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( x)
2
dx
2 d 2 ( x)
2 ( x)
4
2
dx
1 2 p2
E mv V V
2 2m
1
p [2mE V ] 2
h h
1
p
[2mE V ] 2
h 2 d 2 ( x)
2 ( E V ) ( x)
8 m dx 2
Postulates of Quantum Mechanics
Postulate 1:
=> the probability that the particle can be found at a particular point x and a
particular time t. (Born’s / Copenhagen interpretation)
Implications of Born’s Interpretation
(1) Positivity:
P(r) >= 0
(2) Normalization:
d 1
*
all _ space
x
(ii )e (, )
sin x
(iii )
x
1
(iv ) sin x
Exp(x)
Sinx/x
Sin-1x
Postulate 2
ˆ satisfies
A hermitian operator A
* *
f Âgdx g( Âf) dx ; if f and g are well behaved
• Prove Operator x is Hermitian.
xrs r x s dx
*
rx
* *
s dx
*
( s* x * r )* dx x*sr
Hermitian operator or not ??
(i )
x
(ii ) i
x
2
(iii ) 2
x
Linear Operator
• A linear operator has the following properties
A f1 f 2 A f1 A f 2
Acf c A f
Linear operator
Derivative
integrals
log
√
Normalized wave function: N 2 * dx 1
A f ( x) kf ( x)
f(x) is eigenfunct ion of A with eigen valu e k
Q: What are the eigenfunctions and eigenvalues
of the operator d/dx ?
Eigen function and eigen value
f x e ikx
Eigenvalue equation
^
Example: eikx is an eigenfunction of a operator Px = -ih
x
F(x) = eikx
= -i h eikx
x
= -i2 hk2eikx
= h k2eikx Thus eikx is an eigenfunction
Significance of commutation rules
d
B
dx
A B f ( x) xf , ( x)
d
B A f ( x) [ xf ( x)] xf , ( x) f ( x)
dx
A, B f ( x) f ( x)
A, B 1
Postulate 4
The fourth postulates states what will be measured when large number
of identical systems are interrogated one time. Only after large number
of measurements will it converge to <a>.
In QM, the act of the measurement causes the system to “collapse” into
a single eigenstate and in the absence of an external perturbation it will
remain in that eigenstate.
Postulate 5
General form:
H = E
E= T + V
Schrödinger Representation – Schrödinger Equation
Time dependent Schrödinger Equation
( x , y , z , t )
i H ( x , y , z , t )( x , y , z , t )
t
Developed through analogy to Maxwell’s equations and knowledge of
the Bohr model of the H atom.
p2
H classical V Sum of kinetic energy and potential energy.
2m
Hamiltonian kinetic potential
energy energy
Q.M. 2 2
H V (x) one dimension recall p i
2m x 2 x
H
2 2
V ( x, y, z )
2 2 2
three dimensions
2
2m x y z2
2 2
The potential, V, makes one problem different form another H atom, harmonic oscillator.
Copyright – Michael D. Fayer, 2007
Getting the Time Independent Schrödinger Equation
( x , y, z , t ) wavefunction
i ( x , y , z , t ) H ( x , y , z , t )( x , y , z , t )
t
If the energy is independent of time H ( x, y, z )
Try solution
Then
i ( x , y, z )F ( t ) H ( x , y, z ) ( x, y, z )F ( t )
t
i ( x, y, z ) F ( t ) F ( t ) H ( x, y, z ) ( x, y, z ) divide through by
t F
independent of t independent of x, y, z
Copyright – Michael D. Fayer, 2007
dF ( t )
i
dt H ( x , y, z ) ( x , y, z )
F (t ) ( x, y, z )
Equal constant
dF
i
dt E H
F
H ( x, y, z ) ( x, y, z ) E ( x, y, z )
H is energy operator.
Operate on get back times a number.
’s are energy eigenkets; eigenfunctions; wavefunctions.
E Energy Eigenvalues
Observable values of energy
dF ( t )
i E F (t )
dt
dF ( t ) i
E dt . Integrate both sides
F (t )
i Et
ln F C
F ( t ) e i E t / e i t
Time dependent part of wavefunction for time independent Hamiltonian.
Time dependent phase factor used in wave packet problem.