Deadline: 19 Feb, 3:30 pm Assignment 3 Total Marks: 20

1. You are free to use any results with explicit derivation done in lectures directly.
2. You can make any reasonable assumptions as required to solve the problems, with justi-
fication provided.
3. Link for codes:
https://colab.research.google.com/drive/1lpyC9aw3B880kM4U6M0u5UR5FrK4jGSB?usp=sharing

1. (2 marks) Split operator method and time dependent potential: Consider a 1D system in pres-
ence of an electric field. The Hamiltonian is now time dependent and given by

H(t) = T̂ + V (x̂) + E0 x̂ cos(ω0 t)

Can the split operator method be used for such a system to evolve wave function in time? Justify your
answer and suggest any modifications if needed.
2. Convergence in the split operator method: Convergence means that the desired result should not
change with any simulation parameter (dt, DVR range and number of DVR points in this case). For all
parts below, the mass of the particle is m = 2000 a.u. and the initial wave function is

ψ(x, t = 0) = N exp(−x2 /(4σ 2 )) exp(ik0 x)

(a) (2 marks) First let us consider a free particle. Suppose I wish to evolve for a total time of 50000
a.u. with σ = 2 a.u. and k0 = 2 a.u. using split operator method. How large a time-step dt can
be used? Suggest a reasonable range of DVR grid (minimum and maximum values) and number of
DVR points. Justify your answers. The codes for free particle can be found in first example.
(b) (2 marks) Now we consider a harmonic oscillator with frequency ω = 0.001 a.u., and for initial
conditions: σ = 0.7 a.u and k0 = 3 a.u. Identify a reasonable time-step, range of DVR grid and
DVR points with justifications. The codes can be found in second example.
(c) (1 mark) For what value of σ will the width of the wave-packet not change in time for the harmonic
oscillator case? Test your prediction with the code and note your observations.
3. (3 marks) The mad scientist proposes the following ansatz for the time-independent Schrodinger equa-
tion: ψ(x) = R(x) exp(iS(x)/h̄2 ), where R(x), S(x) are real. If S(x) is expanded upto first order in h̄,
show that the WKB result for ψ(x) is obtained.
4. (4 marks) Can WKB theory be applied to time dependent problems? WKB theory is an
approximate solution to the TISE. We justify use of WKB theory for time dependent scattering in this
question.

We start with the general formula:

X
ψ(x, t) = ck ϕk (x)e−iEk t/h̄ (1)
k

dxϕ∗k (x)ψ(x, t = 0), and ϕk (x) are the eigen-functions, calculated using WKB theory.
R
where ck =
√
(a) Calculate ck , assuming ψ(x, t = 0) = N exp(−(x − x0 )2 /(4σ 2 )) exp(ik0 x), (N 2 = 1/( 2πσ) which
is initially localized much to the left of the barrier. Note that WKB eigen-functions diverge, and
cannot be normalized. To resolve this, use a normalization constant for ϕk such dk|ck |2 = 1.
R
Deadline: 19 Feb, 3:30 pm Assignment 3 Total Marks: 20

(b) Now consider the long time limit, where a fraction of the wave function has reached much to the
right of the barrier. Show that the transmission probability can be estimated as
Z (k−k0 )2
1 −
2σ 2
T =√ dke k TW KB (k),
2πσk
where σk = 0.5/σ and TW KB (k) is the WKB estimate of transmission probability.
5. (3 marks) WKB theory vs. numerically exact results: We perform numerically exact simulations
2
for the potential V (x) = V0 e−αx , with V0 = 0.002 a.u. and α = 0.5 a.u., and compare WKB results
with those of the exact ones. Mass m = 2000 a.u.
The provided code (third example) performs the simulation with the initial conditions ψ(x, t = 0) =
N exp(−(x − x0 )2 /(4σ 2 )) exp(ik0 x), with x0 = −10 a.u., σ = 1 a.u. and k0 = 1.5 a.u. The code shows
the dynamics, and prints the WKB estimate and the numerically exact transmission probability.
Estimating the initial kinetic energy as ⟨T ⟩ = h̄2 k02 /(2m), systematically increase k0 to just below the
barrier height (V0 ) and record your observations. Clearly specify the values of k0 tested. For what values
of k0 is WKB in good agreement with the exact results, and why?
6. Bound tunneling This question deals with a different form of tunneling, which is more relevant to
chemical reactions in condensed phase. We consider a special 1D case with V (x) = −Ax2 + Bx4 with
A, B being constants. This is called a symmetric double well potential. The figure below shows the
ground and first excited state wave functions for such a potential. Note the symmetry of the ground and
first excited state eigen-functions of this potential.

Our aim is to start with an initial wave function that is localized on the left and see how long it takes
to tunnel to the right. One can consider the initial wave function to be the ground state eigen-function
of just the left well (i.e. considering the left well to be a harmonic oscillator). To an approximation
(when barrier height is much larger than zero point energy), this wave function can be written as
ψ(x, t = 0) = N (ψ+ (x) + ψ− (x)) where ψ± (x) are the ground and first excited state eigen-functions of
the total Hamiltonian. For the chosen parameters, E+ = −2.0738 × 10−3 a.u. and E− = −2.0735 × 10−3
a.u.
(a) (2 marks) A wave function that is localized to the right well is of the form ψ(x) = N ′ (ψ+ (x) −
ψ− (x)). Mathematically derive the time it will take the initial wave function to localize on the
right.
(b) (1 mark) Open the provided code (fourth example). The initial condition set is ψ(x, t = 0) =
N exp(−mω(x − x0 )2 /(2h̄)) where ω and x0 are the frequency and minima position of the left well.
Set total time in the code long enough to see tunneling. Mention the total time set and note
observations.

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