3.4.
The Quantum Structure of Atoms 115
Note:
The first excited state (n = 2) of the H atom already
needs an excitation energy of about 10.2 eV, which is
3/4 of the ionization energy.
Although Bohrs semiclassical atomic model ex-
plains the observed spectra very well, and also brings
some esthetical satisfaction, because of its resemblance
to the planetary system, it leaves several questions
open. One essential point is that, according to classi-
cal electrodynamics, every accelerated charge should
emit radiation. The electron on its circular path is such
an accelerated charge. It should, therefore, loose energy
by emitting radiation and should spiral down into the
nucleus. Therefore, the Bohr model cannot explain the
existence of stable atoms.
3.4.3 The Stability of Atoms
The stability of atoms is consistently explained by
quantum theory. We will here give a conspicuous ar-
gument based on the uncertainty relation. It should be
only regarded as a simple estimation that is not re-
stricted to circular paths of the electron. If a is the
mean radius of the atom, we can give the distance r
of the electron from the nucleus with an uncertainty
r a, since we know that the electron has to be
found somewhere within the atom. According to the
uncertainty relation the uncertainty pr of the radial
component of the electron momentum p must be lar-
ger than !/a. Therefore we conclude for the uncertainty
p pr !/a (otherwise we could determine p wi-
thin narrower limits than its component pr ). We find the
relation p > p !/a. The mean kinetic energy of the
electron is:
p2 ( p)2 !2
E kin = . (3.92)
2m e 2m e 2m e a2
Its potential energy at a distance a from the nucleus
is
e2
E pot = (3.93)
40 a
and its total energy E = E kin + E pot at the distance a is
then:
!2 e2
E . (3.94)
2ma2 40 a
The largest probability of finding the electron is at a di-
stance amin where the total energy is minimum, i.e.,
where dE/ da = 0. This gives
40 !2 0 h 2
amin = = = a0 (3.95)
me2 e2
which is identical to the Bohr radius a0 .
Therefore, a stable state exists with the minimum
energy limit
me4 me4
E min = 2 2
= 2 2 = Ry ,
2(40 ! ) 80 h
(3.96)
which is consistent with the energy of the lowest state
with n = 1 in Bohrs model.
Although the quantum mechanical results for the
energy confirms Bohrs result, the explanation of the
stability is different.
According to the uncertainty principle the atom can-
not radiate in its lowest state because it has minimum
energy. In order to emit a photon, it would have to make
a transition to a higher energy state, which contradicts
energy conservation. The reason for this energy mini-
mum is the sharp increase of the kinetic energy of the
electron with decreasing distance a, due to the uncer-
tainty of its momentum (Fig. 3.43). In higher energy
states the atom can radiate, in accordance with the
experimental results.
In Bohrs model the stability is explained by the as-
sumption of standing waves for the electron, where the
Poynting vector is zero. However, this does not explain
why higher energy states, which are also represented by
standing waves, do radiate.
3.4.4 FranckHertz Experiment
James Franck and Gustav Hertz [3.18] gave in 1914
an impressive experimental proof for the energy quan-
tization of atoms based on the following experimental
arrangement (Fig. 3.44a).
Electrons, emitted from a hot cathode are accele-
rated to the energy E kin = eU by the grid G at the
voltage U against the cathode in a bulb, filled with
mercury vapor at low pressures. The electrons can only
reach the collecting anode A that is kept at a lower vol-
tage UA = U U, if their energy after having passed
the grid G is at least eU.
116 3. Development of Quantum Physics

G A The electrons suffer elastic and inelastic collisions

K with the Hg atoms. In inelastic collisions,
e (E kin ) + Hg Hg (E a ) + e (E kin E a )
the electrons excite the Hg atoms and transfer the
amount E kin = E kin E a of their kinetic energy to
I the excitation energy E a of the atom. Because of
U this loss of energy the electrons cannot overcome the
U bias voltage U and therefore cannot reach the
U +
detector.
a) + During elastic collisions the electron can at most
transfer the fraction 4m e /m Hg 105 of its kinetic
energy. At sufficiently low pressures each electron suf-
I / A
fers only a few elastic collisions and the total energy
350
4.9 V loss due to elastic collisions is then completely negli-
gible. However, elastic collisions may result in large
300
angular changes of the electrons flight direction and
the electrons may therefore hit the walls of the tube
250 before they reach the anode. Without inelastic collisi-
ons the electron current would follow the dashed curve
in Fig. 3.44b, which resembles the electron current in
200 a diode tube. The further maxima and minima in the ac-
tually measured current I(UA ) are due to the fact that
at sufficiently large voltages U the electron can regain,
150
after n inelastic collisions, the minimum required ki-
netic energy eZ during its flight path to the grid G
100 but has not enough energy for the (n + 1)th inelastic
collision.
The separation between subsequent maxima cor-
50 responds to the excitation energy E a = 4.9 eV of Hg
atoms. The exact form of the curve I(U) in Fig. 3.44 is
determined by
0
5 10 15
b) U/V
The energy dependence of the excitation probability
(Fig. 3.45)
Fig. 3.44a,b. FranckHertz experiment. (a) Experimental se-
tup (b) Electron current as function of the acceleration
The energy distribution of the electrons emitted
voltage U in a tube with mercury vapor from the hot cathode.
With the improved experimental setup of Fig. 3.45a
the energy resolution could be substantially impro-
When measuring the electron current IA (U) as ved. Here, two grids are used and the acceleration of
a function of the acceleration voltage U, one obtains the electrons is essentially restricted to the short flight
a curve like that in Fig. 3.44b. The current increases path between K and G1 , while the small adjustable vol-
with U between U = 0 and U = 4.9 eV and follows tage U2 between G2 and G1 does not change the electron
a typical diode characteristics. Above U1 = 4.9 V the energy much. The excitation probability is then nearly
current decreases sharply, goes through a minimum, ri- the same for all points between G1 and G2 . With such
ses again until it reaches a second maximum at about an improved apparatus the finer details of the excita-
Ue = 9.8 eV. tion function could be resolved, which correspond to
How can this be explained? different excited states of the Hg atoms (Fig. 3.46).
 3.5. What are the Differences Between Classical and Quantum Physics? 117

A exc / 1016 cm2

K Hg atom

G1 G2 0.5
I H atom
U1 U2 0.4
U

+
a) + +
0.2

I/A 4.68
4.9
30 4 8 12 16 20 Eel / eV
Fig. 3.46. Energy dependence of the excitation cross section
25 for the excitation n = 1 n = 2 in the H atom (black curve)
pHg = 50 Pa and on the singlet-triplet transition 61 S0 63 P1 in the Hg
atom (blue curve)
20

5.29
15 short time (typically 108 s) into lower states E k ,
6.73 where
10 E = E k E i = hik = hc/ik .
5.78
Only the lowest atomic states (called the ground states)
5 are stable. Their lifetimes are infinitely long (if not
excited by collisions or absorption of photons). The
wavelength ik of the emission spectrum measured
1 2 3 4 5 6 through a spectrograph allow a much higher accuracy in
b) U/V
the determination of energy levels than those obtained
Fig. 3.45. (a) Improved experimental arrangement for the from the electron impact measurements in Figs. 3.45
FranckHertz experiment with higher energy resolution.
(b) Electron current I(U) measured with the apparatus shown and 3.46.
in (a), where the excitation of many higher levels in the Hg
atom can be seen. The structured maximum corresponds to The experimental results of the electron impact
the first maximum in Fig. 3.44b excitation prove that atoms can acquire energy
only in discrete energy quanta E. Their magni-
tude depend on the specific atom and its level
The excited Hg atoms release their excitation structure.
energy by emission of light
Hg Hg + h .
Measuring this fluorescence light through a mono-
chromator shows that the emitted spectral lines have 3.5 What are the Differences Between
wavelengths k , which exactly correspond to the mea- Classical and Quantum Physics?
sured absorption lines of Hg vapor. Time-resolved
measurements of this fluorescence prove that the excited In the quantum physical description of micropartic-
atomic levels E i are not stable. They decay within a very les, such as atoms, molecules, electrons and photons,