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Observations (experiments)
Hypothesis to explain (modified and refined)
Models and Theory
Laws (general behaviors)
Assumptions/conditions, time-space scopes,
definitions - limitations
Atkins / Paula
Physical Chemistry, 9th Edition
http://ebooks.bfwpub.com/pchemoup
P.249
Outline
1. Why Study Quantum Mechanics?
2. Quantum Mechanics Arose Out of the Interplay
of Experiments and Theory
3. Blackbody Radiation
4. The Photoelectric Effect
5. Particles Exhibit Wave-Like Behavior
6. Diffraction by a Double Slit
7. Atomic Spectra and the Bohr Model of the
Hydrogen Atom
Fig.7.2 The electromagnetic spectrum and the classification of the spectral regions
P.250
Blackbody Radiation ()
(7.4)
(T ) = (, T )d
Total energy:
E(T) = V (T)
(7.5)
P.251
P.252
E=nh
(n=0,1,2,)
(7.7)
h- Plancks constant 6.626x10-34Js
Planck distribution:
8hc
dE= d
(7.8)
( , T ) =
5 (e hc / kT 1)
hc / kT
faster than 5->0
For short wavelength, hc/kT 1, e
as
or
hc
hc
e hc / kT 1 = 1 +
+ ... 1
kT
kT
E = nhv
where h = Plancks constant
n = a positive integer (n 0, 1, 2, . . . )
8hc
d = aT 4
(T) = 5 hc / kT
0 e
1
with
8 5 k 4
a=
15(hc) 3
(7.9 )
Heat Capacity
(7 .10 a )
f E (T ) = E E / T
T
e
Einstein temperatur e E = h / k
1) At high temperatur es (T >> E ) :
E / 2T
(7.11)
1 + E/ 2T + L
f E (T ) = E
1 (7.12a);
T (1 + E/ T + L) 1
2) At low temperatur es (T << E ) :
2
E e
f E (T ) E / T = E e -E / T (7.12b)
Chapter 7. Quantum theory: introduction
P.248
T and
e principles
T
2
/ 2T
T D / T x 4e x
f D (T ) = 3
dx ( 7.13)
2
0
x
e 1
D
Debye temperature : D = h D / k
E = v
where = constant
v = frequency
From energy conservation the energy of the
electron, Ee, is
Ee = v
(7.15)
where = work function, characteristic of the metal,
the energy required to remove an electron from the
metal to infinity, the analogue of the Ionization Energy
of an atom or molecule.
E = hv
P.251
1
mev 2 = h (eqn 7.15) provides a technique for
2
1)
2)
3)
P.251
Example 1
Light with a wavelength of 300 nm is incident on a
potassium surface for which the work function, ,
is 2.26 eV. Calculate the kinetic energy and speed
of the ejected electrons.
Solution
We write Ee = hv = (hc / ) and convert the units
of from electron-volts to joules:
= (2.26eV )(1.602 10 19 J / eV ) = 3.62 1019 J
(
6.626 10 )(2.998 10 )
=
= 6.62 10
34
300 10
19
Solution (contd)
We can obtain Ee = (hc / ) = 2.99 1019 J .
Using
Ee = 1 / 2mv 2
, we calculate that
2 Ee
2 2.99 10 19 J
5
v=
=
=
8
.
10
10
m/ s
31
m
9.109 10
E
Pt
Pt
N=
=
=
h h (c )
hc
(
5.6010
= (6.62610
)(
)
Js )(2.99810
m 100 Js 1 (1.0 s )
34
20
=
2
.
8
10
8
ms1 )
h
=
p
where p = mv (particle momentum) (7.16)
Not only has electromagnetic radiation the character classically
ascribed to particles, but electrons (and all other particles) have
the characteristics classically ascribed to waves. This joint
particle and wave character of matter and radiation is called
waveparticle duality.
P.253
{2 (9.109 10
6.626 10 34 J s
31
) (
) (
kg 1.602 10 19 C 4.0 10 4V
)}
1/ 2
= 6.110 12 m
1 V C = 1 J and 1 J = 1 kg m2 s2.
The wavelength of 6.1 pm is shorter than typical bond lengths in
molecules (about 100 pm). Electrons accelerated in this way are
used in the technique of electron diffraction for the determination
of molecular structure
(see Section 23.3 structure of solid surface p.885).
Example 4
Electrons are used to determine the structure of
crystal surfaces. To have diffraction, the
wavelength of the electrons should be on the order
of the lattice constant, which is typically 0.30 nm.
What energy do such electrons have, expressed in
electron-volts and joules?
Solution:
Using E=p2/2m for the kinetic energy, we obtain
E=
34 2
p
h
6.626 10
18
=
=
=
2
.
7
10
or 17eV
2
31
10
2 m 2 m
2 9.109 10
3.0 10
2
)(
P.252
where = wavelength
1
1
1 1
~
v cm = RH cm 2 2 , n > n1
n1 n
Atomic spectra
Bohr frequency condition:
E = h
(7.14)
Molecular spectra
Fig. 7.11 When a
molecule changes its state,
it does so by absorbing
radiation at definite
frequencies. This
spectrum is part of that
due to the electronic,
vibrational, and rotational
excitation of sulfur
dioxide (SO2) molecules.
This observation suggests
that molecules can possess
only discrete energies, not
an arbitrary energy.
Electron microscopy ()
Traditional light microscopy - illuminating a small area of a sample and
collecting light with a microscope.
The resolution of a microscope, the minimum distance between two
objects that leads to two distinct images, is on the order of the
wavelength of light used as a probe.
Conventional microscopes employing visible light have resolutions in the
micrometre range and are blind to features on a scale of nanometres.
Electron microscopy, in which a beam of electrons with a well defined
de Broglie wavelength replaces the lamp found in traditional light
microscopes. Instead of glass or quartz lenses, magnetic fields are used
to focus the beam.
In transmission electron microscopy ( TEM), the
electron beam passes through the specimen and the image is collected
on a screen.
In scanning electron microscopy ( SEM), electrons
scattered back from a small irradiated area of the sample are detected
and the electrical signal is sent to a video screen. An image of the
surface is then obtained by scanning the electron beam across the
sample.
Outline
1. What Determines If a System Needs to Be
Described Using Quantum Mechanics?
2. Classical Waves and the Nondispersive(
) Wave Equation
3. Waves Are Conveniently Represented as
Complex Functions
4. Quantum Mechanical Waves and the
Schrdinger Equation
Outline
1. Solving the Schrdinger Equation: Operators,
Observables, Eigenfunctions, and
Eigenvalues
2. The Eigenfunctions of a Quantum Mechanical
Operator Are Orthogonal
3. The Eigenfunctions of a Quantum Mechanical
Operator Form a Complete Set
4. Summing Up the New Concepts
ni g i [ei e j ]/ kT
=
e
nj g j
where ni = number of atoms or molecules
i = energy of atoms or molecules
gi = degeneracy () at energy level i
(energy level vs. energy state)
Example 5
Consider a system of 1000 particles that can only have
two energies, = 2 1, with 1 and 2 . The difference
in the energy between these two values is 2 > 1 .
Assume that g1=g2=1.
a. Graph the number of particles, n1 and n2, in states
1 and 2 as a function of kT / . Explain your
result.
b. At what value of kT / do 750 of the particles have
the energy 1 ?
Solution
We can write down the following two equations:
n2 / n1 = e / kT and n1 + n2 = 1000
Solution
Part (b) is solved graphically. The parameter n1 is
shown as a function of kT / on an expanded
scale on the right side of the preceding graphs,
which shows that n1=750 for kT / = 0.91 .
Transverse( ), Longitudinal( ),
and Surface Waves
transverse wave (
)
Longitudinal wave (
)
x
y(x, t) = y0 sin t
c
Where y is the displacement of the point on the traveling sound wave; x is
the distance the point has traveled from the wave's source; t is the time
elapsed; y0 is the amplitude of the oscillations, c is the speed and is the
angular frequency of the wave. The quantity x/c is the time that the wave
takes to travel the distance x.
It is convenient to combine
constants and variables to
write the wave amplitude as
( x, t ) = A sin (kx wt )
where k = 2/ (wave vector)
= 2v (angular frequency)
p = hk ,
h
2
Example 6
The nondispersive wave equation in one dimension
is given by
2 ( x, t ) 1 2 (x, t )
= 2
2
x
v
t 2
Solution:
We have
2 (x, t ) 1 2 (x, t )
= 2
2
x
v
t 2
2 A sin (kx t + )
2
=
k
A sin (kx t + )
2
x
2 A sin (kx t + ) 2
= 2 A sin (kx t + )
2
2
v t
v
Equating these two results gives v = / k
Example 7
a. Express the complex number (4+4i) in the
form rei = r (cos + i sin )
3
e
b. Express the complex number
in the
form (a+ib)
i3 / 2
Solution
a. The magnitude of 4+4i is [(4 + 4i )(4 4i)]1/ 2 = 4
The phase is given by
cos =
4
4 2
1
1
or = cos 1
=
2
2 4
4 2ei ( / 4)
Solution
b. Using the relation e i
can be written
3
3
3 cos
+ i sin
= 3(0 i ) = 3i
2
2
+ V ( x) ( x) = E ( x )
2
2m dx
(7.17)
( x, t ) = ( x)e Et / ih = ( x)e i( E / h ) t
d 2
2m
= 2 (E V )
2
dx
h
= cos kx = cos( 2x / )
(harmonic
2m(E V )
2mEk
k =
= 2
2
h
h
Ek = k 2h 2 / 2 m = p 2 / 2 m
1/ 2
h
h
p = kh =
=
2
1/ 2
wave)
Test 7.3
The wavefunction for the electron in its lowest energy state in the
ion He+ is proportional to exp(2r/a0). Repeat the calculation for
this ion. Any comment?
Answer:
55; more compact wavefucntion
Normalization of wave-function
N - normalization constant
N 2 dx = 1
(7 .18)
N=
1/ 2
dx
(7 .19 )
dx = 1
(7. 20a)
In 3 Dimensions :
dxdydz = 1
d = 1
where
d = dxdydz
(7. 20b)
(7.20c)
r 2dr sin dd = 1
(7.20d )
n!
x e dx = n+1
a
n ax
d = N
2 2 r / a 0
r e
dr sin d d
1
= N 2 a03 2 2 = a03 N 2 = 1
4
1
N = 3
a0
1/ 2
1/ 2
1 r / a0
= 3 e
a0
Example
r
Solution:
N 2 d sin d r 2e 2 r dr = 1
4N 2 r 2 e2 r dr = 1
0
Solution
e r
4
N
we obtain
2!
1
=
1
so
that
N
=
23
e r
Fig. 7.23
The wavefunction
must satisfy stringent
conditions for it to
be acceptable.
(a) Unacceptable
because it is not
continuous;
(b) unacceptable
because its slope is
discontinuous;
(c) unacceptable
because it is not
single-valued;
(d) unacceptable
because it is infinite
over a finite region.
= E
2
2m dx
( 7.21)
Solutions : = Ae + Be
B =0:
= Ae ikx
ik x
ik x
k 2h 2
E=
2m
) (Ae ) = (A e )(Ae ) = A
= Ae
ikx
A = B:
ikx
ikx
ikx
(7.22)
(7.23)
2
(7.24)
(7.25)
probabilit y density :
node
(7.26)
direction of travel.
Chapter 7. Quantum theory: introduction and principles
P.267
H = E
h2 d 2
H =
+ V ( x)
2 m dx 2
( 7.27 a)
( 7.27 b)
+ V ( x ) n ( x ) = E n n ( x )
2
2 m x
)
where {} = total energy operator or H
It can be simplified as H n = En n
Example
2
2
d
/
dx
and
d
/
dx
Consider the operators
. Is the
function (x ) = Aeikx + Be ikx
an eigenfunction of
these operators? If so, what are the eigenvalues?
Note that A, B, and k are real numbers.
Solution
To test if a function is an eigenfunction of an
operator, we carry out the operation and see if the
result is the same function multiplied by a
constant:
d Ae ikx + Be ikx
= ikAeikx ikB ikx = ik Ae ikx Be ikx
dx
Solution
This equation shows that (x ) is an eigenfunction
of the operator d 2 / dx 2 with the eigenvalue k2.
d 2 Aeikx + Be ikx
2
2 ikx
ikx
=
(
ik
)
Ae
+
(
ik
)
B
2
dx
= k 2 Ae ikx + Be ikx
= k 2 (x )
= e = ae ax = a
dx
d ax2
ax 2
= e = 2axe = 2ax
dx
Test 7.5: Is the function cos ax an eigenfunction of
(a) d/dx, (b) d2/dx2?
Correct Answer: (a) No, (b) yes
,
Observables, , are represente d by operators,
built from the following position and momentum operators :
(Energy operator) = (energy)
(Operator correspond ing to an observable) = (value of observable)
Specificat ioon of operators : x = x ,
p x =
h d
i dx
[7.29]
What is the linear momentum of a particle described by the wavefunction in eqn 7.22:
with (a) B = 0, (b) A = 0?
k 2 h2
= Ae ikx + Be ikx , E =
2m
Method Operate on with the operator corresponding to linear momentum eqn 7.29:
Answer:
p x =
(a ) B = 0 :
h d
i dx
h d h deikx h
p x =
= A
= A ikeikx = kh Aeikx = kh
i dx i
dx
i
p x = +kh
(a ) A = 0 :
h d h deikx h
p x =
= B
= B (ik )e ikx = kh Beikx = kh
i dx i
dx
i
p x = kh
In (a) the particle is travelling to the right (positive x ) but in (b) it is travelling to the left
(negative x ).
Test 8.6 The operator for the angular momentum of a particle travelling in a circle in the
xy -plane is
d , where is its angular position. What is the angular momentum
lz = (h / i )
l z = 2h
1 2
V = kx
2
2
2
1
h
d
h
d
h
d
E k =
=
2 m i dx i dx
2m dx 2
(7.30)
(7.31)
2
2
h
d
= E + V =
Hamiltonia n operator : H
+ V (7.32)
k
2
2m dx
j d = j
Hermiticity :
i d
x j d = j x d =
{ x d }
[7.33]
p x j dx =
{ p dx}
integration by parts :
dg
df
f
dx
=
fg
g
dx
dxdx
Test 7.7 Confirm that the operator d 2 /dx 2 is hermitian.
d
=
d
=
d =
d =
= d =
hermiticity
x y = x z = y z = 0
Orthogonal ity :
i
j d = 0 for i j
(7.34)
+ constant (a 2 b 2 )
2( a b )
2(a + b)
cos( ) = cos cos m sin sin
2 sin sin = cos( + ) cos( )
Test 8.8 Confirm that the functions sin x and sin 3x are mutually
orthogonal.
Example
Show graphically that sin x and cos 3x are
orthogonal functions. Also show graphically that
Solution
The functions are shown in the following
graphs. The vertical axes have been offset to
avoid overlap and the horizontal line indicates
the zero for each plot.
Because the functions are periodic, we can
draw conclusions about their behaviour in an
infinite interval by considering their behaviour
in any interval that is an integral multiple of the
period.
Solution
Solution
The integral of these functions equals the sum
of the areas between the curves and the zero
line. Areas above and below the line contribute
with positive and negative signs, respectively,
(7.36)
where the ck are numerical (possibly complex) coefficients and the
k correspond to different momentum states. The functions k
form a complete set in the sense that any arbitrary function can
be expressed as a linear combination of them.
1. When the momentum is measured, in a single observation one
of the eigenvalues corresponding to the k that contribute to the
superposition will be found.
2. The probability of measuring a particular eigenvalue in a series
of observations is proportional to the square modulus (|ck|2) of
the corresponding coefficient in the linear combination.
3. The average value of a large number of observations is given
by the expectation value, <> , of the operator corresponding
to the observable of interest.
1
= 3 e r / a0 (E x.7.4)
a0
Bohr radius a 0 = 52.9pm
d
=
[7.37]
Test 7.9 Evaluate the root mean square distance, <r2>1/2, of the
electron from the nucleus in the hydrogen atom.
Correct Answer: 31/2a0 = 91.6 pm
A wavefunction
as a superposition
of eigenfunction
Complementary observables
General Heisenberg uncertainty principle: It applies to any pair of
observables called complementary observables, which are
defined in terms of the properties of their operators. Specifically,
two observables 1 and 2 are complementary if
(7.40)
When the effect of two operators depends on their order, they do
not commute.
The commutator of the two operators is defined as
(7.41)
The commutator of the operators for position and linear
momentum is
h
xp x p x x = = ih
i
(7.42)
The Heisenberg uncertainty principle in the most general form - For any two
pairs of observables, 1 and 2, the uncertainties (to be precise, the root
mean square deviations of their values from the mean) in simultaneous
determinations are related by:
Postulate 2
The wave function obeys the timedependent Schrodinger equation
H = ih
t
(1)
Postulate 2 (contd)
The time-independent Schrodinger equation can be
derived from the time-dependent equation by assuming
that the wave function is a product of a coordinate factor
and a time factor:
(q, t) = (q)(t)
(2)
where q stands for all of the coordinates of the particles
in the system and where the coordinate wave function
satisfies the time-independent Schrodinger equation.
Not all wave functions consist of the two factors in Eq.(2),
but all wave functions must obey the time-dependent
Schrodinger equation.
Ad
Postulate 5 (contd)
This postulate says very little about the state of the
system prior to a single measurement of the variable A,
because the act of measurement can change the state of
the system.
How a measurement can change the state of a system?
Consider the determination of the position of a particle by
the scattering of electromagnetic radiation:
When an airplane reflects a radar wave, the effect on the
airplane is negligible because of the large mass of the
airplane.
When an object of small mass such as an electron
scatters ultraviolet light or X-rays, the effect is not
negligible.
or, more generally, from operators that satisfy the commutation relation
[x, p x ] = ih
The Heisenberg uncertainty principle. It is impossible to specify simultaneously,
with arbitrary precision, both the momentum and the position of a particle and,
more generally, any pair of observable with operators that do not commute.