IFM – Chemistry Computational Chemistry (7.

5hp) VT10 2010-05-06

Exercise 1: Quantum Chemistry

1. Show that f ( x) = e ax is an eigenfunction to the operator  = d/dx and calculate

the corresponding eigenvalue. Also show that g ( x) = e ax isn’t an eigenfunction
2

to d/dx.

2. Determine which functions that are eigenfunctions to the operator d2/dx2 and for
these cases determine the eigenvalues: a) eikx b) cos kx c) kx and d) exp(kx2).

3. The ground-state wavefunction for a particle, e.g. an electron, in a 1-

dimensional box is
⎛ πx ⎞
1/ 2
⎛2⎞
ψ ( x) = ⎜ ⎟ sin ⎜ ⎟
⎝ L⎠ ⎝L⎠
The length of the box is 10.0 nm. Compute the probability that the particles is
located between a) x = 4,95 and 5,05 nm, b) between x = 9,90 and 10,00 nm, c)
in the right-hand side of the box and d) between x = 1/3 L and 2/3 L.

4. The ground-state wavefunction for an electron in a hydrogen atom is

1/ 2
G ⎛ 1 ⎞
ψ (r ) = ⎜⎜ 3 ⎟⎟ e − r / a0
⎝ πa 0 ⎠
where a0 = 0,529177 Å. a) Calculate the probability that the electron can be
found within a small sphere of radius 0.01 Å when the sphere is centered on the
nucleus. b) Assume instead that the sphere is situated at the distance r = a0 from
the nucleus. What is the probability to find the electron within the sphere ?

5. Calculate the expectation value of the momentum px, whose operator in atomic
units is pˆ x = −i ⋅ d / dx , if the particle is represented by the (non-normalized)
wavefunction ψ ( x) = e − ax , where x is between –∞ and +∞.
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6. Consider an electron in a 1-dim. box of length L, so that 0 ≤ x ≤ L. Assume that

the electron is in a (superposition) state that is not an eigenfunction to the
particle-in-a-box Hamiltonian, and that its wavefunction can be written as:
1 ⎛ πx ⎞ 3 ⎛ 3πx ⎞
ψ ( x) = sin ⎜ ⎟ + sin ⎜ ⎟
2 ⎝L⎠ 4 ⎝ L ⎠
For simplicity, let the length of the box L be 1 Bohr and use atomic units.
Calculate the expectation value of the energy for this state.

7. For a particle-in-a-box the wavefunction for the ground state was guessed to be:
ψ ( x) = N ⋅ x ⋅ ( L − x) 0≤x≤L
ψ ( x) = 0 x < 0, x > L
Determine the value of the constant N so that the function gets to be normalized.
Then calculate the expectation value of the energy. How many percent does this
value differ from the true ground-state energy?

8. Consider the particle-in-a-box. Assume that you don’t know the solutions to its
Schrödinger equation, but instead you guess that the eigenfunction of the ground
state can be approximated by a function of the form:
ψ(x) = (x – x2/L) + k⋅(x – x2/L)2.
Use the variational principle to determine the optimal value for k!
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9. For the H-atom, use the variational principle with a trial function with the form
G
ψ (r ) = e − kr , and determine the optimal value of k.

10. Show that the function f ( x, y, z ) = cos ax cos by cos cz is an eigenfunction of

∇ 2 and determine the corresponding eigenvalue.

11. Write the expression for the Hamiltonian of a) Li and b) HHe+ in atomic units.

12. Consider the H2+ molecule, that only contains one electron. Let’s use the LCAO-
method and approximate the molecular orbital by a linear combination the non-
G
normalized (1s) orbitals of the hydrogen atoms, φ (r ) = e − r / a0 , centered on
nucleus ”A” respective ”B”. The molecule’s approximate ground-state
molecular orbital can then be written:
G
ψ (r ) = N (φ A (rA ) + φ B (rB ))
G G G
where r is the coordinates of the electron and rA = r − R A is the distance to
G G G
nucleus A (with coordinates R A ) and rB = r − RB is the distance to nucleus B.
Assume that the normalization constant N is 1/1218 if the distance is given in
pm. The distance between the nuclei A and B is 106 pm. Consider a small
volume element dV = 1 pm3 (for example a cube with a side length of 1,0 pm).
How large is the probability to find the electron within the volume element dV if
the volume element is situated at the following places: a) at nucleus A b) at
nucleus B c) at the axis in the middle between A and B?

13. If one takes into account the antisymmetry condition for the total state function
for an atom or a molecule one obtains in the independent-particle model after
using the variational principle that the best possible one-electron functions fulfill
the following one-electron equations, the so-called Hartree-Fock equation:
⎡ 1 G 2 * G G
Z g N 4 ψ i ( xi ) G G ⎤ G N 4 ψ ( x )ψ ( x ) G G G G
⎢− ∇ k − ∑
2
+ ∑ ∫ G G dri dσ i ⎥ψ k ( x k ) − ∑ ∫ i i
G G
k i
dri dσ iψ i ( x k ) = ε kψ k ( x k )
⎢⎣ 2 g rkg i =1 ri − rk ⎥⎦ i =1 ri − rk

where the index g denotes atomic nuclei and index i and k the electrons. Write
explicitly this equation for an electron in the He atom. What is the meaning of
the different terms?

14. The molecule ion HHe+ has been observed in stellar spectra. Perform a simple
MO-LCAO calculation for this ion with one (1s) orbital on H and one (1s)
orbital on He as basis functions. Calculate the MO energy levels and the
coefficients in the molecular orbitals if:
F11 = –8 eV, F22 = –16 eV, F12 = –3 eV and if S12 is assumed to be = 0.
Which atom carries the most positive charge?
G G
15. Let ψ 1 ( x1 ) and ψ 2 ( x 2 ) be state functions for each of the electrons in H2. a)
G G
Write the total wavefunction Ψ ( x1 , x 2 ) for the electrons in the H2 molecule
using spin orbitals and a determinant. b) Take also spin into account by letting
each electron state function be a product of a space part and a spin part. What
does now the total wavefunction look like if H2 is in the ground state? c) Finally
we wish to represent each space part by a linear combination of (1s) orbitals φA
and φB for the free H atoms. Give the expression for the total wavefunction.