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Assigned problems for Lectures 25-27 Molecular Orbital Theory and Homonuclear Diatomic Molecules 1. Give the groundstate electron configuration for (a)H-2 , (b)N 2 , (c)O2 What are the bond orders (bo) answer ( a) : H-2 (3 electrons) : 1σ 2 2σ * bo = 0.5 (b) : N 2 (10 electrons) : 1σ 2 2σ *2 1π 4 3σ 2 bo = 3 (c) : O2 (12 electrons) : 1σ 2 2σ *2 1π 4 3σ 2 2π *2 bo = 2 2. From the groundstate electron configuration of B2 and C2 predict which molecule should have the greater dissociation energy Answer : B2 (6 electrons) : 1σ 2 2σ *2 1π 2 b =1 C2 (8 electrons) : 1σ 2 2σ *2 1π 4 b=2 The bond orders of B2 and C2 are respectively 1 and 2; so C2 should have the greater bond dissociation enthalpy. the experimental values are approximately 4eV and 6eV respectively. 3. Consider a bonding electron in a diatomic molecule from the molecular orbital point of view. If the probabilities of finding the electron in atomic orbitals ψ A and ψ B are 0.25 and 0.75, respectively, what is the LCAOwavefunction for the electron (Neglect overlap) Answer : Since the electron moves only in orbitals ψ A and ψ B we must have Ψ = C1ψ A + C2 ψ B . The square of the coefficients equals the corresponding probability since ψ A and ψ B are orthonormal 1 1 = ∫ C1ψ A C1ψ A dv =C12 ∴ c1 = ± 4 2 3 3 likewise = C2 2 ∴ C2 = ± 4 2 The overall probability must be equal to 1 C12 + C2 2 = 1 Thus there are two possible wave functions 1 3 Ψ± = ψA ± ψB 2 2 1 The Ψ+ is the bonding combination. The choice of c1 = − results 2 in two more wavefunctions which are just negatives of the first two , and so describe the same physical states 4. The term symbol for the groundstate of the N+2 ion is 2 Σ g . What is the total spin angular momentum of the molecule? Show that the term symbol agreres with the electron configuration that would be predicted by using the build - up principle. answer : The left superscript is the value of 2S + 1, so 2S + 1 = 2 implies that 1 S = . The symbol Σ indicates that the orbital angular momentum 2 around the molecular axis is zero. The latter implies that the unpaired electron must be in a σ - orbital. From the orbital level diagram for homonuclear diatomic molecules in the text we predict the configuration N2 + (9 electrons) :1σ 2 2σ *2 1π 4 3σ1 bo = 2.5, which is in accord with the 2 Σ g term symbol since 3σ is an even function and all lower energy orbitals are filled, leaving one unpaired 1 electron, thus S = . 2 5. One of the excited states of the C2 molecule has the valence electron configuration 1σ g 2 2σ u *2 1π u1 2π g1. Give the multiplicity and parity of the term. Answer According to Hunds rule, we expect one 1π u electron and one 2π g electron to be unpaired. hence S = 1 and the multiplicity of the spectroscopic term is 3. the overall parity is uxg = u since (apart from the complete core), one electron occupies a u orbital and another a g orbital. 6. The energy of H+2 with internuclear separation R is given by the expression J+K e2 E+ = EH − + 1 + S 4 πε o R where E H is the energy of an isolated H atom, J is the attractive potential energy between the electron centered on one nucleus and the charge of the other nucleus, K is the attraction between the overlap density and one of the nuclei, and S is the overlap integral. The values are given below. Plot the molecular potential energy curve and find the bond dissociation energy (in eV) and the equilibrium bond length R/a o 0 1 2 3 4 e2 ( ) 4 πε o R ∞ 1.000 0.500 0.3333 0.255 RH J / RH 1.0000 0.729 0.473 0.330 0.250 K / RH 1.0000 0.736 0.406 0.199 0.092 S 1.0000 0.858 0.587 0.349 0.189 where R H = 27.3 eV, a o = 52.9 pm , and E H = - 1/2R H For an answer check with the graph in the text 7. The same data as in problem 6 may be used to calculate the molecular potential energy curve for the antibonding orbital , which is given by J-K e2 E- = E H - + 1 - S 4πε o R For answer check with graph in text 8. One of the excited states of H2 is 3Πu , and can be considered to be formed from one H atom in its groundstate and the other in the excited state. Give the electron configuration of the molecule. Answer : Since the molecule has one unit of angular momentum around the axis, and since one electron is in a σ orbital , the other electron must be in a π orbital. This suggests that the configuration is 1σ g11π u1 which is consistent with the designation 3Π u . 9. Normalize the molecular orbital Ψ(1) = ψ A (1) + λψ B (1) in terms of the parameter λ and the overelap S. Here assume ∫ ψ *A (1)ψ A (1)dv = 1, ∫ ψ B (1)ψ B (1)dv = 1, ∫ ψ A (1)ψ B (1)dv = S * * Answer : ∫ Ψ(1) Ψ(1) = N ∫ (ψ A (1) + λψ B (1)) (ψ A (1) + λψ B (1))dv = 1 * 2 * = N 2 ∫ (ψ *A (1)ψ A (1)dv + N 2 λ2 ∫ (ψ *B (1)ψ B (1)dv + 2λN 2 ∫ (ψ *B (1)ψ A (1)dv = N 2 (1 + λ2 + 2 Sλ ) 1 hence N = 1 + λ2 + 2 Sλ 10. use the date in 6 and 7 to show that the antibonding orbital (E- ) is more anti - bonding (destabilized compared to a free hydrogen atom) than the bonding orbital is bonding (stabilized compared to free hydrogen atom) Answer : We need to determine if E- + E+ > 2E H J-K e2 J+K e2 E− + E+ = E H - + + EH − + 1 - S 4πε o R 1 + S 4πε o R e2 [( J − K )(1 + S ) + (1 − S )( J + K ) = 2EH + 2 − 4πε o R (1 − S )(1 + S ) 2( SV2 − V1 ) e2 = + 2 E H + 2 1 − S2 4πε o R 2( SV2 − V1 ) e2 Use the data in 6 to show that + 2 >0 1 − S2 4πε o R