CML101 2020-21 I semester Minor 1

Dec. 28, 2020

Important: This is a 90 min. exam (Organic and Physical together).

Helpful facts:
1 ∂2
 
2 2 1 ∂ ∂
L̂ = −h̄ sin θ +
sin θ ∂θ ∂θ sin2 θ ∂φ2
∂
L̂z = −ih̄
∂φ
 
2 1 ∂ 2∂ 1 ∂ ∂ 1 ∂
∇ = 2
r + 2 sin θ +
r ∂r ∂r r sin θ ∂θ ∂θ r sin θ ∂φ2
2 2
π π
1 · 3 · 5 · · · (2m − 1) π
Z Z
2 2m 2
sin x dx = cos2m x dx = · for m = 1, 2, 3, . . .
0 0 2 · 4 · 6 · · · (2m) 2
π π
2 · 4 · 6 · · · (2m)
Z Z
2 2m+1 2
sin x dx = cos2m+1 x dx = for m = 1, 2, 3, . . .
0 0 1 · 3 · 5 · · · (2m + 1)
Z ∞
n!
x n e−ax dx =
0 a n +1
1. A friend of yours claims that a particle in a box extending from 0 to L is in
a stateqψ = Ax ( L − x ); you argue with her because this looks different from
ψn = 2
L sin nπx
L derived in the class by your teacher.

(a) Given that your friend is a self-declared QM wiz, and, especially, because
of your lack of confidence in your teacher’s ability, you decide to verify
whether she is right (not in her presence, of course). How would you do
so? [1]
(b) Sure enough, you have to swallow your pride as she was right. You are
curious now and decide to evaluate the energy of the particle (mass m) in
this state. What would you find it to be? [2]
(c) This leaves you even more perplexed because you expected the energy to
n2 h2
be of the form 8mL 2 . You do not understand the relevance of the result in
Q. 1b and ask your friend for an explanation. How would she explain your
result? [1]

Solution:

(a) Satisfies the boundary conditions of ψ( x = 0) = 0 and ψ( x = L) = 0, in

addition to the usual conditions on the wavefunction; the first derivative
can have discontinuities at the V = ∞ boundary.
q
(b) The normalization constant is 30 L5
which is determined from
Z L
2
A x2 ( L − x )2 dx = 1
0

3  L
x4 x5  5
Z L 
2x 2L

2 2 2 3 4 2
A L x − 2Lx + x dx = A L − 2L + = A =1
0 3 4 5 0 30
 !Z
30 h̄2 L d2
h Ei = 5 − x( L − x) x ( L − x ) dx
L 2m 0 dx2
!
h̄2
Z L
30
= 5 − (−2) ( Lx − x2 ) dx
L 2m 0

30 h̄2 L3 5h̄2
= =
L5 m 6 mL2

(c) The given ψ is not an energy eigenfunction. The expectation value of energy
n2 h2
could be pretty much anything. It does not have to be 8mL 2 . Aside: It is
gratifying that the energy is greater than the true ground state energy.

2. In class we introduced the idea of a centrifugal potential to explain some of the

features of the radial wavefunction of the hydrogen atom. For an electron in the
 3/2    
r r
state √1 1
a0 a0 exp − 2a0 cos θ, what is this potential? [2]
4 2π
l (l +1)h̄2
Solution: The centrifugal potential, Vcp , was 2mr2
. Here l = 1. Thus
Z ∞
l (l + 1)h̄2 2h̄2 1 h̄2 1 h̄2 1
   
1 1 2 r
Z
∗ 3
hVcp i = ψ ψ dτ = r exp − dr = 2a = .
2m r2 2m 8a30 0 a0
2 a0 m 8a50 0 m 4a20

3. This question pertains to the molecule H3+.

(a) Write down the complete Hamiltonian (the form of any differential operators
need not be specified) for this molecule in atomic units. [1]
(b) In the Hamiltonian in Q. 3a label the terms (as A, B, . . .) that are “easily”
treated in the Born-Oppenheimer approximation. Provide a one sentence
justification in each case. [1]
(c) Do you expect linear H3+ or triangular (equilateral) H3+ to be more stable
(inter-proton distances being the same)? Why? [1]
(d) For the following parts, consider that the inter-proton distances in H3+ are
zero.
i. Write the Hamiltonian in this case. [1]
ii. In the absence of the term or terms in the Hamiltonian in Q. 3(d)i which
makes it difficult to solve the Schrödinger equation exactly, what is the
energy of the ground state (in eV or atomic units or as an expression
containing fundamental constants)? [1]
iii. Write the functional form (which captures the qualitative features) of the
ground state wavefunction for the system if the Schrödinger equation
for this system is solved. In one sentence justify your answer. [1]

Solution:

(a) The Hamiltonian in atomic units is (with the three protons notated A, B,
 and C, and the two electrons 1 and 2)
1 1 1 1 1
Ĥ = − ∇2A − ∇2B − ∇2C − ∇21 − ∇22
2m A 2m B 2mC 2 2
1 1 1 1 1 1 1
+ − − − − − −
r12 r1A r1B r1C r2A r2B r2C
1 1 1
+ + +
r AB r AC r BC

(b) First three terms are zero; nuclei are fixed, KE is zero. Last three terms are
constant; internuclear PE is a constant.
(c) Triangular; more overlap, more delocalization
(d) For the following parts, consider that the inter-proton distances in H3+ are
zero.
i. If R = 0, then it corresponds to Li+, whose Hamiltonian is
1 1 1 1 3 3
− ∇2Li − ∇21 − ∇22 + − −
2mLi 2 2 r12 r1Li r2Li

ii. The energy is dependent on Z2 , so −2 × 9 × 13.6 eV or 9.0 au.

iii. In the independent electron approximation, ψ = g1s (1) g1s (2), where
g1s is similar to R1s of hydrogen atom; has different Zeff .
4. The cobalt complex CpCo(NO)(CH3)(PEt3) undergoes nitroso insertion to give
the nitrosomethane complex CpCo(CH3NO)PEt3. The rate law observed was
kobsd [CpCo(NO)(CH3)(PEt3)].

(a) Qualitatively sketch the variation of [CpCo(CH3NO)PEt3] with time. [1]

(b) Outline the steps to obtain kobsd from your sketch in Q. 4a. [1]
(c) The mechanism proposed for this reaction is
k1
CpCo(NO)(CH3)(PEt3) k −1
CpCo(NO)(CH3) + PEt3

k2
CpCo(NO)(CH3) CpCo(CH3NO)
k3
CpCo(CH3NO) + PEt3 CpCo(CH3NO)PEt3
For this mechanism, obtain the rate of the reaction within the steady state
approximation, and a relationship between kobsd and the rate constants of
the elementary reactions. [2]
kobsd
(d) The mechanism CpCo(NO)(CH3)(PEt3) CpCo(CH3NO)PEt3 could
also explain the observed rate law. How would you establish the mechanism
given in Q. 4c? [1]
(e) Is it possible to determine any of the rate constants of the elementary
reactions? If so, how? [1]

Solution: We call the reactant R, the product P, the two intermediates I1 and I2,
and PEt3 as L.
(a) The concentration of the product grows as [P] = [R]0 1 − e−kobsd t and

would look something like the curve below.

(b) A least squares fit (with [R]0 and kobsd as free parameters) of the concentration-
time graph to the equation given above would be a way. Another possibility
is to plot ln([R]0 − [P]) vs. t, the slope of which is −kobsd . Note that
[R]0 = [P] ∞ .
(c) we have
k 1 [R]
d[I1]/dt = k1 [R] − k −1 [I1][L] − k2 [I1] ≈ 0 =⇒ [I1] =
k −1 [ L ] + k 2
k 2 [ I1 ]
d[I2]/dt = k2 [I1] − k3 [I2][L] ≈ 0 =⇒ [I2] =
k 3 [L]
k 2 [ I1 ] k 1 k 2 [R]
Rate = k3 [L][I2] = k 3 [L] =
k 3 [L] k −1 [ L ] + k 2
k1 k2
kobsd =
k −1 [ L ] + k 2
(d) Note that
1 1 k [L]
+ −1 ,=
kobsd k1 k1 k2
which means that if the reaction is studied at various [PEt3] concentrations,
a linear dependence of k 1 on [L] is observed.
obsd
1 1
(e) In the previous equation the intercept of the plot of kobsd vs. [PEt3] is k1 and
k −1
the slope is k1 k2 . So, one can measure k1 from the intercept, while the slope
k −1
divided by the intercept gives k2 .