Quantum theory and atomic

spectroscopy
Lecture 6
The Schrödinger equation
 We’re all made of waves!!!!
• Replace the idea of particles with quantum
objects which have a wavelength
• The de – Broglie wavelength is inversely
proportional to the momentum
• We can’t have classical trajectories any
more!
• Schrödinger introduced a new way to look
at nature
• Now read on …
 Today’s question is……
• What is the Schrödinger equation and how do
we use it? How should we picture electrons etc
now? Will we uncover quantization of energy?
 The Schrödinger equation
• This is one of the most deceptively simple
equations in science
• It uses an operator called the Hamiltonian, which
“operates” on a mathematical function called a
wavefunction which represents the quantum
object
• The result is the energy x wavefunction

ĤΨ = EΨ
 What is an operator?
• An operator is simply a mathematical operation
you perform on a function

dy
dx
=
d
dx
(y) d
dx
x( )
n
= nx n −1

• Imagine the operator is a machine where you

input a mathematical function, and it spits out a
final mathematical function
 The eigenvalue problem
• The Schrödinger equation is an example of
an eigenvalue problem

ÂΨ = aΨ

ĤΨ = EΨ
 Eigenfunctions
• Some operators have special functions that only
change by a constant multiple under its
operation

( ) ( )
2
d d
e ax
= ae ax
2
e ax
= a e 2 ax

dx dx

• This time, we input the eigenfunction, and the

final result is just the original function multipled
by a constant! Lovely
 The Hamiltonian
• The Hamiltonian is the energy operator:
apply it to a wavefunction to find the
energy.
• For an uncharged
particle moving in h
Hˆ = − 2
2
d 2
+ V (x )
8π m dx 2

1- D we have a
kinetic energy term
and a potential term
Free-particle Schrödinger equation
• Assume there are no forces acting on a
moving particle in 1-D i.e. there is no
potential energy operator.

⎛ h 2
d 2
⎞ d 2Ψ 8π 2 mE
HΨ = −⎜⎜ 2
ˆ ⎟Ψ = EΨ
2 ⎟
=− Ψ
⎝ 8π m dx ⎠
2 2
dx h
 Solving the equation
• We can compare our rearranged Schrödinger eqn with
the earlier eigenvalue problem….

( )
2
d
e ax
= a e
2 ax Ψ=e ax

dx 2

d Ψ
2
8π mE
2 8π mE2

2
=− 2
Ψ a =−
2
2
dx h h
 One little problem….
• Oh dear….. Just one thing if m, h and E
are positive (which they are)

8π mE2
a =−
2
2 a 2
< 0
h

The square root of a negative number!!!!

 Thank you, complex numbers
• To get around this, we need to use
complex numbers
• What we do, is introduce i = √-1

a = ik
8π mE 2
a = i k = −k = −
2 2 2 2
2
h
8π 2 mE
k=
h2
 And the wavefunction is….
• At last we have found the wavefunction to
describe a free particle in terms of its location,
mass and energy

Ψ = e ikx

8π mE 2
k= 2
h
 What a disappointment….
• Not only does the wavefunction look pretty
meaningless, it isn’t the only solution
− ikx
Ψ = e ikx
Ψ = e
− ikx
Ψ = Ae ikx
+ Be

• In fact, with no control over constants A and B

there are an infinite number of solutions!
• And NO quantization for a free particle
 Waves and kinetic energy
• Short wavelengths
indicate high kinetic
energy
p2 h
E= p= • In general, high
2m λ db curvature means high
kinetic energy

h
λ db =
2mE
 Potential barriers
• Short wavelengths indicate high kinetic energy
• In general, high curvature means high kinetic energy
• Kinetic energy changes over a potential well or
barrier
 The Born interpretation
• Max Born noted the
connection between
wavefunctions and light
waves
• In light, the square of the
amplitude gives the
intensity
• He suggested that the
square of the
wavefunction reflects
“likelihood” or probability.
 Squaring complex numbers
• This is not as simple as it looks!
• Need to use the so called complex
conjugate

Take a complex number Get the complex conjugate

A + iB Swap the sign

A − iB
 Using the complex conjugate
• This ensures that the result is REAL and
POSITIVE

( A + iB )( A + iB ) = A 2
+ 2iAB + i B2 2

(
= A − B + 2iAB
2 2
)
No good!
( A − iB )( A + iB ) = A 2
+ iAB − iAB − i B 2 2

= A +B 2 2
This is okay!!!
 The probability density

The probability density is

Ψ 2 = Ψ (x ) Ψ (x )
∗

Therefore, the PROBABILITY

that a particle takes a value

between x and x + dx is given by

Ψ x Ψ ( x )dx
( )∗
Answers to the earlier questions..

• The Schrödinger
equation is used to
find the wavefunction
and the energy of a
quantum object
• For a free particle,
there is no
quantization!
 Just one more thing……

• Can we solve the

Schrödinger equation for
hydrogen? Will it explain
quantization?

• Next time, we will set it up

and solve it and discuss
what it means for atoms!

Enjoy the Easter holidays!