The Schrödinger

equation
FEBI YUSNIYANTI, M.Sc
The Schrödinger equation
 Quantum mechanics acknowledges the wave–particle duality of
matter and the existence of quantization by supposing that,
rather than travelling along a definite path, a particle is distributed
through space like a wave.
 The mathematical representation of the wave that in quantum mechanics replaces
the classical concept of trajectory is called a wavefunction,
ψ (psi)
 In 1926, the Austrian physicist Erwin Schrödinger proposed an
equation for finding the wave-function of any system.
 The time-independent Schrödinger equation for a particle of
mass (m) moving in one dimension with energy E in a system
that does not change with time (for instance, its volume remains constant) is
The Schrödinger equation
 The factor V(x) is the potential energy of the particle at the point
x; because the total energy E is the sum of potential and kinetic
energies
 Heisenberg’s Matrix Mechanics
1924: de Broglie suggests particles are waves
Mid-1925: Werner Heisenberg introduces Matrix Mechanics
•Semi-philosophical, it only considers observable quantities
•It used matrices, which were not that familiar at the time
•It refused to discuss what happens between measurements
•In 1927 he derives uncertainty principles
Late 1925: Erwin Schrödinger proposes wave mechanics
•Used waves, more familiar to scientists at the time
•Initially, Heisenberg’s and Schrödinger’s formulations were competing
•Eventually, Schrödinger showed they were equivalent; different descriptions which
produced the same predictions
Both formulations are used today, but Schrödinger is easier to understand
 The Free Schrödinger Equation
1925: Erwin Schrödinger proposes wave mechanics
•Peter Debye suggested to him he needed to find a wave equation
for quantum mechanics
p2
•He hit on the idea of using complex waves E
• The rest is history   x, t  2m
•Starting point: Energy/Momentum relationship
p2
•Multiply by the wave function on the right E   x, t     x, t 
•Use de Broglie relations to rewrite 2m 2
 2
E   p  k   x, t   k   x, t 
2m
•Use relationships for complex waves to rewrite with derivatives

 ik k
1    x, t  exp  ikx  it 
x i x
   2  2
 i  i i   x, t      x, t 
t t t 2m x 2
The Hamiltonian operator
Time-dependent  2 2 
Schrödinger equation i   V ( x, t ) 
t 2m x 2
Can think of the RHS of the Schrödinger equation as a
differential operator that represents the energy of the
particle.  2 d 2 
 2
 V ( x, t )    Hˆ 
This operator is called the Hamiltonian of the particle,  2m dx 
and usually given the symbol Ĥ

Hence there is an alternative (shorthand)

form for the time-dependent Schrödinger  ˆ Kinetic Potential
equation: i  H energy energy
t operator operator

Hamiltonian is a linear differential operator.

Schrödinger equation is a linear homogeneous partial differential equation
LHS of TDSE  2  2  2 2 
can be written  2

 V ( x, t )     2
 V ( x, t )   Hˆ 
2m x  2m x 
as:

where Ĥ is called the Hamiltonian operator which is the differential

operator that represents the total energy of the particle.
  2
 2
 ˆ
p 2
Thus Hˆ    2
 V ( x)   x
 Vˆ ( x)
 2m x  2m

where the momentum operator is pˆ x  i
x

Thus shorthand for TDSE is: Hˆ   i
t
The time-dependent
Schrödinger equation
For a particle in a potential V p2
(x,t) then E  V ( x, t )
2m
and we have (KE + PE)  wavefunction =  2  2 
(Total energy)  wavefunction   V ( x, t )   i
2m x 2
t
TDSE 
Points of note:
1. The TDSE is one of the postulates of quantum mechanics. Though the SE cannot
be derived, it has been shown to be consistent with all experiments.
2. SE is first order with respect to time (cf. classical wave equation).
3. SE involves the complex number i and so its solutions are essentially complex.
This is different from classical waves where complex numbers are used imply for
convenience.
 Solving the TDSE – Aaargh!
Suppose the potential is
  2  2
independent of time i.e. V(x, i   V ( x) 
t) = V(x) then TDSE is: t 2m x 2

LHS involves variation of  with t while RHS involves

variation of  with x. Hence look for a separated solution:  ( x, t )   ( x)T (t )

then LHS depends only upon x, RHS only on t.

2
 2
T True for all x and t so both sides must
 T 2  V ( x)T  i
2m x t equal a constant, E (E = separation
constant).
Now divide by Thus we have: i 1 T  E
 T: T t
 2 1  2 1 T
  V ( x )  i   2 1  2
2m  x 2 T t   V ( x)  E
2m  x 2
Time-independent
Schrödinger equation
Solving the time 1 dT dT iE
equation: i E    dt  T (t )  Ae iEt / 
T dt T 
This is exactly like a wave e-it with E = ћ. To find out what the energy actually is we
Therefore T(t) depends upon the energy E. must solve the space part of the problem....

The space equation  2  2

becomes  2
 V ( x)  E or Hˆ   E
2m x
This is the time independent Schrödinger equation (TISE) .

The TISE can often be very difficult to solve – it

depends upon V(x)!
 Eigenvalue equations

The Schrödinger Equation is the form of an Eigenvalue Equation: Hˆ   E

2 2
 d
where Ĥ is the Hamiltonian operator,
Hˆ  Tˆ  Vˆ   2
 V ( x)
2m dx

 is the wavefunction and is an eigenfunction of Ĥ;

E is the total energy (T + V) and an eigenvalue of Ĥ. E is just a constant!

 TISE for a free-particle
For a free particle V (x) = 0 and  2
 2

 2
 E
TISE is: 2 m  x
 ikx k 2 2
and has solutions   e or eikx
where E 
2m

Thus the full solution to the full TDSE is:  ( x, t )   ( x) T (t )  e i (  kx  Et /  )

Corresponds to waves travelling in either  x direction
with:
(i) an angular frequency,  = E / ћ  E = ћ ! 
(ii) a wavevector, k = (2mE)1/2 / ћ = p / ћ  p = h /  !

WAVE-PARTICLE DUALITY!
Interpretation of (x,t)
As mentioned previously the TDSE has solutions that are inherently complex  (x,t)
cannot be a physical wave (e.g. electromagnetic waves). Therefore how can  (x,t)
relate to real physical measurements on a system?
The Born Interpretation
Probability of finding a particle in a small length dx at position x and time t is equal to
* 2
 ( x, t ) ( x, t ) dx   ( x, t ) dx  P( x, t ) dx
* is real as required for a probability distribution and is the probability per unit
length (or volume in 3d).
The Born interpretation therefore calls  the probability amplitude, * (= P(x,t) )
the probability density and * dx the probability.
Expectation values
Thus if we know (x, t) (a solution of TDSE), then knowledge of * dx allows the
average position to be calculated:
x   xi P( xi ) x
i

In the limit that x 0 then the summation becomes:

 

 
2
x x  xP( x) dx  x  ( x, t ) dx
 
The average is also know as the expectation value and are very important
in quantum mechanics as they provide us with the average values of
physical properties because in many cases precise values cannot, even in
principle, be determined  

 
2
Similarly x2  x 2 P ( x)dx  x 2  ( x, t ) dx
 
 Normalisation  

 
2
Total probability of finding a particle anywhere must be 1: P( x)dx   ( x, t ) dx  1
 

This requirement is known as the Normalisation condition. (This condition arises

because the SE is linear in  and therefore if  is a solution of TDSE then so is c
where c is a constant.)

Hence if original unnormalised wavefunction is (x,t), then the normalisation integral

is: 
And the (re-scaled) normalised wavefunction norm

2 2
N   ( x, t ) dx
 = (1/N) .
 Boundary conditions for 
In order for  to be a solution of the Schrödinger equation to represent a physically
observable system,  must satisfy certain constraints:
1. Must be a single-valued function of x and t;
2. Must be normalisable; This implies that the   0 as x  ;
3.  (x) must be a continuous function of x;
4. The slope of  must be continuous, specifically d (x)/dx must be
continuous (except at points where potential is infinite).

Y(x) Y(x) Y(x) Y(x)

x x x x
Summary
 2  2 
TDSE:   V ( x , t )   i 
2m x 2 t
2
Born interpretation:  * ( x, t ) ( x, t )dx   ( x, t ) dx  P( x, t )dx
 

 
2
Normalisation: P( x)dx   ( x, t ) dx  1
 
TISE:  2  2
 2
 V ( x)  E or Hˆ   E  ( x, t )   ( x) T (t )   ( x)e iEt / 
2m x
Boundary conditions on : single-valued, continuous, normalisable, continuous first derivative.

ˆ   ( x, t )dx


Expectation value of operator Ω:  ( x , t ) 
