Beruflich Dokumente
Kultur Dokumente
(a) What is the probability for finding the electron within radius of
a0 from the nucleus?
(b) Two excited states of hydrogen atom are given by the following
wavefunctions:
2ar 2ar
1 (r) = A(2 + r)e 0 and 2 (r) = Br sin() cos()e 0
(a) The probability P for finding the electron within a0 (a ball with
radius a0 ; denoted by V below) is:
Z Za0
1 2
P = 0 0 d = 3 e2r/a0 |4r
{z dr}
a0
V 0 =d
4 a30 5a30 e2
= = 1 5e2 0.323
a30 4
Note that the 4 in the volume element above comes from the
fact that the function in the integral does not depend on the an-
gles and and therefore the angular part can be integrated
independently to yield 4 (i.e. the original volume element d =
r2 sin()dddr is then effectively just 4r2 dr). Above we have
used the following result from a tablebook:
Z
2 ax aax 2 2x 2
x e dx = x + 2
a a a
1
This was applied in the following form:
Za0
e2r/a0 r2 dr
0
e2r/a0 2 2r 2 1 2
= r + 2
2/a0 2/a0 (2/a0 ) 2/a0 (2/a0 )2
a0 e2 a2 a3
= a20 + a20 + 0 + 0
2 2 4
3 2 3 3 3 2
5a e a a 5a0 e
0 + 0 = 0
4 4 4
Z Z Z
4A
1 0 d = 4 1 (r)0 (r)r2 dr =p 3 (2 + r)e3r/(2a0 ) r2 dr = 0
a0
0 0
Z
(2 + r)e3r/(2a0 ) r2 dr = 0
0
Z Z
3r/(2a0 ) 2
2 e r dr + e3r/(2a0 ) r3 dr = 0
0 0
16a30 96 4
2 + a =0
27 81 0
1
a30 + a40 = 0 =
a0
2
Z Z Z2
|1 (r, , )|2 r2 sin()drdd
r=0 =0 =0
Z 2
2 r
= 4A 2 er/a0 r2 dr
a0
r=0
Z Z Z
4 1
= 4A2 4 r2 er/a0 dr r3 er/a0 dr + r4 er/a0 dr
a0 a20
r=0 r=0 r=0
2! 2 4 3! 1 4!
= 4A 4 3
4
+ 2
(1/a0 ) a0 (1/a0 ) a0 (1/a0 )5
= 4A2 8a30 24a30 + 24a30 = 32A2 a30 = 1
1 1
A= p 3
= p
32a0 4 2a30
3
Z
n!
xn eax dx =
an+1
Z0
cos(3ax) 3 cos(ax)
sin3 (ax)dx =
12a 4a
Z
x sin(2ax)
cos2 (ax)dx = +
2 4a
d(eikx )
(a) dx
= ikeikx = constant original function. Thus this is
an eigenfunction of the given operator.
d2 (eikx d
dx2
= dx (ikeikx ) = k 2 eikx = constantoriginal function.
Thus this is an eigenfunction of the given operator.
d(k) 2
dx
= ddx(k)
2 = 0. This could be considered as en eigenfunction
4
d2 (cos(kx))
dx2
= d(k sin(kx))
dx
= k 2 cos(kx). This is an eigenfunc-
tion (with eigenvalue k 2 ).
(b) f (x, y, z) = cos(ax) cos(by) cos(cz). The partial derivatives are:
f (x, y, z)
= a sin(ax) cos(by) cos(cz)
x
f (x, y, z)
= b cos(ax) sin(by) cos(cz)
y
f (x, y, z)
= c cos(ax) cos(by) sin(cz)
z
and
2 f (x, y, z)
= a2 cos(ax) cos(by) cos(cz)
x2
2 f (x, y, z)
= b2 cos(ax) cos(by) cos(cz)
y 2
2 f (x, y, z)
2
= c2 cos(ax) cos(by) cos(cz)
z
Therefore f (x, y, z) = (a2 + b2 + c2 )f (x, y, z) = constant
original function and this is an eigenfunction with the corre-
sponding eigenvalue (a2 + b2 + c2 ).
(c) The standard deviation can be calculated as:
1
0 (r) = p er/a0
a30
Z
2 1 4 3a50
r = 3 e2r/a0 r2 |4r 2
{z dr} = = 3a20
a0 a30 4
0 d
Z
1 2 3a0
hri = e2r/a0 r |4r
{z dr} =
a30 2
0 d
9a20
hri2 =
4
2 9a2 4a2
r hri2 = 3a20 0 = 0
q 4 4
3
hr2 i hri2 = a0 0.87a0
2
5
(d) The potential energy expectation can be calculated as:
1 e2
0 (r) = p 3 er/a0 and V (r) =
a0 40 r
Z Z
D E e2 1 2 e 2
V = 2 3 e2r/a0 |4r dr = e2r/a0 rdr
4 0 a0 r {z } 0 a30
r=0 d r=0
2
e a20 e 2
= 3
= 27.2 eV
0 a0 4 40 a0
1
4 2 /2
3. Consider function (x) =
ex . Using (only) this function,
show that:
Note that consideration of just one function does not prove a given
property in general.
Solution:
(a)
1/4 2 /2
(x) = ex
d
px = ih and [x, px ] (x) = (xpx px x) (x)
dx
To obtain the commutator, we need to operate with x and px :
1/4 d 1/4
x2 /2 2
(xpx ) (x) = ih x e = ih x2 ex /2
dx
1/4 d 2
(px x) (x) = ih xex /2
dx
1/4 2
1/4 2
= ih x2 ex /2 ih ex /2
When these are subtracted, we get:
6
1/4 2 /2
(xpx ) (x) (px x) (x) = ih ex
When the wavefunction (x) is removed, we have:
[x, px ] = ih
Solution:
7
(a) The probability for measuring +hk is cos2 (). We have a su-
perposition of the eigenfunctions of momentum and therefore the
squares of the coefficients for each eigenfunction give the corre-
sponding probability.
(b) The probability for measuring hk is sin2 ().
(c) Given cos2 () = 0.90 (hence cos() = 0.95) we use the nor-
malization condition cos2 () + sin2 () = 1 where we solve for
sin() = 0.32. The overall sign for the wavefunction does not
matter and therefore we have two possibilities for our wavefunc-
tion: = 0.95eikx 0.32eikx .
(d) Normalization condition: 1 = (0.9)2 +(0.4)2 +c23 . Thus c3 = 0.17.
(a) What is the average energy of the above superposition state (e.g.
< H >)?
(b) Plot 1 and 2 and determine the most probable positions for a
particle in these states.
(c) What are the most probable
q positions for the particle given by
2
wavefunction 3 (x) = L
sin 3x
L
where the box potential is
now located between [0, L].
Solution:
8
(a) We calculate the expectation value (H1 = E1 1 and H2 =
E2 2 ):
D E Z
H = (x)H(x)dx
Z
1
= (1 (x) + 2 (x)) H (1 (x) + 2 (x)) dx
2
Z
1 1
= (1 (x) + 2 (x)) (E1 1 (x) + E2 2 (x)) dx = (E1 + E2 )
2 2
= 2.5 eV
(b) For a = 1 both 1 (x) (one maximum) and 2 (x) (maximum and
minimum) are shown below:
The most probable values for position can be obtained from the
squared wavefunctions:
9
is then |0 (x)|2 sin2 (3x/L). The extremum points for this
function can be obtained by:
d
sin2 (3x/L) = 0 sin(3x/L) cos(3x/L) = 0
dx
3x 3x 1
= n or = n+
L L 2
n n + 1/2
x = L or x = L
3 3
Second derivatives can be used to identify the extrema:
d2 2
3x 3x
sin (3x/L) cos2 sin 2
dx2 L L
At x = n3 L the values are positive which means that these cor-
respond to (local) minima. For x = n+1/23
L the values are nega-
tive and these points correspond to (local) maxima. For example,
when L = 2 the probability function looks like:
Solution:
10
(a) For momentum:
1/2 nx
2
n (x) = sin , where 0 x L
L L
ZL 1/2 nx 1/2 nx
2 d 2
hpx i = sin ih sin dx
L L dx L L
0 | {z } | {z } | {z }
n
(x) px n (x)
ZL nx d nx
2ih
= sin sin dx
L L dx L
0
ZL nx nx
2nih
= sin cos dx = 0
L2 L L
|0 {z }
=0
ZL 1/2 nx 2 1/2 nx
2 2 d 2
px = sin ih sin dx
L L dx L L
0 | {z } | {z } | {z }
n
p2x n
ZL
2h2 nx d2 nx
= sin sin dx
L L dx2 L
0
ZL
2n2 2 h2 nx nx n2 2 h2
= sin sin dx =
L3 L L L2
0
| {z }
=L
2
q
Now we can calculate p = hp2x i hpx i2 = nh
L
. For position
11
we have:
ZL 1/2 nx 2 1/2 nx
2
hxi = sin x sin dx
L L L L
0
ZL nx
2 2
= x sin dx = L/2
L L
0
ZL 1/2 nx 2 1/2 nx
2 2 2
x = sin x sin dx
L L L L
0
ZL
2 2 2
nx L2 (2 2 n2 3) L2 3
= x sin dx = = 1 2 2
L L 6 2 n2 3 2 n
|0 {z }
L3 (4n2 2 6)
=
24 2 n2
q q q
2 2 2
Now x = hx i hxi = L3 1 232 n2 L4 = L 12
2 1
212 n2 .
Since we have both x and p, we can evaluate the uncertainty
product: r
n2 2 6
px = h
12 12
The smallest value is obtained with n = 1: px 0.568h > h2 .
(b) First recall that:
2 1 1/4
n (x) = Nv Hv x ex /2 , where Nv =
2v v!
Also the following relations for Hermite polynomials are used (lec-
ture notes & tablebook):
12
Denote y = x and hence dy = dx. Now hxi is given by:
Z
2
x2 /2 x2 /2
hxi = Nv Hv x e xHv x e dx
Z
Nv2 2 /2 2 /2
= Hv (y)ey yHv (y)ey dy
Z
Nv2 2
= Hv (y)y Hv (y)ey dy = 0
| {z }
= 1 Hv+1 (y)+vHv1 (y)
2
The last two steps involved using the recursion relation for Her-
mite polynomials as well as their orthogonality property. Next we
calculate hx2 i:
Z
2 Nv2 2
x = 3/2 (yHv (y))2 ey dy
Z 2
Nv2 1 2
= 3/2 Hv+1 (y) + vHv1 (y) ey dy
2
Nv2 2v+1 (v + 1)! 2 v1
= 3/2 + v 2 (v 1)!
4
1 1 1 h 1
= ((v + 1) + v) = v+ = v+
2 2 k 2
q
Combining the above calculations gives x = v + 21 hk . Next
we calculate p:
d
p = ih and dy = dx.
dx
Z
y 2 /2 y 2 /2
hpi = Nv Hv (y)e p Nv Hv (y)e dy
Z
2 /2 d 2
= ihNv2 Hv (y)ey Hv (y)ey /2 dy
dx
13
Above differentiation of the eigenfunction changes parity and there-
fore the overall parity of the integrand is odd. Integral of odd
function is zero and thus hpi = 0. For hp2 i we have:
Z
2 2 /2 2 /2 dy
p = Nv Hv (y)ey p2 Nv Hv (y)ey
The operator
must also be transformed from x to y: p2 = (ihd/dx)2
= (ih d/dx)2 ). The above becomes now:
Z
y 2 /2 2 d2 2
dy
Nv Hv (y)e h 2 Nv Hv (y)ey /2
dy
Z
2
y 2 /2 d2 y 2 /2
= h Nv2 Hv (y)e Hv (y)e dy
dy 2
Z
2
= h2 Nv2 Hv (y) (y 2 1)Hv (y) 2yHv (y) + Hv (y) ey dy
| {z }
=2vHv (y)
Z
2
= h2 Nv2 Hv (y) (y 2 1)Hv (y) 2vHv (y) ey dy
Z Z
2
2 2
Nv2 (2v 1) Hv2 (y)ey dy + y 2 Hv2 (y)
= h ey dy
| {z }
2
| {z } =( 2 Hv+1 (y)+vHv1 (y))
1
= 2v v!
2
1 v+1
= h Nv2
(2v 1) 2 v! + v
2 (v + 1)! + v 2 2v1 (v 1)!
4
2
2
v v+1 v 2 1
= h Nv 2 v! 2v + 1 = h v +
2 2 2
1
= h mk v +
2
14
q
Therefore we have p = h mk v + 21 . Overall we then have
q q
xp = 1 h
v + 2 mk h mk v + 21 = h(v + 21 ) h2 .
I |(x)|2 = B 2 e2Kx
I1
= e2K(x1 x2 )
I2
1/2
K = 2me (V E) /h2
| {z }
=2 eV
1/2
2(9.11 1031 kg)(2.0 eV)(1.602 1019 J/eV)
=
(1.0546 1034 Js)2
2K(x1 x2 ) = 2K (0.10 109 m) 1.45
I1
4.3
I2
8. Show that the sperhical harmonic functions a) Y0,0 , b) Y2,1 and c) Y3,3
are eigenfunctions of the (three-dimensional) rigid rotor Hamiltonian.
What are the rotation energies and angular momenta in each case?
15
Solution:
h2 2
H(r, , ) = E(r, , ) where H =
2I
1 2 1
2 = 2 2
+ sin()
sin () sin()
2
Since h2I is constant, it is sufficient to show that spherical harmonics
are eigenfunctions of 2 . We operate on the given spherical harmonics
by 2 .
(a) = ei
(b) = e2i
(c) = cos()
(d) = cos()ei + sin()ei
Solution:
16
2 2 2
The Hamiltonian for 2-D rotation is H = L2Iz = h2I dd
2 where the
(d) Operation by Lz would change the plus sign in the middle of the
wavefunction into a minus, hence this is not an eigenfunction of
i
Lz . It is an eigenfunction of H: H(cos()e
+ sin()ei ) =
2 2
h2I (i)2 cos()ei + (i)2 sin()ei = h2I cos()ei + sin()ei .
17