s exhaust bubbler) and start slowly stirring the SOCl2. The sample of the HCl was then collected in the gas phase. Remember that, even though a spectrum is experimentally determined, it is traditional to show spectra as solid lines. Gas cells of this type are fragile and very expensive. Vibration-Rotation Spectrum of HCl Add annotation to spectrum. Once you have drawn the molecule, you will proceed to the Configure Job Options Screen. Figure 1. Kirksville, Missouri 63501 When you do this you will need to reduce the nitrogen flow to about 1 bubble per second at the inlet bubbler. The vibrational states also exhibit a quantized characteristic. Place the serum stoppers over the hose nipples and return the drying tube to the desiccator. Rotation de L’Acide Chlorhydrique Gazeux Etude de la Bande ν0->2 à 1.7 Micron” J. de Chimie Physique et de Physico-Chimie Biologique 62 (1965), 600-3. Table 3:  Values for the four constants in question. The fine structure in the diatomic vibrational spectra is based on various population of the rotational levels. B.; Ortiz, J. V.; Cui, Q.; Baboul, A. G.; Clifford, S.; Cioslowski, J.; Stefanov, B. Close the gas cell’s other stopcock and disconnect the drying tube. This therefore excludes molecules such as H2, N2 and O2 [2]. Enter a name for your job and then click on the Preview tab. Polik, W. F and Schmidt, J. R. WebMO Pro 6.1.010p;  WebMO LLC: Holland, MI, 2006. b. Polik, W. F. and Schmidt, J. R. WebMO User’s Guide; 2003,http://www.webmo.net/download/WebMO_Users_Guide.pdf. 3 will be displayed. The vibrational frequency at the DZV level for HCl was calculated as 2897.419922 cm -1. 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