Chem F111

Lecture-5- 31-10-2022

Probability
Normalization
Eigenvalue equations
Hamiltonian operator
Particle in a one dimensional box
Normalized wavefunction/eigenfunction

n=1,2,3….

n can not be zero; then =0

everywhere and particle vanishes;
2 2
nh
Allowed Eigenvalues En  2
8mL
Energy levels are quantized
 2 2
nh
En 
8mL2

Wavefunctions  n  2 sin[ nx ]

L L
n = 1,2,3,4....
 Wavefunctions of Particle in a 1D box

2  nx 
 ( x)  sin  
L  L 

n 2h 2  *
E 2 n = 1, 2, …
8mL
Energy is quantized
 L

Note how the wavelengths of this wave function could

be due to boundary condition imposed by walls
Wave functions
 L

In general  = 2L/n with n = 1,2,3,……

As, k = 2/  ; k = n / L
(x) = N sin(kx) = N sin(n x/ L)
Note that n appeared: quantized ! Not all  possible
 h nh

2L p 
n  2L
p2
E 
2m

n 2h 2  n(x)  2 sin[ nx ]

En  L L
8mL2
n = 1,2,3,4....
 n n2

What happens when n is very large ?

 2  nx  2 2
nh
 n ( x)  sin   where n  1,2,3,... En 
L  L  8mL2
n 0
If n= 0 ψn(x)=0
the particle does not exit at all!

Therefore n cannot be zero! n0

2
The lowest energy or the ground h
E1 
state energy for particle in a box 8mL2

Zero-point energy
Zero-point energy
An irremovable energy:
 n can not be zero; then =0 everywhere and
particle vanishes
 The lowest energy can not be zero;
 consequence of uncertainty principle:
particle is within the box, so uncertainty in
position, x can not be infinite; px can not
be zero.
The ground state energy is not 0, but h2/8mL2
Zero-point energy
An irremovable energy:
 n can not be zero; then =0 everywhere and
particle vanishes
 The lowest energy can not be zero;
 consequence of uncertainty principle:
particle is within the box,
 so uncertainty in position, x can not be
completely indefinite; px x  ħ/2
 px can not be zero. K.E cannot be zero
Zero-point energy

 consequence of uncertainty principle:

The ground state energy is not 0, but h2/8mL2

Energy arising from the ceaseless fluctuating

motion of the particle between the two
confining walls of the box
 Spectroscopy in a 1D box
Absorption of a photon occurs when the
energy of the photon (= h) matches the difference
between the two states involved in the transition (E):

The energy difference between

adjacent levels
For n = 1:
Narrow box : L small

Widely separated levels

Wide box : L large

Closely spaced levels

Separation decreases with increase in mass

Macroscopic objects : Translational motion is
unquantized

Quantization : Important for

• Highly confining regions

• Particles of very small mass

 Example
• Consider the following dye molecule, the length of
which can be considered the length of the “box” an
electron is limited to:

+
 electrons – consider “free”
N
L=8Å in box of length L.
Ignore all coulomb interactions.
N

What wavelength of light corresponds to minimum excitation?

Ans:  corresponding to E from n=1 to n=2

h2 2

2  final initial  2  
h 19
E  n 2
 n 2
 2 2
 1  2.8 x10 J
8mL 8m(8 Å )

  700nm (experimental: 680 nm)