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Midterm_revised

The midterm exam consists of four main problems covering topics such as units conversion, Morse potential, Fermi's golden rule, and the molecular dimer H2+. Students are required to perform calculations, derive equations, and explain physical concepts related to quantum mechanics and molecular Hamiltonians. Each question has specific tasks and hints to guide the students in their responses.

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5 views

Midterm_revised

The midterm exam consists of four main problems covering topics such as units conversion, Morse potential, Fermi's golden rule, and the molecular dimer H2+. Students are required to perform calculations, derive equations, and explain physical concepts related to quantum mechanics and molecular Hamiltonians. Each question has specific tasks and hints to guide the students in their responses.

Uploaded by

704576944
Copyright
© © All Rights Reserved
Available Formats
Download as PDF, TXT or read online on Scribd
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Midterm

Due Arp 16, 2025

1. Units Conversion. Transform 1 eV x mP/A to atomic units. (mP is the mass of proton.)
(10)

2. Morse potential is widely used to describe the potential energy of a bond.

Find the best harmonic approximation to the Morse potential. Describe which
vibrationally excited state is not physical (Hint: Beyond the dissociation limit.) (20)

3. Validity of Fermi’s golden rule. Image a system |0⟩ is weakly coupled to 𝑁 levels
with energies 𝐸! , |𝑛⟩, 𝑛 = 1, … , 𝑁. Initially, the system is in state |0⟩, solving the time-
dependent Schrodinger equation (TDSE) numerically for, e.g., 𝑁 = 1, 𝑔! = 0.05; 𝑁 =
10, 𝑔! = 0.01; 𝑁 = 100, 𝑔! = 0.001. (You are free to tune these parameters. We can
choose 𝐸! to be uniformly distributed within the energy window [-W/2, W/2], W = 0.1)
Compute the population dynamics of state 0 with time. Does the rate behavior
emerge when N is large, or in other words, do you see exponential decay?（40）
(Hint: Build the Hamiltonian matrix with diagonals corresponding to the energies and
off-diagonal elements the couplings; it should be of size (𝑁 + 1) × (𝑁 + 1). Then
the TDSE is a matrix equation that standard numerical integrators can solve.)

4. Consider the molecular dimer H2+, which has a single electron (with coordinate r) and
one vibrational mode (with coordinate R). Neglecting translation and rotation, the
molecular Hamiltonian is given by
1 1
𝐻 = − ∇#" − ∇#$ + 𝑉(𝑟, 𝑅)
2𝜇 2
where µ is the effective mass.
(1) Explain the physical meaning of each term in the Hamiltonian. (10)
(2) The Born-Oppenheimer approximation assumes the following ansatz for the
molecular wavefunction
𝜓(𝑟, 𝑅, 𝑡) = 𝜙(𝑟, 𝑅)𝜒(𝑅, 𝑡). Eq. 2
where 𝜙(𝑟, 𝑅) is the ground eigenstate of the electronic Hamiltonian 𝐻%& (𝑅) =
'
− # ∇#$ + 𝑉(𝑟, 𝑅), i.e.,
𝐻%& (𝑅)𝜙(𝑟, 𝑅) = 𝑉( (𝑅)𝜙(𝑟, 𝑅) Eq (3).

Derive the equation of motion for the nuclear wavepacket 𝜒(𝑅, 𝑡) using the following
)*
steps. (i) Inserting Eq. 2 into the time-dependent Schrodinger equation*+ 𝜓(𝑟, 𝑅, 𝑡) =

𝐻𝜓(𝑟, 𝑅, 𝑡), （ii） left-multiplying 𝜙(𝑟, 𝑅) and (iii) integrating over r. (10)

(3) What terms are neglected in the Born-Oppenheimer approximation? (10)

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