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h 2 d 2
= E
2
2m dx
= Aeikx + Be ikx
k 2h 2
E=
2m
+
V(x)
V(x)
V(x) = 0
0
h 2 d 2
= E
2
2m dx
= Aeikx + Be ikx = C cos kx + D sin kx
Outside the box: V = , so that outside the box = 0, and because is continuous,
must also be 0 at the edges of the box, i.e.(0) = 0 and (L) = 0.
For (0) = 0 then C = 0, and so (x) = D sin(kx).
For (L) = 0 then either D = 0 (SILLY!) or (L) = D sin(kL) = 0.
sin(n) = 0 where n = 1, 2, 3, and so k is now restricted as follows:
n
k=
L
Quantisation of energy
Boundary conditions lead to wavefunctions (eigenfunctions) of the form (x) = D sin kx
with quantised values of k (= n/L) and results in quantised values for the energy E:
k 2h 2 n 2 h 2
E=
=
2m 8mL2
Eigenvalues:
n = 1, 2, 3,....
2
*
sin
x
D
d
=
kx dx = 1 D =
2
Eigenfunctions:
( x) =
2
nx
sin
L L
n = 1,2,....
2
L
5.
Consistent with De Broglie: The longest wavelength is = 2 L and the higher modes have
wavelengths given by = 2L/n (n = 1,2,...). Therefore the De Broglie relationship yields
momentum p = (nh/2L) = h/.
Orthogonality
Often we are interested in integrating products of wavefunctions. If the integral turns
out to be zero then the functions, n and m are said to be orthogonal:
*
n ( x)
2
nx mx
sin
m ( x ) dx =
sin
dx = 1 if n = m
L0 a a
= 0 if n m
Importantly, note that the eigenfunctions for the particle in a box are orthogonal to one
another.
Indeed they are said to be orthonormal in that each function is also normalised.
Examples: (i) Show pictorially that the hydrogen atom 2s and 2pz orbitals are orthogonal;
(ii) Shown that the two lowest energy wavefunctions for a particle in a box are orthogonal.
n=1
-1
0.0
1
0.2
0.4
0.6
x/a
0.8
1.0
0.0
0.2
0.4
0.6
0.8
1.0
x/a
L
1
x = xP( x) dx =
x dx =
L0
2
0
L2
= x P ( x ) dx =
3
0
then
L
2
x
x =
x sin 2 dx =
L0
2
L
x2
L2
L2
2 2 2 x
x sin dx =
=
2
L0
L
3
2
2
x
sin
L L
p x =
h d
h
( D sin kx) = k D cos kx cons.
i dx
i
is not an eigenfunction px (see later) but we can evaluate the expectation value
(see last lecture).
L
p x =
* p x dx
* d x
h
i
(sin kx)
d
dx
(sin kx) dx
kh
i
D 2 (sin 2 kx) dx
E=
2m
2m
D 2 (sin 2 kx) dx
p x2
=0
p x = p
(where p is a constant)
h d
= p
i dx
General solution:
( )x = Ae ikx
= Ae
ip
h
&& (CH )
(CH 3 ) 2 N = CH (CH = CH ) k N
3 2
Dye I: k = 1
Dye II: k = 2
Dye III: k = 3
Resonance condition
Absorption of a photon occurs when the energy of the photon (= h) matches the
difference in the energy between the two states involved in the transition (E):
E photon
h2
2
2
n
n
= h = E = E f Ei =
(
f
i )
8mL2
where ni and nf are quantum numbers for the initial and final states respectively.
Which values of ni and nf have to be used? Depends on the number of electrons and
the Pauli Exclusion Principle which allows a maximum of 2 electrons per orbital.
Electron pairs must have opposite spins.
Thus, for Dye I, k =1 and we have a total of (3+3) = 6 electrons that will pair in
levels n = 1, 2 and 3.Therefore the highest occupied molecular orbital (HOMO) has n
= 3, while the lowest unoccupied molecular orbital (LUMO) has n = 4.
Hence lowest energy transition involves promotion of a electron from n = 3 n = 4.
Example: If the length of the box L is 8.5, what is the peak absorption wavelength for dye I?
U = .E
= qi ri
i
fi = *f i d
Just like the probability density is given by *, so the probability for a transition (as
measured by the absorption coefficient) is proportional to fi* fi..
If fi = 0 then the interaction energy is zero and no transition occurs the transition is
said to be electric dipole forbidden. Conversely, if fi is large, then the transition
probability and absorption coefficient are large.
The intensity of the transition is therefore
proportional to.
*
k
j d
fi = e *f ( x) x i ( x)dx
0
Now evaluate fi for various wavefunctions to see which are allowed (fi 0) and which
are forbidden (fi = 0).
Example: Is n = 1 n = 2 an allowed transition?
n f x
2e
n x
x sin i dx
fi =
sin
L 0 L
L
L
L
(n + ni )x
e ( n f ni )x
cos f
dx
=
x cos
L 0
L
L
eL 1
1
1
1
fi = 2 (cos(n ) 1) 2 (cos(ntot ) 1) +
sin( n )
sin( ntot )
n
ntot
L n
ntot
n is odd is allowed
If n is odd then ntot is also odd and overall fi 0 and is given by
2eL 1
1 8eL ni n f
fi = 2 2 2 = 2
2
2
2
ntot n (n f ni )
The general selection rule is n is odd.
However, we only really see a single peak in the absorption spectrum for each dye
because other allowed transitions have very much smaller transition moments.
Example: For dye 1, compare the values of the transition dipole moment integrals for
the two transitions n = 3 n = 4 and n = 3 n = 6.
*Also note that longer molecules have larger absorption coefficients because fi increases
with the length of the molecule (see uv spectra earlier in notes).
x x' = x L / 2
n ( x) =
2
nx
cos
= + n ( x) ; odd n even parity
L
L
2
nx
sin
= n ( x) ; even n odd parity
L
L
n=1
L
2
n=2
L
2
L
2
L
2
Symmetry II
For transition n =1 n = 2 the transition dipole moment integral is:
L/2
L/2
e
e
x
x
sin x cos
f (x )dx
21 =
dx =
2
L
L
L L / 2 L
L / 2
n=1
L
2
L
2
L
2
f ( x) 0
L
2
L/ 2
n=2
L/2
L
2
L
2
L
2
L
2
Clearly f (x)dx 0 and the transition is allowed. In contrast, for the transition n = 1 n = 3, f(x)
L/2
dx = 0 and transition is forbidden.
f (x) = 0
x
n=1
L
2
L
2
L
2
L/2
n=3
L
2
L
2
L
2
L
2
L
2
Conclusion: if integrand is odd / antisymmetric / ungerade then f(x) dx = 0 and transition is forbidden.
Jz
2
h2 2
2 + 2
H =
2m x
y
1 2
h2 2 1
2+
+ 2
H =
2
2m r
r r r
2
2
2
2
1
h
H =
=
2
2
2m r
2 I 2
where I = mr2 is the moment of inertia of the mass m on the ring of radius r.
SE is of the (familiar) form:
2 IE
d 2
=
= ml2
2
2
dx
h
ml ( ) = Ae iml
with ml =
2 IE
h2
ml ( ) = ml ( + 2 )
has to be single-valued!
|mL| = 1
Eigenvalues:
ml2 h 2
E=
2I
ml = 0, 1, 2, 3,....
Normalisation of wavefunctions:
2
* d = A * A e
0
mL = 0
Eigenfunctions
:
iml iml
ml ( ) =
d = A * A d A =
0
1 iml
e
2
1
2
ml = 0, 1, 2, 3,....
h
1
2
2
2
2 + 2 + 2
T =
p x + p y + p z =
2m
2m x
y
z
2m x
y
z
h2 2
+ V ( x, y, z ) = E
2m
Kinetic
energy
Potential
energy
Total
energy
Separation of variables
Once again lets assume that the potential energy inside the the box is 0.
Now we assume that the wavefunction is separable:
( x, y, z ) = X ( x)Y ( y ) Z ( z )
dY 2
dZ 2
h 2 dX 2
YZ 2 + XZ 2 + XY 2 = EXYZ
2m
dz
dx
dy
and so SE becomes:
h 2 1 dX 2 1 dY 2 1 dZ 2
=E
+
+
2m X dx 2 Y dy 2 Z dz 2
First term only depends on x, and must be constant because the RHS does not contain x.
(Similarly for the other terms). Now we have three 1d equations to solve.
h 2 1 dX 2
= Ex
2m X dx 2
h 2 1 dY 2
= Ey
2m Y dy 2
h 2 dX 2
= Ex X
2m dx 2
h 2 dY 2
= E yY
2m dy 2
h 2 1 dZ 2
= Ez
2m Z dz 2
h 2 dZ 2
= Ez Z
2m dz 2
where
Ex + E y + Ez = E
L
L
x y z
( x, y, z ) = N sin
2
h 2 n x2 n y n z2
E (nx , n y , nz ) =
+
+
8m L2x L2y L2z
n x , n y , n z = 1,2,....
Eigenfunctions
n x , n y , n z = 1, 2, 3,....
Eigenvalues
nx
1
2
ny
1
1
nz
1
1
1
1
2
1
1
2
h2
2
2
2
n
+
n
+
n
E (n x , n y , nz ) =
x
y
z
8mL2
1 level
3 levels
n x , n y , n z = 1, 2, 3,....