Solving the Schrodinger Equation
Time-dependent Schrödinger Equation:
! ! 2 !2
i! " (x,t) = # " (x,t) + U(x)" (x,t)
!t 2m !x 2
Stationary Solutions: ! (x,t) = " (x) # (t)
"i# t E
! (t) = e , #=
!
Time-independent Schrödinger equation:
!2 d 2
! 2
" (x) + U(x)" (x) = E" (x)
2m dx
This equation is not always easy to solve analytically, but can be
solved numerically on a computer.
However we can analytically solve some special cases….
Solving the Schrodinger Equation
Time-independent Schrödinger Equation: Particle in a box
(infinite square well potential):
Consider a particle inside a box of length L with impenetrable walls:
Outside the box the particle wave function is 0.
Inside the box, U(x) = 0
Inserting into the TISE,
!2 d 2
! 2
" (x) + U(x)" (x) = E" (x)
2m dx
!2 d 2
! 2
" (x) = E" (x)
2m dx
Solutions inside the box:
2mE
! (x) = A cos(kx) + Bsin(kx), k =
!
Solving the Schrodinger Equation
Time-independent Schrödinger Equation: Particle in a box
(infinite square well potential):
The wave function is continuous so the wave function inside the box
must match the wave function outside the box at x=0 and x=L.
Outside the box, the wavefunction is always 0.
Solutions inside the box at x=0 and L:
! (0) = A cos(k0) + Bsin(k0) = A = 0
! (L) = A cos(kL) + Bsin(kL) = 0
A = 0, kL = n! , n = 1, 2...
Acceptable solutions are thus
# n" x &
!n (x) = Bsin % ( , n = 1, 2, 3..
$ L '
(For n=0, ψ(x)=0, particle not found in the box, hence not acceptable
solution)
Solving the Schrodinger Equation
Time-independent Schrödinger Equation: Particle in a box
(infinite square well potential):
Solutions :
# n" x &
!n (x) = Bsin % , n = 1, 2, 3.., 0 ) x ) L
$ L ('
! (x) = 0, x > L, x < 0
Energy is quantized:
1 2 p 2 ! 2 k 2 ! 2 n 2! 2
En = mv = = =
2 2m 2m 2mL2
Non-zero minimum energy E1 (zero-point energy)
This satisfies the uncertainty principle. If the minimum energy were
0, then the momentum would be precisely 0, and then the location of
the particle would be unknown - it would not be confined to the box.
Solving the Schrodinger Equation
Time-independent Schrödinger Equation: Particle in a box
(infinite square well potential):
Solutions :
# n" x &
!n (x) = Bsin % , n = 1, 2, 3.., 0 ) x ) L
$ L ('
! (x) = 0, x > L, x < 0
Normalization:
2 $ n# x ' 2 1$ $ 2n# x ' '
L L L
"0 !n (x) dx = "0 B sin &% L )( dx = "0 B 2 &% 1 * cos &% L )( )( dx
2 2
L L
B2 x L $ 2n# x ' B2 L
= * sin & ) = =1
2 0 2n# x % L ( 0
2
2
B=
L
Solving the Schrodinger Equation
Time-independent Schrödinger Equation: Particle in a box
(infinite square well potential):
Solutions :
2 # n" x &
!n (x) = sin % (' , n = 1, 2, 3.., 0 ) x ) L
L $ L
! (x) = 0, x > L, x < 0
! 2 n 2! 2
En = 2
, n = 1, 2, 3...
2mL
Solving the Schrodinger Equation
Time-independent Schrödinger Equation: Particle in a box
(infinite square well potential):
A particle is in a box of length L in the ground state (lowest energy
state). Where is the particle most likely to be found? What is the
probability of finding the particle in the middle half of the box?
2 # "x&
!1 (x) = sin % ( , n = 1
L $ L'
The particle is most likely to be at
x=L/2 where the probability density
curve is a maximum.
Solving the Schrodinger Equation
Time-independent Schrödinger Equation: Particle in a box
(infinite square well potential):
The middle half of the box is the region from x=l/4 to x=3L/4.
Probability of finding the particle in the middle half of the box:
2 # "x&
!1 (x) = sin % ( , n = 1
L $ L'
3L / 4
#
2
P(L / 4 ! x ! 3L / 4) = "1 (x) dx
L/4
3L / 4
2 2 % $x( x 1 % $x( % $x(
3L / 4
#
L/4
L
sin ' * dx = + sin ' * cos ' *
& L) L $ & L) & L) L/4
1 1
, P(x) = + = 0.818 = 81.8%
2 $
Solving the Schrodinger Equation
Time-independent Schrödinger Equation: Particle in a box
(infinite square well potential):
Solutions :
2 # n" x &
!n (x) = sin % (' , n = 1, 2, 3.., 0 ) x ) L
L $ L
! (x) = 0, x > L, x < 0
Orthonormality: Notice that
" ! (x)!
n m (x)dx = # mn
i.e. the above integral is zero except when m=n.
For the case of m=n, the integral is 1 (normalization).
This property holds for stationary solutions of other potentials as well.
Solving the Schrodinger Equation
Time-independent Schrödinger Equation: Particle in a box
(infinite square well potential):
Solutions :
2 # n" x &
!n (x) = sin % (' , n = 1, 2, 3.., 0 ) x ) L
L $ L
! (x) = 0, x > L, x < 0
Completeness: Any function f(x) can be written as a linear combination of ϕn(x)
"
f (x) = # cn! n (x)
n =1
This is nothing but the use of Fourier series or Dirichlet’s theorem
Solving the Schrodinger Equation
Time-independent Schrödinger Equation: Particle in a box
(infinite square well potential):
Solutions :
2 # n" x &
!n (x) = sin % (' , n = 1, 2, 3.., 0 ) x ) L
L $ L
! (x) = 0, x > L, x < 0
Completeness: Any function f(x) can be written as a linear combination of ϕn(x)
"
f (x) = # cn! n (x)
n =1
How to calculate the coefficients cn ? Well,
" "
cn = # cm! mn = # cm % $ n* (x)$ m (x)dx = % $ n* (x) f (x)dx
m =1 m =1
Solving the Schrodinger Equation
Time-independent Schrödinger Equation: Particle in a box
(infinite square well potential):
Correspondence principle: Recall that the correspondence principle
as formulated by Bohr states that generally when the quantum number
of a system becomes large it should behave classically.
For a particle moving with constant speed
v inside a box, the classical probability
density is constant:
1
Pclassical (x) =
L
Average classical probability density
matches the quantum value for large
quantum numbers n
