Problem Set 6 Solutions

Distributed: March 12, 2016

Due: March 16, 2016

McQuarrie Problems
7-9 Show also that the electron must be tunneling whenever it is in the region beyond 2a0 .

Calculate the probability that a hydrogen 1s electron will be within a distance of 2a0
of the nucleus. From table 7.2, R1s (r) = 2 −r/a0 .
3/2 e
a0

The probability that the electron is within 2a0 is

∫ 2a0
∗
Prob {0 ≤ r ≤ 2a0 } = dr r2 R1s (r) R1s (r)
0
∫ 2a0
4 2 2
= 3 dr r2 e−2r/a0 Use x = r and xd = dr
a0 0 a0 a0
∫ 4
4 a0 ( a0 )2 −x
= 3 dx x e
a0 0 2 2
∫
1 4
= dx x2 e−x u = x2 , du = dx 2x, dv = −dx e−x , v = e−x
2 0
[ ∫ 4 ]
1 
2 −x 4 −x
= −x e 0 + 2 dx xe Use w = x, dw = dx, and v from before.
2 0
[ ∫ 4 ]
1 4
= −x2 e−x + 2xe−x 0 + 2 dx e−x
2 0
1 [ 2 −x −x
 ]
−x 4
= −x e + 2xe − 2e 0
2
1[ ]
= −16e−4 + 8e−4 − 2e−4 + 2
2
1[ ]
= 2 − 26e−4
2
= 1 − 13e−4
= 0.762

Is it tunneling beyond 2a0 ? Tunneling happens when a particle is beyond its classical
energetic limits. To find the classical limit, E1s = Tcl + Vcl for a classical particle
with the same energy as an electron in the 1s orbital, the maximum potential occurs
when Tcl = 0, so Vcl = E1s . Arranging this to solve for the radius:

Vcl = E1s
e2 e2
− =− =⇒ r = 2a0 .
4πϵ0 r 8πϵ0 a0

So the classical limit of the nuclear distance of a particle with an energy of a 1s

orbital is 2a0 . We just found that the probability of finding an electron with a nuclear

Boekelheide CH342: Quantum Chemistry

Problem Set 6 Solutions 2

distance less than 2a0 is less than 1, so yes , this does demonstrate tunneling.

7-14 Do only the 2pz .

[ ]
Compute ⟨r⟩ for 2s and 2pz , comparing results to ⟨rnl ⟩ = a20 3n2 − l(l + 1) .
( )3
2 r −
r
For the 2pz , ψ2pz = ψ210 = 4√12π a10 a0 e
2a0 cos θ. The expectation value of r is

∫ 2π ∫ π ∫ ∞ ( )2
1 1 r − ar
⟨r⟩ = dϕ dθ sin θ 2
dr r re 0 cos2 θ
32π a30 a0
| {z }
0 0 0
2π
∫ π ∫ ∞ ( )
1 2 1 − r
= 3 dθ cos θ sin θ dr 2 r 5 e a0
16a0 0 a0
| {z } |0 {z }
From integral tables1 Use x= ar
π ) ∫ ∞
0
( ( )
1 cos3 θ  1 5 −x
= 3 −  dx a0 2 (a0 x) e
16a0 3 0 a
( ( )) ∫0 ∞ 0
∫ ∞
a0 −1 1 5 −x n!
= − − dx x e Use dx xn e−ax = n+1
16 3 3 0 0 a
( )
a0 2
= (5 × 4 × 3 × 2)
16 3
= 5a0
[ ]
Compared to ⟨r21 ⟩ = a0
2 3 × 22 − 1(1 + 1) = a0
2 [12 − 2] = 5a0 , this is the same,
again.

The general formula for ⟨rnl ⟩ seems to hold. Also, we confirmed that the 2pz orbital
has a smaller average radius than the 2s.

7-47 By what percentages do the perturbed energies differ from their original values?

We’re calculating the energy of the transition between the upper 2p 2 P1/2 state and
the lower 1s 2 S1/2 state. Following example 7-9 we see the strategy:

For the upper state (2p 2 P1/2 ), the l, j, and mj quantum numbers are 1, 12 , and − 12 .
Thus, g = 32 , and suing equation 7.75,

∆Eupper =gβB mj Bz
( )( )( )
2 J 1
= 9.2740 × 10−24 − (1.00 T)
3 T 2
( ) ( )−1 ( ) ( m )
m −1
= −3.0913 × 10−24 J 6.6261 × 10−34 J · s 2.9979 × 108 s 100 cm
= − 0.156 cm−1

Using the values from table 7.7, the energy of the 2p 2 P1/2 state in the absence of
∫b b

1
From the integral tables, a
dx sin x cosn x = − n+1
1
cosn+1 x .
a

Boekelheide CH342: Quantum Chemistry

Problem Set 6 Solutions 3

a magnetic field is is 82258.9206 cm−1 . Thus, the energy of the upper state is

Eupper = 82258.9206 cm−1 − 0.156 cm−1 = 82258.765 cm−1

For the lower state (1s 2 S1/2 ), the l, j, and mj quantum numbers are 0, 21 , and 12 ,
respectively. Thus, g = 2, and suing equation 7.75,

∆Elower =gβB mj Bz
( )( )
−24 J 1
= (2) 9.2740 × 10 (1.00 T)
T 2
( ) (
J ( )−1 ( )
m −1 m )
= 9.2740 × 10−24 J 6.6261 × 10−34 J · s 2.9979 × 108 s
T 100 cm
= + 0.467 cm−1

Using the values from table 7.7, the energy of the 1s 2 S1/2 state in the absence of
a magnetic field is is 0 cm−1 . Thus, the energy of the lower state is

Elower = 0 cm−1 + 0.467 cm−1 = 0.467 cm−1

So the energy of the transition in the field is ∆E = Eupper −Elower = 82258.765 cm−1 −
0.467 cm−1 = 82258.298 cm−1 .

Comparing this result to the energy of the transition in the absence of the field, the
energy of the 2p 2 P1/2 state reported in table 7.7, 82258.9206 cm−1 , the ratio of the
82258.9206 cm−1
unperturbed to the perturbed energy is 82258.298 cm−1
≈ 1.00001, or a difference of
a magnitude 0.1 cm−1 . Our IR spectrometer has a precision of 1 cm−1 , so this really
highlights the insensitivity of magnetic techniques.

Problem 1:
Table 7.3 gives you the exact wavefunctions to use for n = 1, 2 and 3. Use information from lecture or
the chapter construct the correct and complete hydrogenlike atomic wave functions for the 4s orbital.

In general the hydrogen-like wavefunctions take the form ψnlm (r, θ, ϕ) = Rnl (r) Ylm (θ, ϕ)
where
{ }1/2 ( )l+3/2 ( )
(n − l − 1)! 2 l −r/na0 2r
Rnl (r) = − re L2l+1
n+l
2n [(n + l)!]3 na0 na0

and [ ]1/2
(2l + 1) (l − |m|)! |m|
Ylm (θ, ϕ) =i m+|m|
Pl (cos θ) eimϕ
4π (l + |m|)!
where L are the Laguerre polynomials (sent in an email) and P are the Legendre
polynomials (table 6.4).

Boekelheide CH342: Quantum Chemistry

Problem Set 6 Solutions 4

( )
For the 4s orbital n = 4, l = 0, and m = 0, and the Laguerre polynomial is L14 2ar 0 =
[ ( ) ( )2 ( )3 ]
−4! 4 − 6 2a0 + 2 2a0 − 6 2ar 0
r r 1
and the Legendre polynomial P00 (cos θ) =
1. Using these, R part of the wavefunction is
 
( )1/2 ( )3/2  [ ( ) ( )2 ( )3 ]
3! 1  r r 1 r 
R40 (r) = − e−r/4a0 ×
−4! 4 − 6 + 2 − 

2 × 4(4!)3 2a0  2a0 2a0 6 2a0 
| {z }
BLAH
√ √
3 
2 1 1
=√

√ √ √ √ √ √ √ √ e−r/4a0 · 4
· 3
· 2
× BLAH

2 ·   
2 · 2 · 2 · 23 3 3 2 2 2 2
2 a0 a0
1 1
= √ e−r/4a0 × BLAH
2 · 2 · 2 · 2 a0 a0
1 1
= √ e−r/4a0 × BLAH
16 a0 a0

The Y part is
[ ]1/2
(1) 0!
Y00 (θ, ϕ) =i 0
(1) e0ϕ
4π 0!
1
= √ .
2 π

Combining these terms and simplifying BLAH, the wavefunciton for the 4s orbital is

ψ400 (r, θ, ϕ) =R40 (r) Y00 (θ, ϕ)

[ ]
1 1 r 1 r2 1 r3 −r/4a0
= √ 3/2 4 − 3 + − e
32 π a a0 2 a20 48 a30
0

Problem 2:
For an electron in a 1s orbital of hydrogen:

For a 1s orbital, ψ100 = √1 3/2

πa
1
e−r/a0 .
0

2.a: Calculate ⟨x⟩, where x = r sin θ cos ϕ. Interpret your result.

Boekelheide CH342: Quantum Chemistry

Problem Set 6 Solutions 5

The expectation value for x using the above definition of x is

∫ 2π ∫ π ∫ ∞
1 1 −2r/a0
⟨x⟩ = dϕ dθ sin θ dr r2 r sin θ cos ϕ e
0 0 0 π a30
∫ 2π ∫ π ∫ ∞
1
= 3 dϕ cos ϕ dθ sin θ2
dr r2 re−2r/a0
a0 π
| 0
{z } 0 0
=0 Hey-yo!

=0

This should be the average position of an electron on the x-axis, because x =

r sin θ cos ϕ is the conversion from spherical to Cartesian coordinates. This result
tells us that the average position is 0. This makes sense because of symmetry of
the 1s wavefunction (and wavefunctions in general) over the nucleus along the x-axis.

2.b: Calculate σr (the square root of the variance of the electron’s distribution in the radial direction).
Use the fact that ⟨r⟩ = 3a0
2 for the 1s state. This problem points out exactly how wrong Bohr was when
he developed a theory in which σr = 0!
√
The square root of the variance σr = ⟨r2 ⟩ − ⟨r⟩2 where we’re given ⟨r⟩ = 3a0
2 . I
⟨ ⟩
guess we have to calculate r2 .
∫ 2π ∫ π ∫ ∞
1 1 −2r/a0
⟨x⟩ = dϕ dθ sin θ dr r2 r2 e
π a30
|0 {z
0
} 0

∫ ∞ 4π ∫ ∞
4π n!
= 3 dr r4 e−2r/a0 Use dx xn e−ax =
a0 π 0 0 an+1
4 4!
= 3 ( )5
a0 2
a0
2 · 2 · 2 · 2 · ·3 · 2 2
= a
2·2·2·2·2 0
=3a20

⟨ ⟩ { [ ]}
l(l+1)− 31
which is the same as we get for the general form of r2 nlm = a20 n4 1 + 32 1 − n2

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Problem Set 6 Solutions 6

from table 7.4. Plugging this result into σr

√
σr = ⟨r2 ⟩ − ⟨r⟩2
√
9a20
= 3a20 −
√ 4
2
12a0 9a20
= −
√ 4 4
2
3a0
=
√ 4
3
= a0
2
√
3a0 3
If the mean value for r is 2 , and the square-root of the variance is 2 a0 , that’s a
√
relative error of σr /r = 1/ 3 ≈ 57.7%! Bohr was very wrong to assume we could
exactly know r.

Problem 3:
The typical picture of the angular part of a hydrogen-like dz 2 -orbital is shown on page 339 of the text.
Haven’t you always wondered how probable it is to find the electron in that p-orbital’s tutu? Here’s you
chance! Think about how to find the exact limits on the θ integral.
+z
20a0

+z θA

θB
15a0 +y

+x
+y

We’re going to integrate over the full range of ϕ and r. The bounds of θ are more
complicated, but are demonstrated in the figure to the left. We just need to figure
out what those bounds are—or where the angular nodes are.

The wavefunction for the dz 2 -orbital is ψ320 (r, θ, ϕ) = R32 (r) Y20 (θ, ϕ) the Y function
determines the nodes on θ. Setting that equal to zero and solving for θ should give

Boekelheide CH342: Quantum Chemistry

Problem Set 6 Solutions 7

the values of θ:
( )1
5 2 ( )
Y20 (θ, ϕ) = 3 cos2 θ − 1 =0
16π
( )
3 cos2 θ − 1 =0
1
cos2 θ =
3
1
cos θ = ± √ θ ≈ 0.304π or 0.696π = 54.7◦ or 125.3◦ .
3

So the nodes in θ occur at about 54.7◦ and 125.3◦ . The tutu is bounded by these
angles, so these are the ranges to integrate. Setting this up, I’m going to keep it
general initially, because the R term will fall out and because we’ll be able to use
cos θB = − √13 and cos θA = √1 :
3

∫ ∞ ∫ ∫
2π θB ( )2
Probtutu = dr dϕ dθ r2 sin θ R32 (r) Y20 (θ, ϕ)
0 0 θA
∫ ∞ ∫ ∫
2 2
2π θB ( )2
= dr r (R32 (r)) dϕ dθ sin θ Y20 (θ, ϕ)
|0 {z } 0 θA
=1
∫ ∫ (( )1 )2
2π θB
5 2 ( )
= dϕ dθ sin θ 3 cos θ − 1
2
16π
| 0 {z } θA
=2π
∫
10π θB ( )2
= dθ sin θ 3 cos2 θ − 1
16π θA
[∫ θB ∫ θB ∫ θB ]
5
= dθ sin θ − 6 2
dθ sin θ cos θ + 9 4
dθ sin θ cos θ
8 θA θA θA
[ θB ]
5 6 9 
= − cos θ + cos3 θ − cos5 θ
8 3 5 θA
[ ] [ ]
5 6 9 5 6 9
= − cos θB + cos θB − cos θB −
3 5
− cos θA + cos θA − cos θA
3 5
8 3 5 8 3 5
[ ] [ ]
5 1 6 1 9 1 5 1 6 1 9 1
= 1/2
− 3/2
+ 5/2
− − 1/2 + 3/2
−
8 3 33 53 8 3 33 5 35/2
[ ]
5 2 12 1 18 1
= √ − √ + √
8 3 3 3 3 5 9 3
[ ]
5 4 2
= √ 2− +
8 3 3 5
5 16
= √
8 3 15
2
Probtutu = √ ≈ .3849 = 38.49%
3 3

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Problem Set 6 Solutions 8

So there’s a 38.49% chance that the electron will be found in the equatorial tutu in
the dz 2 -orbital, where the tutu is defined as the volume bounded by the two angular
nodes.

Useful integrals to remember:

∫ ∑
m
m!rm−x
dr rm ebr = ebr (−1)x
(m − x)!bx+1
x=0
∫ ∞
n!
dx xn e−ax =
0 an+1
∫ b
b
1 
dx sin x cosn x = − cosn+1 x
a n+1 a

Boekelheide CH342: Quantum Chemistry