4. Which experimental technique is the most direct method to determine the valence-band electronic structure and density of states of a solid-state material?
(A) UV-Vis absorption spectroscopy
(B) Infrared (IR) spectroscopy
(C) X-ray diffraction (XRD)
(D) Ultraviolet photoelectron spectroscopy (UPS)
(E) Thermogravimetric analysis (TGA)

5. In a character table, the labels g and u refer to symmetry with respect to: (A) Inversion (i) (B) Reflection in $\sigma_{\mathrm{h}}$ (C) Rotation about $\mathbf{C}_{\mathrm{n}}$ (D) Improper rotation $S_{n}$ (E) Translation along $z$

6. Which of the following correctly describes the oxidation state and electron count of the complex $\left[\mathrm{Fe}(\mathrm{CO})_{2}\right]$? (A) Fe(II), 18 electrons (B) Fe(III), 16 electrons (C) Fe(0), 16 electrons (D) Fe(II), 16 electrons (E) Fe(0), 18 electrons 

7. What is the primary role of CuI in the Sonogashira coupling? (A) Acts as a Lewis acid to activate the aryl halide (B) Forms a copper acetylide intermediate from the terminal alkyne (C) Reduces Pd(II) to Pd(0) (D) Stabilizes the phosphine ligand (E) Serves as the main oxidative addition catalyst

8. The number of IR-active CO stretching bands in cis-M(CO)₂L₂ vs trans-M(CO)₂L₂ differs mainly because: (A) The force constant differs only (B) Cis has higher symmetry than trans (C) The reducible representation of CO stretches reduces differently (D) Raman selection rules forbid all CO stretches in cis (E) CO stretches are always degenerate

9. Which statement about phosphine ligands (PR₃) in transition-metal catalysis is correct? (A) Electron-withdrawing phosphine ligands generally accelerate oxidative addition (B) Bulky phosphine ligands tend to stabilize low-coordination-number metal centers (C) Trialkylphosphines (e.g., PMe₃) are weaker σ-donors than triarylphosphines (e.g., PPh₃) (D) Increasing the cone angle of a phosphine ligand always decreases the reaction rate (E) Phosphine ligands mainly function as π-acceptors rather than σ-donors

10. A 0.10 M solution of CH₃COOH has a measured pH = 2.87 at 25 °C. Which of the following pKa values is closest to that of acetic acid? (A) 1.0 (B) 2.0 (C) 3.0 (D) 4.0 (E) 5.0

11. For an octahedral d⁵ high-spin complex, the very weak visible absorption is best rationalized by: (A) Δ₀ is zero (B) Only Laporte-forbidden transitions exist (C) Only spin-forbidden transitions exist (no spin-allowed excited states) (D) Charge-transfer bands dominate and remove all d-d transitions (E) The complex is colorless by definition 

12. Which of the following statements correctly defines or describes a *superacid*? (A) A superacid is any acid stronger than sulfuric acid in terms of molarity (B) A superacid is an acid whose Hammett acidity function $(\mathrm{H}_{\mathrm{a}})$ is lower than that of pure sulfuric acid (C) A superacid is an acid that can protonate only strong bases such as amines (D) A superacid always contains fluorine and antimony elements (E) A superacid is an acid that is always stronger than sulfuric acid in water

13. In an $\mathrm{O_h}$ field, the ground term for a $d^2$ free ion $(^{3}F)$ splits into: (A) $\mathrm{A_{1g} + E_g}$ (B) $\mathrm{A_{2g} + T_{1g} + T_{2g}}$ (C) $\mathrm{T_{1u} + T_{2u}}$ (D) $\mathrm{E_g + T_{2u}}$ (E) $\mathrm{A_{2u} + E_u}$

14. Which of the following acids is the *strongest* under aqueous conditions? (A) Chloroacetic acid (B) Acetic acid (C) Phenol (D) Prussic acid (E) Propionic acid

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