4-3 The Bohr Model of the Hydrogen Atom 165

5. Substituting the given values and computed results into Equation 4-6 gives N:
3.12 109 s 5 10 6 m2 5.85 1028 atoms m3 10 6 m
N 2 2
2 10 sin4 75 2
9 109 47 1.60 10 19 2 2

13
2 9.60 10
528 s

EXAMPLE 4-5 Radius of the Au Nucleus The radius of the gold (Au) nucleus
has been measured by high-energy electron scattering as 6.6 fm. What kinetic
energy particles would Rutherford have needed so that for 180 scattering, the
particle would just reach the nuclear surface before reversing direction?

SOLUTION
From Equation 4-11, we have
1 2 kq Q 9 109 2 79 1.60 10 19 2
mv
2 rd 6.6 10 15

12
5.52 10 J 34.5 MeV
Alpha particles of such energy are not emitted by naturally radioactive materials
and hence were not accessible to Rutherford. Thus, he could not have performed an
experiment for Au equivalent to that for Al illustrated by Figure 4-14.

Questions
1. Why can’t the impact parameter for a particular particle be chosen?
2. Why is it necessary to use a very thin target foil?
3. Why could Rutherford place a lower limit on the radius of the Al nucleus but not
on the Au nucleus?
4. How could you use the data in Figure 4-9a to determine the charge on a silver
nucleus relative to that on a gold nucleus?
5. How would you expect the data (not the curve) to change in Figure 4-9 if the foil
were so thick that an appreciable number of gold nuclei were hidden from the
beam by being in the “shadow” of the other gold nuclei?

4-3 The Bohr Model of the Hydrogen Atom

In 1913, the Danish physicist Niels H. D. Bohr10 proposed a model of the hydrogen
atom that combined the work of Planck, Einstein, and Rutherford and was remarkably
successful in predicting the observed spectrum of hydrogen. The Rutherford model
assigned charge and mass to the nucleus but was silent regarding the distribution of
the charge and mass of the electrons. Bohr, who had been working in Rutherford’s
laboratory during the experiments of Geiger and Marsden, made the assumption that
the electron in the hydrogen atom moved in an orbit about the positive nucleus, bound
by the electrostatic attraction of the nucleus. Classical mechanics allows circular or
elliptical orbits in this system, just as in the case of the planets orbiting the Sun. For

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 166 Chapter 4 The Nuclear Atom

simplicity, Bohr chose to consider circular orbits. Such a

model is mechanically stable because the Coulomb poten-
tial V kZe 2 r provides the centripetal force
kZe 2 mv 2
F 4-12
r 2 r
necessary for the electron to move in a circle of radius r at
speed v, but it is electrically unstable because the electron
is always accelerating toward the center of the circle. The
laws of electrodynamics predict that such an accelerating
charge will radiate light of frequency f equal to that of the
periodic motion, which in this case is the frequency of
revolution. Thus, classically,
v kZe 2 1 2
1 kZe 2 1 2
1 1
f
2 r rm 2 r 4 2m r3 2 r3 2
4-13
Niels Bohr explains a point
in front of the blackboard
The total energy of the electron is the sum of the kinetic and the potential energies:
(1956). [American Institute of 1 2 kZe 2
Physics, Niels Bohr Library, E mv
2 r
Margrethe Bohr Collection.]
From Equation 4-12, we see that 12mv 2 kZe 2 2r (a result that holds for circular
motion in any inverse-square force field), so the total energy can be written as
kZe 2 kZe 2 kZe 2 1
E 4-14
2r r 2r r
Thus, classical physics predicts that, as energy is lost to radiation, the electron’s orbit
will become smaller and smaller while the frequency of the emitted radiation will
become higher and higher, further increasing the rate at which energy is lost and end-
ing when the electron reaches the nucleus (see Figure 4-15a). The time required for
the electron to spiral into the nucleus can be calculated from classical mechanics and
electrodynamics; it turns out to be less than a microsecond. Thus, at first sight, this
model predicts that the atom will radiate a continuous spectrum (since the frequency
of revolution changes continuously as the electron spirals in) and
(a ) (b ) will collapse after a very short time, a result that fortunately does
not occur. Unless excited by some external means, atoms do not
radiate at all, and when excited atoms do radiate, a line spectrum is
emitted, not a continuous one.
Bohr “solved” these formidable difficulties with two decidedly
nonclassical postulates. His first postulate was that electrons could
move in certain orbits without radiating. He called these orbits sta-
tionary states. His second postulate was to assume that the atom
radiates when the electron makes a transition from one stationary
state to another (Figure 4-15b) and that the frequency f of the emit-
ted radiation is not the frequency of motion in either stable orbit but
FIGURE 4-15 (a) In the classical orbital model, is related to the energies of the orbits by Planck’s theory
the electron orbits about the nucleus and spirals hf E i E f 4-15
into the center because of the energy radiated.
(b) In the Bohr model, the electron orbits without where h is Planck’s constant and Ei and Ef are the energies of the
radiating until it jumps to another allowed radius of initial and final states. The second assumption, which is equivalent
lower energy, at which time radiation is emitted. to that of energy conservation with the emission of a photon, is

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 4-3 The Bohr Model of the Hydrogen Atom 167

crucial because it deviated from classical theory, which requires the frequency of
radiation to be that of the motion of the charged particle. Equation 4-15 is referred to
as the Bohr frequency condition.
In order to determine the energies of the allowed, nonradiating orbits, Bohr made
a third assumption, now known as the correspondence principle, which had profound
implications:

In the limit of large orbits and large energies, quantum calculations must
agree with classical calculations.

Thus, the correspondence principle says that, whatever modifications of classical physics
are made to describe matter at the submicroscopic level, when the results are extended
to the macroscopic world, they must agree with those from the classical laws of phys-
ics that have been so abundantly verified in the everyday world. While Bohr’s detailed
model of the hydrogen atom has been supplanted by modern quantum theory, which
we will discuss in later chapters, his frequency condition (Equation 4-15) and the cor-
respondence principle remain as essential features of the new theory.
In his first paper,11 in 1913, Bohr pointed out that his results implied that the angular
momentum of the electron in the hydrogen atom can take on only values that are integral
multiples of Planck’s constant divided by 2 , in agreement with a discovery made a year
earlier by J. W. Nicholson. That is, angular momentum is quantized; it can assume only
the values nh 2 , where n is an integer. Rather than follow the intricacies of Bohr’s
derivation, we will use the fundamental conclusion of angular momentum quantization
to find his expression for the observed spectra. The development that follows applies not
only to hydrogen, but to any atom of nuclear charge Ze with a single orbital electron—
for example, singly ionized helium He or doubly ionized lithium Li2 .
If the nuclear charge is Ze and the electron charge e, we have noted (Equa-
tion 4-12) that the centripetal force necessary to move the electron in a circular orbit
is provided by the Coulomb force kZe 2 r 2. Solving Equation 4-12 for the speed of
the orbiting electron yields
kZe 2 1 2
v 4-16
mr
Bohr’s quantization of the angular momentum L is
nh
L mvr n n 1, 2, 3, c 4-17
2
where the integer n is called a quantum number and h 2 . (The constant , read
“h-bar,” is often more convenient to use than h itself, just as the angular frequency
2 f is often more convenient than the frequency f.) Combining Equations 4-16
and 4-17 allows us to write for the circular orbits
1 2
n n rm
r
mv m kZe 2
Squaring this relation gives
n 2 2 rm
r2
m 2 kZe 2
and canceling common quantities yields
n2 2 n2a 0
rn 4-18
mkZe 2 Z

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 168 Chapter 4 The Nuclear Atom

where
2
a0 0.529 A 0.0529 nm 4-19
mke 2
is called the Bohr radius. The Å, a unit commonly used in the early days of spectros-
copy, equals 10 10 m or 10 1 nm. Thus, we find that the stationary orbits of Bohr’s
first postulate have quantized radii, denoted in Equation 4-18 by the subscript on rn.
Notice that the Bohr radius a0 for hydrogen (Z 1) corresponds to the orbit radius
with n 1, the smallest Bohr orbit possible for the electron in a hydrogen atom.
Since rn Z 1, the Bohr orbits for single-electron atoms with Z 1 are closer to the
nucleus than the corresponding ones for hydrogen.
The total energy of the electron (Equation 4-14) then becomes, on substitution of
rn from Equation 4-18,
kZe 2 kZe 2 mkZe 2
En
2rn 2 n2 2
mk 2 Z 2 e 4 Z2
En E0 n 1, 2, 3, c 4-20
2 2n2 n2
where E 0 mk 2 e 4 2 2. Thus, the energy of the electron is also quantized; that is, the
stationary states correspond to specific values of the total energy. This means that
energies Ei and Ef that appear in the frequency condition of Bohr’s second postulate
must be from the allowed set En and Equation 4-15 becomes
Z2 Z2
hf E ni E nf E0 E0
n 2i n 2f
or
E 0Z 2 1 1
f 4-21
h n 2f n 2i
which can be written in the form of the Rydberg-Ritz equation (Equation 4-2) by sub-
stituting f c and dividing by c to obtain
1 E0 Z 2 1 1
hc n 2f n 2i
or
1 1 1
Z2R 4-22
n 2f n 2i
where
E0 mk 2 e 4
R 4-23
hc 4 c 3
is Bohr’s prediction for the value of the Rydberg constant.
Using the values of m, e, c, and known in 1913, Bohr calculated R and found
his result to agree (within the limits of uncertainties of the constants) with the value
obtained from spectroscopy, 1.097 107 m 1. Bohr noted in his original paper that
this equation might be valuable in determining the best values for the constants e, m,
and because of the extreme precision possible in measuring R. This has indeed
turned out to be the case.

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 4-3 The Bohr Model of the Hydrogen Atom 169

The possible values of the energy of the hydrogen atom predicted by Bohr’s
model are given by Equation 4-20 with Z 1:
mk 2 e 4 E0
En 4-24
2 2n2 n2
where
mk 2 e 4 18
E0 2.18 10 J 13.6 eV
2 2
is the magnitude of En with n 1. E1( E0) is called the ground state. It is conve-
nient to plot these allowed energies of the stationary states as in Figure 4-16. Such a

(a ) n
0
– 0.54 5
– 0.85 4
Paschen
–1.51 3
Balmer

– 3.40 2
Energy, eV

Lyman series

–13.60 1

(b ) Lyman Balmer Paschen

100 200 500 1000 2000

, nm

FIGURE 4-16 (a) Energy-level diagram for hydrogen showing the seven lowest stationary states and the four lowest energy
transitions each for the Lyman, Balmer, and Paschen series. There are an infinite number of levels. Their energies are given by
En 13.6 n 2 eV, where n is an integer. The dashed line shown for each series is the series limit, corresponding to the energy
that would be radiated by an electron at rest far from the nucleus (n ) in a transition to the state with n nf for that series.
The horizontal spacing between the transitions shown for each series is proportional to the wavelength spacing between the lines
of the spectrum. (b) The spectral lines corresponding to the transitions shown for the three series. Notice the regularities within
each series, particularly the short-wavelength limit and the successively smaller separation between adjacent lines as the limit is
approached. The wavelength scale in the diagram is not linear.

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 170 Chapter 4 The Nuclear Atom

plot is called an energy-level diagram. Three series of transitions between the station-
ary states are shown in this diagram by vertical arrows drawn between the levels. The
frequency of light emitted in each of these transitions is the energy difference divided
by h according to Bohr’s frequency condition, Equation 4-15. The energy required to
remove the electron from the atom, 13.6 eV, is called the ionization energy, or bind-
ing energy, of the electron.
At the time Bohr’s paper was published, there were two spectral series known for
hydrogen: the Balmer series, corresponding to nf 2, ni 3, 4, 5, . . . , and a series
named after its discoverer, Paschen (1908), corresponding to nf 3, ni 4, 5, 6, . . . .
A bit different sort of
Equation 4-22 indicated that other series should exist for different values of nf. In
application, the Bohr-
1916 Lyman found the series corresponding to nf 1, and in 1922 and 1924 Brackett
Rutherford model of
and Pfund, respectively, found series corresponding to nf 4 and nf 5. As can be
the nuclear atom and
easily determined by computing the wavelengths for these series, only the Balmer
electron orbits is the
picture that, for millions
series lies primarily in the visible portion of the electromagnetic spectrum. The
of people, provides their
Lyman series is in the ultraviolet, the others in the infrared.
visual link to the world of
the atom and subatomic EXAMPLE 4-6 Wavelength of the H Line Compute the wavelength of the
phenomena. H spectral line, that is, the second line of the Balmer series predicted by Bohr’s
model. The H line is emitted in the transition from ni 4 to nf 2.

SOLUTION
1. Method 1: The wavelength is given by Equation 4-22 with Z 1:
1 1 1
R
n 2f n 2i
2. Substituting R 1.097 107 m 1
and the values of ni and nf :
1 1 1
1.097 107 m 1
22 42
or
7
4.86 10 486 nm
3. Method 2: The wavelength may also be computed from Equation 4-15:
hf hc Ei Ef
or
1 1
E Ef
hc i
4. The values of Ei and Ef are given by Equation 4-24:
13.6 eV 13.6 eV
Ei 0.85 eV
n 2i 42
13.6 eV 13.6 eV
Ef 3.4 eV
n 2f 22
5. Substituting these into Equation 4-15 yields
19
1 0.85 eV 3.4 eV 1.60 10 J eV
34 8
6.63 10 J s 3.00 10 m s
6 1
2.051 10 m

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 4-3 The Bohr Model of the Hydrogen Atom 171

or
4.87 10 7 m 487 nm

Remarks: The difference in the two results is due to rounding of the Rydberg con-
stant to three decimal places.

Reduced Mass Correction

The assumption by Bohr that the nucleus is fixed is equivalent to the assumption that
it has infinite mass. In fact, the Rydberg constant in Equation 4-23 is normally written
as R , as we will do from now on. If the nucleus has mass M, its kinetic energy will be
1 2
2 Mv p 2 2M , where p Mv is the momentum. If we assume that the total momen-
tum of the atom is zero, conservation of momentum requires that the momenta of the
nucleus and electron be equal in magnitude. The total kinetic energy is then
p2 p2 M m 2 p2
Ek p
2M 2m 2mM 2
where
mM m
4-25
m M 1 m M
This is slightly different from the kinetic energy of the electron because , called CCR
the reduced mass, is slightly different from the electron mass. The results derived
earlier for a nucleus of infinite mass can be applied directly to the case of a nucleus
of mass M if we replace the electron mass in the equations by reduced mass , 29
defined by Equation 4-25. (The validity of this procedure is proven in most inter-
mediate and advanced mechanics books.) The Rydberg constant (Equation 4-23) is
then written
k 2e4 mk 2 e 4 1 1
R R 4-26
4 c 3 4 c 3 1 m M 1 m M
This correction amounts to only 1 part in 2000 for the case of hydrogen and to even
less for other nuclei; however, the predicted variation in the Rydberg constant from
atom to atom is precisely that which is observed. For example, the spectrum of a sin-
gly ionized helium atom, which has one remaining electron, is just that predicted by
Equations 4-22 and 4-26 with Z 2 and the proper helium mass. The current value
for the Rydberg constant R from precision spectroscopic measurements12 is
R 1.0973732 107 m 1
1.0973732 10 2 nm 1
4-27

Urey13 used the reduced mass correction to the spectral lines of the Balmer series to
discover (in 1931) a second form of hydrogen whose atoms had twice the mass of
ordinary hydrogen. The heavy form was called deuterium. The two forms, atoms with
the same Z but different masses, are called isotopes.

EXAMPLE 4-7 Rydberg Constants for H and He Compute the Rydberg con-
stants for H and He applying the reduced mass correction (m 9.1094 10 31 kg,
mp 1.6726 10 27 kg, m 6.6447 10 27 kg).

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