Problem Set 7. Due Mar.

13 in class
1. This is a “don’t forget” problem- can you know the momentum of a wavefunction and its kinetic
energy the same time? (10 pts)
  2 2 
Hint: show that p̂ x ,  0.
 2m x 2 
Answer: First, write out the expression for the commutator:
  2 2   2 2  2 2
p̂ x , 2m x 2   p̂ x  2m x 2  2m x 2  p̂ x Now, write out the momentum operator and have all of it
 
act on a wavefunction:
  2 2      2 2  2 2   
p̂ x , 2m x 2  ( x )   i x  2m x 2  2m x 2  i x ( x ) . Now, factor the constants:
   
  2 2   3    2 2    3  3 3 
 x 2m x 2 
p̂ ,  ( x )        ( x )    ( x ) . The inside of the
  2im  x x 2 x 2 x  2im  x 3 x 3 
commutator is 0, thus, there is no uncertainty principal between kinetic energy and momentum. This is
one of the few examples you can evaluate a commutator without necessarily acting on a wavefunction
like you do in number 8.

2. In class, we derived that the angular momentum of light imparts a l = ±1 and m or

selection rule for hydrogen atom transitions (where m depends on the polarization of light and
orientation of the hydrogen atom). However I didn’t specify what n was. I can tell you that n cannot
be 0. Why? (5 pts)
Hint: l = ±1 and m or come abo t from conservation of ang lar moment m can yo thin
of another, very basic conservation law that must be obeyed?

Answer: Conservation of energy- thus while it appears a 2p to 2s transition is allowed, these states are
degenerate and thus it takes no energy to make the transformation. No light has no energy, therefore n
cannot be 0.

3. Here is another way back question- is the 1s wavefunction, 1s  N1secr  Yl0,m0 , an eigenfunction of
 2  2 2   2 2
the kinetic energy operator, which is:  2     ? To make it easier, note that
2m  r r r  2mr 2
2 2
  operates on the angular part to give
2
l(l  1) , which simplifies the problem to
2mr 2 2mr 2
 2  2 2   2
 2    l(l  1) operating on 1s (r)  N1secr . (7 pts)
2m  r r r  2mr 2

Answer: The question is even easier than it seems as l=0 the angular term is gone entirely. So you just
 2  2 2  
have to see if the operation does the following:    N1s e cr  (some number)  N1s e cr . If
2m  r 2 r r 
  2  2 2     2 2 cr  2 c cr
we do the operation we get:    cr
N1s e  c e    e . So it doesn’t since
2m  r 2 r r  2m 2m r
1
yo have to get “rid” of that factor of in the second term and yo can’t. So its not an eigenf nction of
r
kinetic energy, and in fact none of the wavefunctions are.

4. a. We found that quantum mechanics can allow a harmonic oscillator to stretch beyond the classical
t rning point (that’s where the potential energy is eq al to the inetic energy beyond the t rning point
you must technically have negative kinetic energy). Electrons in the 1s state of hydrogen can do the
same; can you calculate the turning point? (10 pts)
4
me
Hint, it should have 0 , , e 2 , and m in it, and the energy of the 1s state is  (m is the mass of
322  02  2
 2 2 2 e2
the electron), and note that Ĥ  r  l( l  1)  .
2m r 2 2mr 2 4 0 r

me 4
b. Since the energy of the 2s state is  , 1/4th the energy of the 1s state, can you show that the
128  0 
2 2 2

32 0 2
turning point is rtp  ? If you got pt. a right yo sho ldn’t even have to show any derivation to
me 2
answer this question. (4 pts)

c. I was wondering why the turning point keeps getting longer, and then I remembered to use extreme
examples. For the n ∞ state what is the t rning point? (4 pts)

d. To calculate rtp for the 2p state, you start with the following expression:
e2 2 me 4
    . Disc ss how yo wo ld go abo t solving it (don’t do it it ta es
4 0  rtp m  rtp2 1282 02 2
forever). (4 pts)
16 0 2
e. I found that the turning point of the 2p state to be rtp  1.71 ; just slightly less than the 2s
me 2
state even though they have the same total energy. Why does this ma e sense? Hint: let’s write the
e2 me 4 2
expression to pt. d differently:    ; thus the second term on the right makes
4 0 rtp 1282 02 2 mrtp2
the total right hand term a “bigger” negative n mber. Still not s re? Thin abo t how the answer to pt. c
8 0 2
rtp ∞ compares to pt. a: rtp  . (7 pts)
me 2

Answer: a. Questions within questions: first note that the Hamiltonian is:
 2 2 2 e2
r  l( l  1)  , so I am hoping that you recognize that the potential energy is:
2m r 2 2mr 2 4 0 r
 2 e2 e2
l( l  1)  . Since l=0, the potential energy is just  which you set equal to:
2mr 2 4 0 r 4 0 r
me 4
 and recognize that the r term in the potential energy is the turning point rtp.
32 2  02  2
e2 me 4
  ; the negative signs cancel and you can now factor:
4 0 rtp 322 02 2
e 2 322 02 2
 rtp . If you felt like simplifying it:
4 0 me 4
8 0 2
rtp 
me 2
1
b. If the energy is four times less, which is proportional to , then the turning point gets four times
rtp
32 0 2
bigger making rtp  .
me 2
1
c. If the energy was which it is for n ∞ then I am basically left with  0 , making rtp ∞.
rtp
d. Multiply by rtp2 and use the quadratic equation.
e. When the energy is a “bigger” negative n mber then the t rning point gets closer to the nucleus. The
me 4 2
effect of the right hand term in   ma es the right hand side a “bigger” negative which
1282 02 2 mrtp2
ultimately will shrink the length of the turning point.

5. The ground state 1s wavefunction of the hydrogen atom is 1s (r)  N1secr  Yl0,m0 and the 2s state is
2s (r)  N 2s 2  cr   e
cr
2
 Yl0,m0 , where Yl0,m0 is the correct spherical harmonic.
a. As eigenstates of the Hamiltonian must be orthogonal, do you think the spherical part will be 0? i.e.
 2

 Y l  0 , m 0  Yl0,m0  sin       0 ? Hint: yo sho ldn’t even have to try to do the act al math to
0 0
show it is not 0. (5 pts)

b. Given the result from part a, can you show that  (r )
0
2s  (r )1s  r 2  r  0 ? i.e. use the radial

wavefunctions. (10 pts)

  
2 6 24
Also,  x 2  e ax dx  x
3
 e ax dx  x
4
 e ax dx 
0
a3 0
a4 0
a5

Answer: a. This is the same as checking whether is normalized, which is it (since both states are s-
states). Therefore, the integral is 1.

cr
b. First, set up the proper integral:  N 2s 2  cr   e 2
 N1s e cr  r 2  r and now simplify it a bit:
0
 
cr
N 2s  N1s  2  cr   e 2
 e cr  r 2  r 
0

3cr
N 2s  N1s  2  cr   e 2
 r 2  r 
0
 
3cr 3cr
N 2s  N1s  2   r  e 2 2
 r  N 2s  N1s  c   r 3  e 2
 r . Now we are ready to use the identities:
0 0


3cr 2 8 32
N 2s  N1s  2   r 2  e 2
 r  N 2s  N1s  2  3
 N 2s  N1s  and
0
27c 27c3

3cr 6 16 32
 N 2s  N1s  c   r 3  e 2
 r   N 2s  N1s  c  4
  N 2s  N1s  c  . Thus, add them up and you get 0.
0
81c 27c3

6. It turns out that the orbital designations px, py, and pz are because the correct angular momentum
wavefunctions for the three p orbitals are of the form x, y, and z. I did a few of the d-orbitals in class,
now you do the rest.
Knowing that x  r  cossin() , y  r  sinsin() , and z  r  cos , can you fill out the remaining
table:
 result d-function
r  cos 
2
r ×Yl=2,m=0 2 2 z2

r2×(Yl=2,m=2 + Yl=2,m=-2) r 2  sin 2  cos 2   sin 2  x2-y2 
2
r ×(Yl=2,m=2 - Yl=2,m=-2) a. a.
r2×(Yl=2,m=1 + Yl=2,m=1) r  cossincos
2 xz
2
r ×(Yl=2,m=1 - Yl=2,m=1) b. b.
You can look at table 8.2 to get the spherical harmonic wavefunctions. (10 pts)
Hint: sin2x   2 sin(x) cos(x)

Answer: a. r2×(Yl=2,m=2 - Yl=2,m=-2) = r 2  sin 2 e2i  e2i   r 2  sin 2 sin2 . Using the identity in
the hint: r 2  sin 2 sin2  r 2  sin 2 sincos() , which is obviously xy.

b. r2×(Yl=2,m=1 - Yl=2,m=-1) = r 2  cos() sinei  ei   r 2  cos() sinsin , which is obviously yz.

7. More on spin wavefunctions. Right now, we have just said that the spin up wavefunction is  and the
spin down is ; they have no functional form but they do a few things. For one, they must make
wavefunctions orthogonal. Given that two electrons may have the radial and angular parts of the 1s
wavefunction but different spins, i.e. the spin up electron has this wavefunction:
1s  N  R n1,l0  Yl1,m0   while the spin down wavefunction is 1s  N  R n1,l0  Yl1,m0   , can you
therefore determine what the following integrals are equal to? (6 pts)
  2

  r sin()  r    
2
a.
0 0 0
   2

     r sin()  r    
2
b.
0 0 0
  2

     r sin()  r    
2
c.
0 0 0

Answer: a. 0. b. 0. c. 1.