Title: ETH_Sem4 / Advanced_Kinetics / TrueFalse
On every note of this deck, unless a note says otherwise:
QType (0=kprim,1=mc,2=sc): 1

Question: Lecture 1
Title: Which of the following statements are true?
Q_1: Classical and Quantum statistics are the same at low temperature
Q_2: Classical and Quantum statistics are the same for heavy particles
Q_3: Classical and Quantum statistics are the same for harmonic oscillators
Q_4: Classical and Quantum statistics are the same for translational degrees of freedom
Q_5: Transition-state theory approximates the rate of a chemical reaction
Answers: 0 1 0 1 1

Question: Lecture 1 (2)
Title: Which of the following statements are true?
Q_1: Quantum tunnelling slows down reactions
Q_2: Chemistry is best described by classical mechanics
Q_3: Chemistry is best described by quantum mechanics
Q_4: Chemistry is best described by a careful mixture of the two
Q_5: Chemistry is best described by learning long lists of named reactions
Answers: 0 0 1 1 0

Question: Lecture 2 (1)
Title: Which of the following statements are true?
Q_1: Given a Hamiltonian and some initial conditions (\(x\) and \(p\)), we can in principle run classical dynamics
Q_2: Given a Hamiltonian and some initial conditions (\(\psi\) or \(\rho\)), we can in principle run quantum dynamics
Q_3: Given a Hamiltonian and some final conditions, we can compute the state of the system at an earlier time (both QM and classical)
Q_4: The thermal average of the energy is conserved
Q_5: Quantum and classical equations of motion give the same dynamics for a particle in a harmonic oscillator
Answers: 1 1 1 1 1

Question: Lecture 2 (2)
Title: Which of the following statements are true?
Q_1: The thermal average of any operator is conserved
Q_2: In the microcanonical distribution, the average energy is conserved
Q_3: In the microcanonical distribution, the average of any operator is conserved
Q_4: In a non-equilibrium distribution, the average energy is conserved
Q_5: In a non-equilibrium distribution, the average of any operator is conserved
Answers: 1 1 1 1 0

Question: Lecture 4 (1)
Title: Which of the following statements are true?
Q_1: The time-ordering operator is necessary to preserve causality
Q_2: Time-dependent perturbation theory provides a useful method for studying weak light-matter interaction
Q_3: FT of dipole-dipole correlation function gives same result as weighted sum over transition dipole moments
Q_4: In the spectrum of a harmonic oscillator, there are no ”hot bands” (\(\psi_1 \to \psi_2\))
Q_5: In the spectrum of a harmonic oscillator, there are no ”overtones” (\(\psi_0 \to \psi_2\))
Answers: 0 1 1 0 1
Extra 1: 1. Only if expansion \(\hat H(t)\) not commutative
2. But not for studying strong ones
4. Just unlikely
5. Selection rules!

Question: Lecture 4 (2)
Title: Which of the following statements are true?
Q_1: In the spectrum of a harmonic oscillator, there is no ”sponteneous emission” (\(\psi_1 \to \psi_0\))
Q_2: The stronger the light field, the faster the Rabi oscillations
Q_3: The stronger the light field, the larger the amplitude of the Rabi oscillations
Q_4: The better the field oscillation matches the energy gap, the faster the oscillations
Q_5: The better the field oscillation matches the energy gap, the stronger the amplitude
Answers: 0 1 1 0 1
Extra 1: 1. There is a delta function for \(\omega = \pm \omega_0\) which makes both ways possible
2. \(\Omega\) increases with \(\varepsilon\)
4. No, a better match results in a slower oscillation

Question: Lecture 5 (1)
Title: Which of the following statements are true?
Q_1: Wavepackets are superpositions of eigenstates
Q_2: Wavepackets are statistical mixtures of eigenstates
Q_3: The centre of the wavepacket follows a classical trajectory
Q_4: A propagating wavepacket gets wider with time
Answers: 1 0 0 0

Question: Lecture 5 (2)
Title: Which of the following statements are true?
Q_1: A propagating wavepacket gets narrower with time
Q_2: The width of the wavepacket is fixed for all time
Q_3: Propagating the wavepacket on the ground state gives the vibrational spectrum
Q_4: Propagating the wavepacket on the excited state gives the electronic spectrum
Answers: 0 0 1 1

Question: Lecture 6 (1)
Title: Which of the following statements are true?
Q_1: The golden rule was discovered by Fermi
Q_2: FGR describes intramolecular electron-transfer rates in big molecules
Q_3: FGR describes coherent oscillations between two vibronic states F
Q_4: FGR describes absorption spectroscopy
Answers: 0 1 0 1

Question: Lecture 6 (2)
Title: Which of the following statements are true?
Q_1: FGR describes emission spectroscopy
Q_2: FGR requires knowledge of the wavefunctions of the reactant and product systems
Q_3: A short light pulse populates many excited vibronic states
Q_4: A long light pulse populates few excited vibronic states
Answers: 1 1 1 1

Question: Lecture 7 (1)
Title: Which of the following statements are true?
Q_1: It is easier to tunnel through the barrier at the bottom than the top
Q_2: Tunnelling is important for fat barriers, but not for thin barriers
Q_3: Tunnelling is important for light masses, but not for heavy masses
Q_4: Tunnelling is more important at low temperature than at high temperature
Q_5: Tunnelling makes reactions at low temperature proceed faster than they otherwise would
Answers: 0 0 1 1 1

Question: Lecture 7 (2)
Title: Which of the following statements are true?
Q_1: Tunnelling makes reactions at low temperature proceed faster than those at high temperature
Q_2: Tunnelling makes reaction rates independent of temperature
Q_3: Tunnelling effects show up most clearly in kinetic-isotope effects
Q_4: Tunnelling can only be described using the wavefunction, not with classical trajectories
Q_5: “Tunnelling” should be spelled “tunneling”
Answers: 0 0 0 1 0

Question: Lectrue 8 (1)
Title: Which of the following statements about rate theory are true?
Q_1: Classical rate theory is defined from the long-time limit of \(C_{fs}\)
Q_2: Classical rate theory is defined from the short-time limit of \(C_{fs}\)
Q_3: TST is an upper bound to Classical rate theory
Q_4: Classical rate is an upper bound to quantum rate
Q_5: Classical rate is independent of the dividing surface
Answers: 1 0 1 0 1

Question: Lecture 8 (2)
Title: Which of the following statements about rate theory are true?
Q_1: TST is independent of the dividing surface
Q_2: Quantum rate is independent of the dividing surface
Q_3: One can variationally improve classical rate theory
Q_4: One can variationally improve quantum rate theory
Q_5: One can variationally improve TST
Answers: 0 1 0 0 1

Question: Lecture 9 (1)
Title: Which of the following are assumptions/approximations made in Eyring TST?
Q_1: There is no recrossing
Q_2: Dynamics along the reaction coordinate can be separated
Q_3: Dynamics along the reaction coordinate is classical
Q_4: Dynamics perpendicular to the reaction coordinate is classical
Q_5: Rigid rotors are used for rotations
Answers: 1 1 1 0 1

Question: Lecture 9 (2)
Title: Which of the following are assumptions/approximations made in Eyring TST?
Q_1: Harmonic oscillators are used for vibrations
Q_2: The dynamics are adiabatic (Born-Oppenheimer)
Q_3: Reactants are in a thermal distribution
Q_4: Friction is neglected
Q_5: Tunnelling is neglected
Answers: 1 1 1 0 1

Question: Lecture 10 (1)
Title: What are the underlying assumptions of Marcus theory?
Q_1: Assumes Born-Oppenheimer approximation is valid
Q_2: Assumes golden-rule limit is valid
Q_3: Assumes all degrees of freedom are described by harmonic oscillators
Q_4: Assumes the free-energy curves are described by harmonic oscillators
Q_5: Assumes partition functions are purely classical
Answers: 0 1 0 1 1

Question: Lecture 10 (2)
Title: What are the underlying assumptions of Marcus theory?
Q_1: Assumes dynamics is purely classical
Q_2: Assumes constant velocity through the interaction region
Q_3: Assumes that tunnelling is negligible
Q_4: Assumes that the rate increases with driving force
Q_5: Assumes the reorganization energy must be overcome in order for the reaction to proceed
Answers: 1 1 1 0 0

Question: Lecture 11 (1)
Title: What are the underlying assumptions of RRKM theory?
Q_1: Born–Oppenheimer approximation is valid
Q_2: Fermi’s golden rule is valid
Q_3: Thermal equilibrium
Q_4: Microcanonical equilibrium
Q_5: Classical (no tunnelling) dynamics of reaction coordinate
Answers: 1 0 0 1 1

Question: Lecture 11 (2)
Title: What are the underlying assumptions of RRKM theory?
Q_1: System described globally by one set of harmonic oscillators
Q_2: Neglects recrossing
Q_3: Classical densities of states
Q_4: Equivalent to those of Marcus theory
Q_5: Equivalent to those of TST
Answers: 0 1 1 0 1

Question: Lecture 12 (1)
Title: Which of the following statements are true?
Q_1: Path integrals provide an equivalent description of reality as the Schrödinger equation
Q_2: Path integrals provide an equivalent description of reality as Newton’s equation
Q_3: Quantum statistics can be described by path integrals using a classical-like description
Q_4: With \(N = 1\), path integrals give classical statistics
Q_5: With any \(N\), path integrals give quantum statistics
Answers: 1 0 1 1 1

Question: Lecture 12 (2)
Title: Which of the following statements are true?
Q_1: RPMD provides an upper limit to the exact rate
Q_2: RPMD provides a lower limit to the exact rate
Q_3: RPTST provides an upper limit to the RPMD rate
Q_4: RPTST provides an lower limit to the RPMD rate
Q_5: The RPMD rate is always faster than the classical rate
Answers: 0 0 1 0 0