Molecular Spectra and Molecular Structure - 1976 Fin Ex

Final Examination Answer all questions. Each part is worth 10 points, 120 points total. Open book, open notes, no time limit, no collaboration, pocket calculators strongly recommended. Good luck! I never did like the smell of formaldehyde. The formaldehyde molecule is planar and has two equal C–H bond lengths. H C O H A. Determine the point group for H2 CO and generate the character of the 12 dimensional reducible Cartesian representation. Reduce this representation and list the irreducible representation labels of the 3N−6 vibrational degrees of freedom of H2 CO. B. Construct reducible representations using various internal coordinate basis functions. Which normal modes are pure stretching, in–plane bending, out–of–plane bending? Do not list modes that involve combinations of bending and stretching motions. C. Suppose we did not know that H2 CO was planar, but we were certain that the two CH bonds had equal lengths. Describe how you might use a comparison of the Infrared and Raman Vibrational Spectra to distinguish between the planar and nonplanar possibilities. D. The geometric structue of planar H2 CO is completely determined by three parameters: r1 = rHC , r2 = rCO , θ = θHCH H r1 θ C r1 r2 • O Center of mass H The center of mass is on the C–O bond axis somewhere between the C and O atoms. Define a coordinate system in which the origin is at the center of mass, the z–axis is along C–O, and the xz plane is the plane of the molecule. Express the coordinates of each atom in this system in terms of r1 , r2 , and θ. page 2 E. Express the principal moments of inertia in terms of r1 , r2 , and θ. The principal axes (located by symmetry, labeled according to Ia ≤ Ib ≤ Ic ) are: Ia Ib Ic (CO axis) (axis in molecular plane perpendicular to CO axis) (axis perpendicular to molecular plane). F. Calculate Ia , Ib , and Ic for H2 12 C16 O, D2 12 C16 O, H2 13 C16 O, and H2 12 C18 O using the following atomic masses. H 1.008142 amu D 2.014735 12 C 12.003804 13 C 13.007473 16 O 16.000000 18 O 18.004874 and estimated values for r1 , r2 , and θ: θHCH = 117.6◦ rCH = 1.086˚ A (from H2 C = CH2 ) A rCO = 1.216˚ (from CH3 CHO). (from H2 C = CH2 ) You are free to make your own estimates, but please do not look up the actual structure of H2 CO and use “exact” values. You are going to use these calculations to assign the H2 CO microwave spectrum, therefore reasonably accurate structural estimates will be to your advantage. Calculate Δ = Ic − Ia − Ib for all four isotopes. This quantity is called the inertial defect. It is zero for planar molecules. Δ is the best test for planarity, especially when the state in question is electronically excited and a comparison of infrared and Raman Spectra is not possible. G. For all four isotopic variations of part F, convert Ia , Ib , and Ic to the rotational constants A, B, C in units of MHz(106 Hz). 5.05376 × 105 � � A, B, C(MHz) = 2 A Ia,b,c amu˚ Which rotational constant(s) are completely insensitive to carbon or oxygen isotope? Why are all three constants less sensitive to carbon than to oxygen isotope (two reasons)? Hydrogen is very light and should make a small contribution to moments of inertia, yet replacement of D for H causes a very large change in one rotational constant and a negligible change in the other two. Explain. H. When you calculated rotational constants in part G, you probably noticed that two of the three rotational constants were almost equal to each other. Thus H2 CO is an almost symmetric top and its rotational spectrum should resemble that of a symmetric top. However, each symmetric top transition will be asymmetry-split into several resolvable transitions. In order to predict the qualitative features of the pure rotational spectrum you need to know: page 3 (i) Is H2 CO more nearly prolate or oblate? (ii) Does H2 CO have a permanent electric dipole moment and, if so, onto which principal axes can it have projections? (iii) What are the ΔJ and ΔK selection rules for this almost symmetric top? I. Using the asymmetric top energy level expressions on page 192 of Bernath (1995 edition) (in which centrifugal distortion effects are neglected) and your predicted rotational constants from part G, calculate the rotational energy levels 000 , 110 , 111 , 101 , 220 , 221 , 211 , 212 , 202 for H2 12 C16 O and H2 13 C16 O. Construct an energy level diagram and draw in the transitions that would be allowed in the correct symmetric top limiting case. J. Following is a complete list of observed transitions involving levels J = 0, 1, 2 for two isotopes H2 12 C16 O 71.14 MHz 4829.66 14488.65 72837.97 140839.54 145602.98 150498.36 H2 13 C16 O — 4593.09 MHz 13778.86 71024.80 137449.97 141983.75 146635.69 Assign as many of these transitions as possible. Note that, in a real spectrum, you could not arrange to see only transitions involving J = 0, 1 and 2. In fact, there are more than 54 observed H2 12 C16 O transitions below 150498.36 MHz. K. Determine rotational constants from the observed spectra and compare with your predicted constants. Do not be alarmed that any set of A, B, or C constants cannot exactly reproduce all observed transitions. This is due to neglect of centrifugal distortion effects. L. Ignoring the fact that you have measured rotational constants for the (0, 0, 0, 0, 0, 0) vibrational level and not for the equilibrium molecular configuration, calculate values of rCH , rCO , θHCH from the observed rotational constants.