MIT OpenCourseWare http://ocw.mit.edu 5.80 Small-Molecule Spectroscopy and Dynamics Fall 2008 For information about citing these materials or our Terms of Use, visit: http://ocw.mit.edu/terms.MASSACHUSETTS INSTITUTE OF TECHNOLOGY Chemistry 5.76 Spring 1985 Problem Set #4 1. Steinfeld, page 177, # 1. The corners of a cube are numbered 1, 2, 3, 4 clockwise around the top face of the cube, and 5, 6, 7, 8 clockwise around the bottom face, corner 5 lying under corner 1, corner 6 under corner 2, and so on. A face center is denoted by the two numbers of the corners between which a face diagonal can be drawn which passes through that face center (for example, either 13 or 24 would denote the center of the top face). (a) The structures of several kinds of AB4 molecules are described as follows with the above numbering system. The A–atom is placed at the center of the cube, and the A—B bond distances are given by the cube dimensions. However, the B–atoms are not necessarily all equivalent, the actual equivalence being determined by the symmetry elements remaining in the AB4 structures. (i) AB4(1, 2, 3, 4) (ii) AB4(1, 3, 5, 7) (iii) AB4(1, 3, 6, 8) (iv) AB4(1, 5, 16, 18) (v) AB4(13, 36, 68, 18) Give the point-group symbol for each AB4 structure (for example, C3v, D6h, and so on). (b) Classify the five molecules of Part (a) as to type of molecular rotator (linear, symmetrical top, and so on). (c) Which of the five molecules of Part (a) will give a pure-rotational spectrum in the far-infrared or mi-crowave region? Which will give a pure-rotational Raman effect? 2. Steinfeld, page 196, # 1. The harmonic oscillator (mass m) in two dimensions has a potential energy V expressed in polar coordinates r, θ, of the general form 2V = k1r2cos2θ + k2r2sin2θ, where k1 and k2 are force constants. For the special case k1 = k2 = k, the oscillator has a single frequency v = (k/m)1/2/2π, and its Schr¨odinger equation has solutions of the form � � ψv,� = Nv,� exp −αr2 exp(i�θ)P(r)25.76 Problem Set #4 Spring, 1985 page 2 where v, � are quantum numbers (v = 0, 1, 2, . . . , ∞; ±� = 0, 2, 4, . . . , v for v even, ±� = 1, 3, 5, . . . v for v odd); Nv,� is a normalization constant; α = 4π2mv/h; P(r), a polynomial in r only, depends for its form on the values of v and � and is an even function for even v, odd for odd v. (a) The energy levels of this two-dimensional oscillator are Ev = (v + 1)hv. What is the degeneracy of the v–th level? (b) Find Nv,� for v = 1, � = +1, for which P(r) = α1/2r . (c) Show that any two ψ’s of the same v but different � are orthogonal. (d) Find the average value of the angular momentum pθ for any state v, �. (e) Find the average value of r−2 for the state v = 1, � = +1. Substitute the results of the above in the equation for the relationship between E and pθ in the plane rotor and find E for the state v = 1, � = +1. Explain the difference between this value of E and that given by the equation of Part (a). 3. Steinfeld, page 197, # 2 The carbon suboxide molecule C3O2, is believed to be linear and symmetrical. (a) Classify the normal vibrations of C3O2 according to the symmetry species of point group D∞h. (b) Draw the modes of vibration of C3O2. (c) How many polarized lines should appear in the vibrational Raman spectrum? How many fundamental infrared bands should have P–, Q–, and R–branches? (d) The ground electronic state of C3O2is nondegenerate. What is the degeneracy of ψmol when C3O2is in its ground electronic state with v1 = v2 = v3 = v4 = v5 = v6 = 0, v7 = 1, and the rotational quantum number J = 5? The normal coordinate Q7 is antisymmetric with respect to simultaneous interchange of all pairs of equivalent nuclei. What is the degeneracy of ψmol for the above state with J = 6 instead of 5? 4. Steinfeld, page 199, # 8. (a) Let ψa ≡ ψv1=1(Q1)ψv2=0(Q2) and ψb ≡ ψv1=0ψv2=2be the normalized harmonic-oscillator wave functions of a polyatomic molecule corresponding to excited vibrational states of unperturbed energies Ea and Eb. If these two states are in Fermi resonance, second-order non-degenerate theory can be applied. Assume that the interaction energies Haa�and Hbb�are zero and that H�arises from one or more anharmonic ab terms in the potential function. In a certain molecule, the levels ψa and ψb are observed to be in Fermi resonance, the transitions to the perturbed levels being observed at 1400 and 1500 cm−1, whereas the� � � � 5.76 Problem Set #4 Spring, 1985 page 3 level ψv1=0ψv2=1 has an energy of 740 cm−1 above the zero level (see diagram). Deduce the unperturbed Ea–value from the above data (H�is to be evaluated from the data, not by integration). ab (b) The intensity of the Raman line for the transition from the ground state ψ0,0 to the unperturbed state ψa in the absence of Fermi resonance is proportional to the square of the matrix element ����� ����� ψa ∂α ψ0,0 Q1∂Q1 where ∂α/∂Q1 is a non-zero constant. The corresponding matrix element ����� ����� ψb ∂α ψ0,0 Q2∂Q2 is zero because Δv2 = 2. Find the ratio of the intensities of the two Raman lines for the transitions from state |ψ00� to the perturbed states |ψA� and |ψB�. 5. 16O12C32S is a linear molecule. The bond lengths are rCO = 1.16 Å rCS = 1.56 Å and the observed fundamental vibrational frequencies are ν1 = 858.9 cm−1 stretch ν2 = 520.4 cm−1 bend ν3 = 2062.2 cm−1 stretch. (a) Obtain kCS, kCO, and kΘ [rCOrCS]−1 in dynes/cm. (b) What are the amplitudes for C–O and C–S stretch in ν1? (c) What are the vibrational frequencies for