Basic postulates of Quantum mechanics and
Schroedinger equation
2
Basic ingredients of wave mechanics
The wave mechanics formulated such a way that the postulates and the
experimental observations should come as outcome of the theory
Explanation of photoelectric effect says that energy of wave representing
fundamental particles should be quantized
E=h+
Einstein's relation
De Broglie's further generalization of the waveparticle dual nature extended
to electrons leads to
\=
h
p
ince wave nature of the particle are confirmed we may choose simple form
of wave to represent the matter wave
3
ince wave nature of the particle are confirmed we may also choose simple
form of wave to represent the matter wave
1( x , t )=sin2n
(
x
\
−+t
)
!e are familiar with such waves in a string under "artesian coordinates
#f we consider Bohr model of atoms such wave exist in spherical
coordinates$ therefore we may choose generalized coordinates for the
formalism of the wavemechanics with "artesian as special case%
chroedinger equation may be regarded an equation that gives form of the
wave under correct potential% &or example in Bohr model it is spherically
symmetrical potential
4
chroedinger equation is and equation from first principles of experimental
observations listed as and
E=h+
\=
h
p
#t should be consistent with relation with energy momentum of a classical
system
E=
p
2
2m
+V
ince quantum waves interfere same as in the way classical wave the
solutions they should be linear as in classical waves such as water waves%
Therefore if and are two independent solution
of the differential equation then
also must be solution to this equation ' ee Davisson and (ermer
experiment for interference of quantum waves
1
1
( x , t )
1
2
( x , t )
1( x , t )=C
1
1
1
( x , t )+C
2
1
2
( x , t )
5
#n case of free particles the function should be free sine or cosine wave
with a constant frequency or wave length%
"ombining the equation we have we can rewrite the classical equations as
p
2
2m
+V=E
h
2
2m\
2
+V ( x , t )=h+
E=h+
\=
h
p
)sing the change of variable
k=
2n
\
o=2n+
ℏ
2
k
2
2m
+V ( x , t )=ℏo
#n order to maintain linearity assumption term on the differential equation
depend only on the first power of $ i%e%$ all term should contain
this function
1( x , t )
wavenumber
6
1( x , t )=sin2n
(
x
\
−+t
)
1( x , t )=sin ( k x−ot )
)sing the change of variable
k=
2n
\
o=2n+
ℏ
2
k
2
2m
+V ( x , t )=ℏo
#n this equation if expressed in the form of the differential equation in
order to get in the *+ we need second order differential
operator with space
k
2
,lso in order to get on + we need a differential equation that
is first order in time%
!e may propose an empirical form of the equation of a matter wave
o
o
∂
2
1( x , t )
∂ x
2
+V ( x , t )1( x , t )=ß
∂1( x , t )
∂t
7
o
∂
2
1( x , t )
∂ x
2
+V ( x , t )1( x , t )=ß
∂1( x , t )
∂t
!here and are undetermined constants
o ß
1( x , t )=sin ( k x−ot )
!ith the trial solution under constant potential the differential
equation becomes
−osin(k x−ot )k
2
+sin(k x−ot )V
0
=−ßcos(k x−ot )o
V
0
This is possible in the special case of where
cos ( k x−ot ) =sin ( k x−ot )
x , t
This difficulty can be overcome by using a trial solution that is a
combination of sine and cosine waves
1( x , t )=cos ( k x−ot ) +¸sin( k x−ot )
8
1( x , t )=cos ( k x−ot ) +¸sin( k x−ot )
&inding the derivatives with space
∂
2
1( x , t )
∂ x
2
=−k
2
cos ( k x−ot ) −k
2
¸sin ( k x−ot )
∂1( x , t )
∂t
=−osin ( k x−ot ) −o¸cos ( k x−ot )
&inding the derivatives with time
o
∂
2
1( x , t )
∂ x
2
+V ( x , t )1( x , t )=ß
∂1( x , t )
∂t
ubstituting in the equation with constant potential V
0
9
ubstituting in the equation with constant potential
o
∂
2
1( x , t )
∂ x
2
+V ( x , t )1( x , t )=ß
∂1( x , t )
∂t
−ok
2
cos ( k x−ot ) −ok
2
¸sin( k x−ot ) +
V
0
cos ( k x−ot ) +V
0
¸sin ( k x−ot ) =
−ßosin ( k x−ot ) +ßo¸cos ( k x−ot )
(
−ok
2
+V
0
+ßo¸
)
cos ( k x−ot )
.lacing together the coefficients of sine and cosine functions
(
−ok
2
¸+V
0
¸−ßo
)
sin( k x−ot ) =0
/eaningful solutions are possible when the coefficients vanish
leading to two algebraic equations
10
(
−ok
2
+V
0
+ßo¸
)
cos ( k x−ot )
(
−ok
2
¸+V
0
¸−ßo
)
sin( k x−ot ) =0
−ok
2
+V
0
=−ßo¸
The two equations are
−ok
2
+V
0
=ßo/ ¸
By subtracting one from other
0=−ßo¸−ßo/ ¸
−¸=1/ ¸
¸
2
=−1
¸=!i
)sing this result we may obtain value of other constants
11
−ok
2
+V
0
=−ßo¸
¸=!i
−ok
2
+V
0
=∓i ßo
By comparing with the equation equating different parts of the energy
ℏ
2
k
2
2m
+V
0
=ℏo
o=−
ℏ
2
2m
ℏ=∓i ßo
ß=!i ℏ
0o specific difference is there for selection of either positive or
negative sign for beta$ therefore choosing positive sign as choice
ß=+i ℏ
12
!ith the selection of constants we arrive at the form the equation
o
∂
2
1( x , t )
∂ x
2
+V ( x , t )1( x , t )=ß
∂1( x , t )
∂t
o=−
ℏ
2
2m
ß=+i ℏ
!ith new value of the constants
−
ℏ
2
2m
∂
2
1( x , t )
∂ x
2
+V ( x , t )1( x , t )=i ℏ
∂1( x , t )
∂t
This is the wave equation satisfying all assumption of the quantum
mechanics
o far we have not proved that this equation is valid for any arbitrary
potential other than free particle% #n any arbitrary potential we need to
prove the validity from the experimental results
13
Meaning and properties of wave functions
!ave functions give state of a system$ the time evolution of a classical
state is given time variation of the wave functions
is interpreted as the probability amplitude of the particle's
presence
µ(¯r , t )
.osition vector in a three dimensional space
!ave function contains all information about the state of system
µ(¯r , t )
¯r
can ta1e any value in the space
d P(¯r , t )
.robability of finding a particles in the
in the volume element
d r
3
=dx dy dz
∣µ(¯r , t )∣
2
#s interpreted as probability density
14
d P(¯r , t )=C∣µ(¯r , t )∣
2
d
3
r
#s interpreted as probability density
0ormalization constant
µ(¯r , t )
"onsider the wave function representing total solution of the chrodinger
equation
µ(¯r , t )=c
1
µ
1
(¯r , t )+c
2
µ
2
(¯r , t )+.......+c
n
µ(¯r , t )
The total solution of the system may be decomposed in terms multiple
states in which system exist
µ(¯r , t )=
∑
i=1
n
c
i
µ
i
(¯r , t )
complex coefficient
15
Ze
+
e
−
r
v
n=1
n=2
n=3
#n the case of atomic orbitals
we may identify the following
µ
1
(¯r , t )
µ
2
(¯r , t )
µ
3
(¯r , t )
µ(¯r , t )=
∑
i=1
n
c
i
µ
i
(¯r , t )
0ormalized wave function
.robability finding particle in a
specific i th orbital is given by
P
i
(¯r , t )=
∣
c
i
∣
2
∑
i=1
n
∣
c
i
∣
2
16
−
ℏ
2
2m
∇
2
µ(¯r , t )+V (¯r , t )µ(¯r , t )=i ℏ
∂µ(¯r , t )
∂t
The general form the chrodinger equation for three dimensional
space
This is a fully phenomenological equation that can be arrived only by
argument validity of which can verified only by experiments%
&or a system consists of one particle the total probability of finding a
particle anywhere in space is given by
∫
d P(¯r , t )=1
#n this case the wave function must be square integrable$ that is
∫
∣µ(¯r , t )∣
2
d
3
r
is finite
∫
∣µ(¯r , t )∣
2
d
3
r=
1
C
is
normalizatio
n constant
∫
∣µ(¯r , t )∣
2
d
3
r=1
for normalized wave
function
17
The state of classical particle at time is determined by position
and the momentum
t ¯r
¯p
#n 2uantum mechanics infinite number of parmeters is associated with
the state of a particle at any time 3infinite number of points
are in this function4
µ(¯r , t )
Quantum mechanical description of the free particle
chroedinger equation for a free particles
−
ℏ
2
2m
∇
2
µ(¯r , t )=i ℏ
∂µ(¯r , t )
∂t
This differential equation is satisfied by the equation of the form
18
This differential equation is satisfied by the equation of the form
−
ℏ
2
2m
∇
2
µ(¯r , t )=i ℏ
∂µ(¯r , t )
∂t
,ccording to de Broglie hypothesis a plane wave should satisfy the
condition
ℏo=
ℏ
2
¯
k
2
2m
E=
p
2
2m
!hich is equivalent to classical condition
This differential equation can have trial solution
µ(¯r , t )=Ae
i (
¯
k⋅¯r −ot )
∣µ(¯r , t )µ
∗
(¯r , t )∣=
∣
A e
i(
¯
k⋅¯r −ot )
A
∗
e
−i(
¯
k⋅¯r −ot )
∣
2
∣µ(¯r , t )∣
2
=∣A∣
2
.lane wave predict uniform probability in the space
wavevector
19
principle of super position says that plane wave with any wave length is
a solution to chroedinger equation
µ(¯r , t )=A
1
µ
1
(¯r , t )+A
2
µ
2
(¯r , t )+...+A
n
µ
n
(¯r , t )............
A
n
=A
n
(k)
0ormalization factor of the wavefunction at a particular momentum
&or free particle there must be a continuous distribution of wavelengths$
then the summation can be replaced with an integral
µ( x , t )=
1
(2n)
1/2
∫
g(k) e
i (
¯
k x−o(k )t )
d k
, constant arising from the normalizing factor of &ourier transform 5d
0ow for the sa1e of simplicity let us assume plane waves parallel to
axis
x
µ(¯r , t )=
1
(2n)
3/2
∫
g(
¯
k)e
i(
¯
k⋅¯r −o(
¯
k )t )
d
3
k
20
#f we choose at a particular origin of time this wave can be further
simplifies as
µ( x , 0)=
1
(2n)
1/ 2
∫
g(k) e
i k x
d k
This is the mathematical representation a &ourier transform of function$
therefore the validity of the formula is not limited to free particle%
g(k)
Form of wave packet at given time
Ak
k
0
k
∣g(k)∣
Behavior of such wave
pac1ets may be studies using
simple case of interference of
waves
21
The qualitative behavior of the interference of the wave can be identified
with interference of three waves
*et the wavenumber corresponding these three waves are given by
k
0
,
k
0
+
Ak
2
k
0
−
Ak
2
,
, nd let their amplitudes are proportional respectively
1
2
, 1,
1
2
!e then have
µ( x , t )=
g(k
0
)
(2n)
1/2
(
e
i k
0
x
+
1
2
e
i
(
k
0
−
Ak
2
)
x
+
1
2
e
i
(
k
0
+
Ak
2
)
x
)
=
g(k
0
)
(2n)
1/2
e
i k
0
x
(
1+cos
(
Ak
2
x
)
)
22
k
0
−
Ak
2
k
0
+
Ak
2
k
0
µ( x , t )=
g(k
0
)
(2n)
1/2
e
i k
0
x
(
1+cos
(
Ak
2
x
)
)
−
Ax
2
Ax
2
x
0
23
The interference between completely destructive when the phase
difference between
e
i k
0
x
e
i
(
k
0
!
Ak
2
)
x
and
out of phase
e
i
(
!Ak
2
)
x
=e
i n
(
Ak
2
)
x=!n
That mean between two destructive interference we can have
relation for the products
Ak Ax=4n
, single particle moving in space given as interference of collection waves
of different wavelengths and frequencies which constructively interfere in a
region around mean position of the particle ' from this relation we may
derive a relation between mean change in position and momentum of the
particle
Ak Ax=4n
24
(k−k
0
)( x−x
0
)=4n
mean wavenumber
mean position
(
2n
\
−
2n
\
0
)( x−x
0
)=4n
/ultiplying both sides with .lanc1's constant
(
2nh
\
−
2nh
\
0
)( x−x
0
)=4nh
( p−p
0
)( x−x
0
)=2h
ApAx=2h
This means that when we measure the momentum or position of a
particle simultaneously we cannot measure the with accuracy
specified by this relation
25
This result is spacial case of the +eisenberg )ncertainty principle
which is in the form of an inequality
ApAx≥
ℏ
2
Ta1e the case of a single plane wave
µ( x , 0)=A e
i k x
ince this wave have a well defined wavenumber the the uncertainty
in the position is infinite
#n the similar fashion for a point particle the uncertainty in the
momentum is infinite
#n stead of considering a stationary wave$ if we ta1e the case of time
variation only in a wave we can get an uncertainty relation connecting
energy and time associated with wave
AEAt ≥
ℏ
2
26
Uncertainty relation and atomic parameters
V (r)=−
1
4nc
0
e
2
r
"onsider an electric field in the "oulomb field of an electron
V (r)=
−k
2
r
,ll constants of the problem
,ssume that the wavefunction of ground state is described by a spherically
symmetrical wave function let the average position of the electron is given by
r
0
Therfore the potential energy becomes
¯
V≃
−k
2
r
0
0ote that as electrons have wave nature position is not exact
#f electron is confined in a space having dimension the momentum is
given by
r
0
ApAx≥
ℏ
2
27
#f electron is confined in a space having dimension the momentum is
given by
r
0
ApAx≥
ℏ
2
Ap ≥
ℏ
r
0
The average momentum in this case is zero however average 1inetic energy
is not zero
¯
T≥T
min
=
(Ap)
2
2m
=
ℏ
2
2mr
0
2
Total energy compatible with the uncertainty relation is given by
¯
E=
¯
T+
¯
V =
ℏ
2
2mr
0
2
−
k
2
r
0
¯
V≃
−k
2
r
0
The value of is given by minimum of this function
r
0
*et
f (r)=
a
r
0
2
−
b
r
0
28
f (r)=
a
r
0
2
−
b
r
0
d f (r
0
)
d r
0
=
−2a
r
0
3
+
b
r
0
2
0=
−2a
r
0
3
+
b
r
0
2
/inimum is at value
br
0
=2a
k
2
r
0
=2
ℏ
2
2m
r
0
=
ℏ
2
mk
2
ubstituting this in energy relation
¯
E=
ℏ
2
2mr
0
2
−
k
2
r
0
=
ℏ
2
2m
(
ℏ
2
mk
2
)
2
−
k
2
(
ℏ
2
mk
2
)
29
¯
E=
ℏ
2
2m
(
ℏ
2
mk
2
)
2
−
k
2
(
ℏ
2
mk
2
)
=−
mk
4
2ℏ
2
=
mk
4
2ℏ
2
−
mk
4
ℏ
2
E
n
=−
(
1
(
4nc
0
)
2
mZ
2
e
4
2ℏ
2
)
1
n
2
∣
Z=1, n=1
k=
e
2
4nc
0
¯
E=−
m
(
e
2
4nc
0
)
4
2ℏ
2
=−
m
(
e
2
4nc
0
)
4
2ℏ
2
E=−
(
1
(
4nc
0
)
2
me
4
2ℏ
2
)
This is the same expression we get the Bohr model for first orbit of
+ydrogen
30
Phase space and Hilert Space
+amiltonian dynamics is best represented in phase space which is similar
to configuration space but include the momentum coordinates also
(q , p)
q
p
epresentation of one
dimensional motion in the
phase space
#n phase space for system that have
n degrees freedom is represented
by a point that have 6n coordinates
(q
1,
q
2,
.... q
n
, p
1,
p
2,
.... p
n
)
31
#n quantum mechanics state of system is represented in +ilbert space it is a
form of the abstract linear vector space
µ(¯r , t )=
∑
i=1
n
c
i
µ
i
(¯r , t )
#n quantum mechanics state of system is represented in +ilbert space$
each vector
, particular state of the system is given by
µ
i
(¯r , t )
#n +ilbert space the inner product is defined as
µ
i
(¯r , t )
Each vector is orthogonal to
each other
∫
µ
i
∗
(¯r , t )µ
j
(¯r , t )d
3
r
!hen the state vectors are orthogonal
∫
µ
i
∗
(¯r , t )µ
j
(¯r , t )d
3
r=C6
ij
32
Summary ! Postulates of Quantum Mechanics
2uantum mechanics is formulated based on these postulates$ we have
already discussed some these$ therefore$ we may summarize
74 tate of system is represented by a vector in the +ilbert space
µ
i
(¯r , t )
64 Every measurable physical quantity is is described by an
operator acting on the +ilbert space representing the system
A
´
A
"onsider the example of a plane wave here wavefunction is given by
µ( x , t )=A e
i (k x−ot )
,s every information is contained in this function the momentum also
may be obtained from this
33
/omentum of this plane wave is obtained from the wavefunction by
application of the operator
´ p=−i ℏ
¯
∇
´
p=−i ℏ
∂
∂ x
#n one dimension
/omentum of the plane wave is given by
´
pµ(r , t )=−i ℏ
∂
∂ x
Ae
i (k
x
x−ot )
=ℏk
x
Ae
i(
¯
k
x
x−ot )
i
=ℏk
x
µ( x , t )
!e can identify from the de Broglie relation that
ℏ k
x
=
h
2n
2n
\
x
=p
x
´ pµ(r , t )=ℏk
x
µ( x , t )=p
x
µ( x , t )
34
´ pµ( x , t )=p
x
µ( x , t )
This is the form of an eigenvalue equation ' 8ust li1e in the theory of
matrices and linear algebra
´
Aµ(¯r , t )=aµ(¯r , t )
The general form of this equation is
operator
vector 0umber vector
This form is called eigenvalue equation familiar in matrix form
9perator transform a vector 3wavefunction4 to a new one% #f the
transformation involves only the scaling of a vector 3wavefunction4 then
it is the eigenvalue of the problem
Eigenvalue problem is also a part of matrix algebra
35
#n the same manner in which we obtain the value of momentum we can
obtain other observables li1e position and energy from the wave
function ta1e case of 7d plane wave wavefunction
´ x µ( x , t )=x µ( x , t )
´ x=x
´ x A e
i (k
x
x−ot )
=x Ae
i(k
x
x−ot )
=x µ( x , t )
form of the operator
´
Eµ( x , t )=e µ( x , t )
The energy operator is given as
form of the operator
´
E=i ℏ
∂
∂t
i ℏ
∂
∂t
µ( x , t )=i ℏ
∂
∂t
Ae
i(k x−ot )
=ℏoA e
i (k x−ot )
µ( x , t )=A e
i (k x−ot )
Eigenvalue of energy
36
,ccording the principle of super position the system exist in a super
position of all possible states of the system
µ(¯r , t )=
∑
i=1
n
c
i
µ
i
(¯r , t )
n can have finite or infinite number of states
!hen the states are orthogonal we have the relation
∫
µ
i
∗
(¯r , t )µ
j
(¯r , t )d
3
r=C6
ij
!hen they are orthogonal and normalized
∫
µ
i
∗
(¯r , t )µ
j
(¯r , t )d
3
r=6
ij
!hen an observation is made on the system the system falls into one of
the possible states of the system
µ(¯r , t )=µ
i
(¯r , t )
with probability
∣
c
i
∣
2
0ow ta1e the case of full wavefunction representing the state of a system
37
54 ,ny possible result of measurement of a physical quantity is one
of the eigenvalue of corresponding observable
´
A
A
#n the case of discrete solution of the wave function we can write
0ow the postulate regarding the measurement can be stated as
µ(¯r , t )=
∑
i=1
n
c
i
µ
i
(¯r , t ) ∫
µ
∗
(¯r , t )µ(¯r , t ) d
3
r=1
´
Aµ
i
(¯r , t )=a
i
µ
i
(¯r , t )
Each of the state vectors obey eigenvalue equation
!hen the operator operates on the total wave function of the system the
probability finding a particular eigenvalue is given by
P(a
i
)
P(a
i
)=
∣
c
i
∣
2
=
∣∫
µ
i
∗
(¯r , t )µ(¯r , t )d
3
r
∣
2
=
∣
∫
µ
i
∗
(¯r , t )
∑
i=1
n
c
i
µ
i
(¯r , t )d
3
r
∣
2
38
:4 !hen the physical quantity is measured on a system in the
normalized state the probability of finding the non
degenerate eigenvalue of the corresponding observable is
where is the normalized eigenvector of associated
eigenvalue
A
µ(¯r , t )
a
i
P(a
i
)=
∣∫
µ
i
∗
(¯r , t )µ(¯r , t )d
3
r
∣
2
µ
i
(¯r , t )
´
A
a
i
;4 time evolution of the state vector is governed by the
chroedinger equation
µ(¯r , t )
´
Hµ(¯r , t )=i ℏ
∂µ(¯r , t )
∂t
+amiltonian operator of the system< corresponding observable give total energy of
the system
39
"#pectation value
´ ¯r , =
∫
¯r P(¯r , t ) d
3
r
The expectation value is the mathematical expectation$ for the result of a
single measurement% 9n otherwise$ it is the average of results of large
number of measurements on an independent system
=
∫
µ
∗
(¯r , t )¯r µ(¯r , t )d
3
r
40
Particle in a time$independent scalar potential
eparation of variables in chrodinger equation
−
ℏ
2
2m
∇
2
µ(¯r , t )+V (¯r , t )µ(¯r , t )=i ℏ
∂µ(¯r , t )
∂t
*et us loo1 if there exist solutions of the form
µ(¯r , t )=¡(¯r )X(t )
*et us loo1 if there exist solutions of the form
−X(t )
ℏ
2
2m
∇
2
¡(¯r )+X(t )V (¯r , t )¡(¯r )=i ℏ¡(¯r )
∂X(t )
∂t
Dividing all terms by the relation ¡(¯r )X(t )
−
1
¡(r)
ℏ
2
2m
∇
2
¡(¯r )+V (¯r , t )=i ℏ
1
X(t )
∂X(t )
∂t
space dependent part time dependent part
41
The space dependent part and time dependent part of the can be
equated if and only if both sides of the equation can be equated to a
constant we choose that constant to be
−
1
¡(r)
ℏ
2
2m
∇
2
¡(¯r )+V (¯r , t )=i ℏ
1
X(t )
∂X(t )
∂t
ℏo
−
1
¡(r)
ℏ
2
2m
∇
2
¡(¯r )+V (¯r , t )=i ℏ
1
X(t )
∂X(t )
∂t
−
1
¡(r)
ℏ
2
2m
∇
2
¡(¯r )+V (¯r , t )=ℏo
i ℏ
1
X(t )
dX(t )
d t
=ℏo
The time dependent part can be solved get solution in the differential
equation as
42
i ℏ
1
X(t )
dX(t )
d t
=ℏo
=
d X(t )
X(t )
=−i odt
X(t )=A e
−i ot
By integration
!e may set the constant as one and move that part to space dependent
solution$ that is
µ(¯r , t )=¡(¯r ) e
−i ot
imilarly the space dependent part should satisfy the differential equation
−
1
¡(r)
ℏ
2
2m
∇
2
¡(¯r )+V (¯r , t )=ℏo
−
ℏ
2
2m
∇
2
¡(¯r )+V (¯r , t )¡(r)=ℏo¡(r)
43
, stationary state is state with well defined energy
−
ℏ
2
2m
∇
2
¡(¯r )+V (¯r , t )¡(r)=E¡(r)
ℏo=E

−
ℏ
2
2m
∇
2
+V (¯r , t )
¦
¡(r)=E¡(r)
#n the compact form
´
H¡(r)=E¡(r)
The *+ of the equation may be written as
9perator form of the +amiltonian
´
H
is a linear operator since
´
H
(
\
1
¡
1
(r )+\
1
¡
1
(r)
)
=\
1
´
H¡
1
(r)+\
1
´
H¡
1
(r)
´
H¡(r)=E¡(r)
Eigenvalue equation of a linear operator
44
%equired properties of eigenfunctions &wavefunctions'
This is a fundamental requirement as
the evaluation of position and
momentum involves these conditions
for conservation and for ma1ing these
quantities well defined
µ( x)
finite
single valued
continuous
d µ( x)
d x