11. If a system at equilibrium is perturbed in the forward direction, the system will approach equilibrium with a rate determined by
(A) the forward rate constant
(B) the reverse rate constant
(C) a combination of the two
(D) neither

12. What is the physical meaning of $\Delta A$ in thermodynamics? (T: temperature; V: volume)(A) Maximum heat at constant T and V (B) Maximum non-expansion work at constant T and V(C) Maximum work at constant T and V (D) Maximum work at constant T

13. $\left(\frac{\partial \left(\frac{A}{T}\right)}{\partial \left(\frac{1}{T}\right)}\right)_V = ?$(A) $G$ (B) $H$ (C) $U$ (D) $S$

14. What is the expression of entropy change $(\Delta S)$ for the isothermal reversible expansion at temperature $T$ from $V_{1}$ to $V_{2}$ of $n$ moles of a van der Waals gas?(A) $nRT\ln \frac{V_1 - nb}{V_2 - nb} + an^2\left(\frac{1}{V_1} -\frac{1}{V_2}\right)$ (B) $-nR\ln \frac{V_1 - nb}{V_2 - nb} -\frac{an^2}{T}\left(\frac{1}{V_1} -\frac{1}{V_2}\right)$(C) $nR\ln \frac{V_1 - nb}{V_2 - nb} +\frac{an^2}{T}\left(\frac{1}{V_1} -\frac{1}{V_2}\right)$ (D) $-nRT\ln \frac{V_1 - nb}{V_2 - nb} -an^2\left(\frac{1}{V_1} -\frac{1}{V_2}\right)$

15. The equation of $C_{P,m} - C_{V,m}$ can be expressed in terms of $V_{m}, T,$ and the gas constants $R, a$ and $b$ as follows: $C_{P,m} - C_{V,m} = R / \left(\Gamma - \frac{\Theta a(V_m - b)^\Phi}{RTV_m^\Omega}\right)$ , where $\Gamma, \Theta, \Phi$ and $\Omega$ are real integers. Which of the description about $\Gamma, \Theta, \Phi$ and $\Omega$ is correct? (A) $\Gamma \neq \Omega$ (B) $\Theta \neq \Phi$ (C) $\Theta = \Phi = \Omega = 1$ (D) $\Omega = \Phi$

16. The rate equation of $A^{*}$ is (A) $[A^{*}] = [A]_{0}e^{-(k_{1} + k_{2})t}$ ; (B) $[A^{*}] = [A^{*}]_{0}e^{-(k_{3})t}$ ; (C) $[A^{*}] = [A^{*}]_{0}e^{-(k_{1} + k_{2} + k_{3})t}$ ; (D) $[A^{*}] = [A]_{0}e^{-(k_{1} + k_{2} + k_{3})t}$

17. The fluorescence lifetime of $A^{*}$ is (A) $\frac{1}{k_1}$ (B) $\frac{1}{k_1 + k_2}$ (C) $\frac{1}{k_1 + k_2 + k_3}$ (D) $\frac{1}{k_2}$

18. The branching percentage of $A_{hot}$ , is (A) $\frac{k_2}{k_1 + k_2}$ (B) $\frac{k_2}{k_1 + k_2 + k_3}$ (C) $\frac{k_1}{k_2}$ (D) $\frac{k_2}{k_1}$

19. The rate equation of species $A_{T}$ is (A) $[B] = \frac{k_3}{k_1 + k_2 + k_3} [A_T]_0 e^{-(k_1 + k_2 + k_3)t}$ (B) $[A_T] = [A_T]_0 e^{-(k_3)t}$ (C) $[A_T] = \frac{k_3}{k_1 + k_2 + k_3} [A_T]_0 [1 - e^{-(k_3)t}]$ (D) $[A_T] = \frac{k_3}{k_1 + k_2 + k_3} [A^*]_0 [1 - e^{-(k_1 + k_2 + k_3)t}]$

20. To increase the fluorescence quantum yield, the chemist may design a molecule with the following properties. Which of the following is incorrect?(A) A shorter fluorescence lifetime(B) Slower internal conversion rate(C) Slower intersystem crossing rate(D) Faster radiative decay

複選題21. In ultrafast photochemical processes, molecules are often excited by femtosecond laser pulses to electronically excited states, followed by rapid nuclear motion and electronic relaxation. In such situations, the validity of the Born–Oppenheimer approximation (BOA) becomes a central issue. The BOA exploits the large mass difference between nuclei and electrons to simplify the molecular Schrödinger equation by separating electronic and nuclear motions. Which of the following statements regarding the Born–Oppenheimer approximation (BOA) are correct?(A) The BOA assumes that electrons respond instantaneously to nuclear motion due to their much smaller mass.(B) Within the BOA, the total molecular wavefunction is expressed as a product of an electronic wavefunction and a nuclear wavefunction.(C) Zero-point vibrational energy is neglected in the BOA.(D) Immediately after vertical photoexcitation, the BOA is typically valid because the nuclear geometry has not yet changed.(E) Within the BOA, ultrafast population transfer between different electronic states can be fully described without considering the interaction between nuclear motion and electronic states.

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