Quantum Theory
of the Atom
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When the
wavelength is
reduced by a
factor of two,
the frequency
increases by
a factor of
two.
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= 6.4 1014/s
c = 3.00 108 m/s
c = so
= c/
m
3.00 x 10
c
s
14 1
6.4 x 10
s
8
= 4.7 10-7 m
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E = h
where h (Plancks constant) is assigned a value of
6.63 x 10-34 J. s and n must be an integer.
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Li+
Ca2+
Cu2+
Sr2+
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Ba2+
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Emission
(line)
spectra of
some
elements.
Blackbody radiation
The photoelectric
effect.
E = h
In 1905, Einstein used this concept to explain the
photoelectric effect.
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The photoelectric
effect.
Photoelectric effect
For a given metal, a
certain amount of
energy is needed to
eject the electron
This is called the work
function
Since E=h, the
photons must have a
frequency higher than
the work function in
order to eject electrons
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Energy-Level Postulate
An electron can have only certain energy values,
called energy levels. Energy levels are quantized.
For an electron in a hydrogen atom, the energy is
given by the following equation:
RH
n
RH = 2.179 x 10-18 J
n = principal quantum number
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E R H
n2
f
1
2
ni
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h R H
n2
f
1
2
ni
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Energy-level diagram
for the hydrogen atom.
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1
E R H
2
2
n
n
i
f
hc
hc
E
so
ni = 6
nf = 3
RH = 2.179 10-18 J
1
1
-19
=
-1.816
x
10
J
2
2
6
3
E 2.179 x 10 18 J
m
6.626 x 10 J s 2.998 x 10
1.094 10-6 m
19
- 1.816 x 10 J
34
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Planck
Vibrating atoms have only certain energies:
E = h or 2h or 3h
Einstein
Energy is quantized in particles called photons:
E = h
Bohr
Electrons in atoms can have only certain values of
energy. ForR hydrogen:
E
H
2
n
RH 2.179 x 10 18 J, n principal quantum number
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Quantum Mechanics
Bohrs theory established the concept of atomic
energy levels but did not thoroughly explain the
wave-like behavior of the electron.
Current ideas about atomic structure depend on
the principles of quantum mechanics, a theory that
applies to subatomic particles such as electrons.
Quantum Mechanics
The first clue in the development of quantum
theory came with the discovery of the
de Broglie relation.
In 1923, Louis de Broglie reasoned that if light
exhibits particle aspects, perhaps particles of
matter show characteristics of waves.
He postulated that a particle with mass m and a
velocity v has an associated wavelength.
The equation = h/mv is called the de Broglie
relation.
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de Broglie Relation
For a photon that has both wave and particle
characteristics:
E = h = hc/ (recall c= )
E = mc2
mc2 = hc/ or = h/mc
Since mc is the momentum of a photon, can we
replace this with the momentum of a particle?
= h/mv
This suggests that particles have wave-like
characteristics!
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Quantum Mechanics
If matter has wave properties, why are they not
commonly observed?
The de Broglie relation shows that a baseball
(0.145 kg) moving at about 60 mph (27 m/s) has a
wavelength of about 1.7 x 10-34 m.
2
34 kgm
10
s
6.63
(0.145 kg )(27 m / s )
1.7 10
34
Quantum Mechanics
If matter has wave properties, why are they not
commonly observed?
Electrons have wavelengths on the order of a few
picometers (1 pm = 10-12 m).
Under the proper circumstances, the wave character
of electrons should be observable.
Molecules are of the dimension of a few pm, so the
wave character of electrons is very important in
molecules
Quantum Mechanics
If matter has wave properties, why are they not
commonly observed?
In 1927, Davisson and
Germer was
demonstrated that a
beam of electrons,
just like X rays, could
be diffracted by a
crystal.
Davisson-Germer experiment
Quantum Mechanics
Quantum mechanics is the branch of physics
that mathematically describes the wave
properties of submicroscopic particles.
We can no longer think of an electron as having
a precise orbit in an atom.
To describe such an orbit would require knowing
its exact position and velocity.
In 1927, Werner Heisenberg showed (from
quantum mechanics) that it is impossible to
know both simultaneously.
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Quantum Mechanics
Heisenbergs uncertainty principle is a
relation that states that the product of the
uncertainty in position (x) and the
uncertainty in momentum (mvx) of a particle
can be no larger than h/4.
h
(x)(mvx )
4
When m is large (for example, a baseball) the
uncertainties are small, but for electrons, high
uncertainties disallow defining an exact orbit.
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Heisenbergs Uncertainty
Principle
(x)(mvx ) h
Quantum Mechanics
Although we cannot precisely define an
electrons orbit, we can obtain the probability
of finding an electron at a given point around
the nucleus.
Erwin Schrodinger defined this probability in a
mathematical expression called a wave function,
denoted (psi).
The probability of finding a particle in a region of
space is defined by .
( x) 0
2
2
x
v
2
2
4
since v=
(
x
)
0
2
2
x
( x) A cos(2 x / )
2
Schrodinger equation
mv 2
E
V ( x), rearrange to give mv={2m[E-V ( x)]}1/ 2
2
h
h
de Broglie relation
mv {2m[E-V ( x)]}1/ 2
2 4 2
2 2m[E-V ( x)]
classical wave eqn.
2 ( x) 2
( x) 0
2
2
x
x
(h / 2 )
(h / 2 ) 2 2
Schrodinger eqn. V ( x) ( x) E ( x)
2
2m x
Postulates of Quantum
Mechanics
The state of a quantum mechanical system is completely
specified by its wavefunction, (x,t)
For every classical observable there is a linear, Hermitian
operator in quantum mechanics
In any measurement associated with an operator, the only
values observed are eigenvalues of the operator,
A (x,t) = a (x,t)
The average values of an observable is given by its
expectation value,
*
A Ad
H ( x, t )
The wavefunction
The square of the wavefunction 2 is the
probability density for finding the particle at that
location
The wavefunction must be
Single valued
Continuous
Continuous first derivative
Quadratically integrable
d must be finite
*
*
energy state
H d
Evar
d
*
Eexact
( x) 0
inside the box V ( x) 0,
( x)
1/ 2
n x
sin(
)
l
n2h2
E
, n 1, 2,...
2
8ml
1-Dimensional Harmonic
Oscillator
Schrodinger equation
(h / 2 ) 2 2 1 2
H E , H
kx
2
2m x
2
E h (n 1/ 2), n 0,1, 2,...
v
k
km
,
2
m
(
h
/
2
1
2
0 ( x)
1/ 4
exp( x 2 / 2),
1/ 4
2 ( x)
4
1/ 4
1 ( x)
1/ 2
(2 1/ 2 x) exp( x 2 / 2)
(2 x 2 1) exp( x 2 / 2)
Hydrogen-like Atom
Nucleus with charge Ze at origin,
Electron with charge -e at (x,y,z) or (r, , )
Schrodinger equation for hydrogen-like atom
H E ,
2
2
2
Ze 2
x 2 y 2 z 2 4 r
0
2
(h / 2 ) 2 2 2
1
Ze
2
H
2
2
2m r
r r
2mr
4 0 r
(h / 2 ) 2
H
2m
2
2
2
2
L (h / 2 )
cot
2
2
2
sin
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K
1
L
2
M
3
N
4
...
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0
s
1
1
p
2
2
d
3
3
f
4
...
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The figure
shows
relative
energies for
the hydrogen
atom shells
and
subshells;
each orbital
is indicated
by a dashedline.
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Other Resources
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