Formalism of Quantum Mechanics: Time-Dependent Schrödinger Equation

Formalism of Quantum Mechanics
Time-dependent Schrödinger Equation:

! ! 2 !2
i! " (x,t) = # " (x,t) + U(x)" (x,t)
!t 2m !x 2
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….
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 =
!
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)
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.
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
$ 2n# x '
2
B x L B2 L
= * sin & ) = =1
2 0 2n# x % L ( 0
2
2
B=
L
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
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.
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 $
Macroscopic objects: What is the energy quantum number of a
3.00mg object moving at speed 1.00 cm/s in a box of of length 2cm?
From quantization of energy,
1 2 ! 2 n 2! 2
En = mv =
2 2mL2
mLv
"n= = 18 # 10 23
!!
For macroscopic objects, the quantum number is very large, and the
spacing between energy levels is very small, so the energy seems to
be continuous. However, quantization of energy is very important at
the scale of atoms, electrons, nucleii etc.
Time-independent Schrödinger Equation: Finite square well
potential:
Consider a box of finite depth such that
U(x) = 0, 0 ! x ! L
U(x) = U, x < 0 and x > L
A particle with energy E > U is not

confined in the box. It is a free
particle with kinetic energy E-U.
potential:
Consider a box of finite depth such that
U(x) = 0, 0 ! x ! L
U(x) = U, x < 0 and x > L
A particle with energy E < U is

confined in the box.
Classically the bound particle can only
be found inside the box.
Quantum mechanically, the bound
wave functions can leak into the
classically forbidden regions I and
III….
potential:
Inside the box, U(x) = 0
!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 =
!
potential:
Outside the box, U(x) = U
!2 d 2
! 2
" (x) + U(x)" (x) = E" (x)
2m dx
!2 d 2
! 2
" (x) = (E ! U )" (x)
2m dx
Solutions outside the box:
! (x) = Ce" x , x < 0 2m(U " E)

!=
! (x) = De#" x , x > L !
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.
Matching ψ(x) at x=0:
! (0) = A cos(k0) + Bsin(k0) = Ce" 0
#A=C
Matching ψ(x) at x=L:
! (L) = A cos(kL) + Bsin(kL) = De"# L

potential:
The wave function is smoothly varying so dψ/dx inside the box must
match dψ/dx outside the box at x=0 and x=L.
Matching dψ/dx at x=0:
" !(0) = #kAsin(k0) + kB cos(k0) = $ Ce$ 0
% kB = $ C
Matching dψ/dx at x=L:
! (L) = "kAsin(kL) + kB cos(kL) = "# De"# L

Time-independent Schrödinger Equation: Finite square well potential:
The boundary conditions give us the following relations:
A=C A k
=
kB = ! C B !
A cos(kL) + Bsin(kL) = De!" L !kAsin(kL) + kB cos(kL)

= !"
A cos(kL) + Bsin(kL)
!kAsin(kL) + kB cos(kL) = !" De!" L
Thus we get a transcendental equation which can only be satisfied for

certain values of k and α (and hence E):
! sin(kL) + (" k ) cos(kL) "

=!
cos(kL) + (" k ) sin(kL) k
The solutions to the transcendental equation result in wave functions that
decay into the classically forbidden regions:
! sin(kL) + (" k ) cos(kL) " 2m(U " E) 2mE
=! != , k=
cos(kL) + (" k ) sin(kL) k ! !
x<0:
! (x) = Ce" x
x>L:
! (x) = De#" x
0!x!L:
" (x) = A cos(kx) + Bsin(kx),
Penetration depth: Outside the box, the wave function amplitude falls to
1/e of its value at the edge of the box at a distance δ from the edge:
1 !
!= =
" 2m(U # E)
Quantized energies: The exterior wave function is almost 0 at a distance
δ on either side of the box.
Thus we can model the finite well as an infinite well of length L+2d.
The energies are then
n 2" 2 ! 2
En ! , n = 1, 2...
2m(L + 2# ) 2
Time-independent Schrödinger Equation: Harmonic Oscillator:
Consider a particle moving in a quadratic potential (spring force):
1 2 1
U(x) = kx = m! 2 x 2
2 2
Inserting this potential into the TISE:
!2 d 2 1
! 2
" (x) = (E ! m# x )" (x)
2 2
2m dx 2
This differential equation can be solved exactly (although we will not do

so here).
We will examine the ground state wave function (lowest energy wave
function) and qualitatively look at higher energy wave functions:
Consider a particle moving in a quadratic potential:
1 2 1
U(x) = kx = m! 2 x 2
2 2
The ground state is a Gaussian function:

! " x2
C0 e
# m! & m!
1/ 4
C0 = % , )=
$ " ! (' 2!
Higher energy wave functions are

products of a polynomial function
and a Gaussian function:
Number of peaks for nth level

wavefunction = n+1
Quantized energy levels are equally spaced with a non-zero minimum: :

! 1$
En = # n +
" &% !'
2
Vibrational levels of a diatomic molecule:
Two atoms in a molecule are held together by spring-like molecular
forces.
The bottom of the molecular potential can be modeled by a harmonic
oscillator with quantized vibrational energy levels.
Absorption spectra of molecules show dips corresponding to transitions
between vibrational levels
If the vibrational absorption spectrum of a molecule shows a dip at
wavelength λ corresponding to jumps between adjacent levels, what is
the spring constant k/m of the molecular bond?
! 1$
En = # n + & !'
" 2%
1 hc
!E = !" =
2 #
k c
$" = = 2%
m #
k 4% 2 c 2
$ =
m #2

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Formalism of Quantum Mechanics

Time-dependent Schrödinger Equation:

Solutions: ! (x,t) = " (x) # (t)

This equation is not always easy to solve analytically, but can be

This satisfies the uncertainty principle. If the minimum energy were

"0 !n (x) dx = "0 B sin &% L )( dx = "0 B 2 &% 1 * cos &% L )( )( dx

The particle is most likely to be at

From quantization of energy,

A particle with energy E > U is not

A particle with energy E < U is

Solutions inside the box:

Solutions outside the box:

! (x) = Ce" x , x < 0 2m(U " E)

! (L) = A cos(kL) + Bsin(kL) = De"# L

! (L) = "kAsin(kL) + kB cos(kL) = "# De"# L

A cos(kL) + Bsin(kL) = De!" L !kAsin(kL) + kB cos(kL)

Thus we get a transcendental equation which can only be satisfied for

! sin(kL) + (" k ) cos(kL) "

Inserting this potential into the TISE:

This differential equation can be solved exactly (although we will not do

The ground state is a Gaussian function:

Higher energy wave functions are

Number of peaks for nth level

Quantized energy levels are equally spaced with a non-zero minimum: :

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