Bohr's model of hydrogen

How Bohr's model of hydrogen explains atomic emission spectra.

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Key points
 Bohr's model of hydrogen is based on the nonclassical assumption that electrons travel
in specific shells, or orbits, around the nucleus.
 Bohr's model calculated the following energies for an electron in the shell, nnnn:

 Bohr explained the hydrogen spectrum in terms of electrons absorbing and emitting
photons to change energy levels, where the photon energy is

hν=ΔE=(1nlow2−1nhigh2)⋅13.6 eVh\nu =\Delta E = \left(\dfrac{1}{{n_{low}}^2}-\dfrac{1}

{{n_{high}}^2}\right) \cdot 13.6\,\text{eV} hν=ΔE=(nlow21−nhigh21)⋅13.6eVh, \nu, equals,
delta, E, equals, left parenthesis, start fraction, 1, divided by, n, start subscript, l, o, w, end
subscript, squared, end fraction, minus, start fraction, 1, divided by, n, start subscript, h, i, g, h,
end subscript, squared, end fraction, right parenthesis, dot, 13, point, 6, start text, e, V, end text

 Bohr's model does not work for systems with more than one electron.
The planetary model of the atom
At the beginning of the 20th century, a new field of study known as quantum mechanics
emerged. One of the founders of this field was Danish physicist Niels Bohr, who was interested
in explaining the discrete line spectrum observed when light was emitted by different elements.
Bohr was also interested in the structure of the atom, which was a topic of much debate at the
time. Numerous models of the atom had been postulated based on experimental results including
the discovery of the electron by J. J. Thomson and the discovery of the nucleus by Ernest
Rutherford. Bohr supported the planetary model, in which electrons revolved around a positively
charged nucleus like the rings around Saturn—or alternatively, the planets around the sun.

Image of Saturn and rings

Many scientists, including Rutherford and Bohr, thought electrons might orbit the nucleus like
the rings around Saturn. Image credit: Image of Saturn by NASA
However, scientists still had many unanswered questions:

 Where are the electrons, and what are they doing?

 If the electrons are orbiting the nucleus, why don’t they fall into the nucleus as predicted
by classical physics?

[Why does classical physics predict that?]

 How is the internal structure of the atom related to the discrete emission lines produced
by excited elements?
Bohr addressed these questions using a seemingly simple assumption: what if some aspects of
atomic structure, such as electron orbits and energies, could only take on certain values?

Quantization and photons

By the early 1900s, scientists were aware that some phenomena occurred in a discrete, as
opposed to continuous, manner. Physicists Max Planck and Albert Einstein had recently
theorized that electromagnetic radiation not only behaves like a wave, but also sometimes like
particles called photons. Planck studied the electromagnetic radiation emitted by heated objects,
and he proposed that the emitted electromagnetic radiation was "quantized" since the energy of
light could only have values given by the following equation:

Ephoton=nhνE_{\text{photon}}=nh\nuEphoton=nhνE, start subscript, start text, p, h, o, t, o, n,

end text, end subscript, equals, n, h, \nu, where nnnn is a positive integer, hhhh is Planck’s
constant—6.626×10−34 J⋅s6.626 \times10^{-34}\,\text {J}\cdot \text s6.626×10−34J⋅s6, point,
626, times, 10, start superscript, minus, 34, end superscript, start text, J, end text, dot, start text, s,
end text—and ν\nuν\nu is the frequency of the light, which has units of 1s\dfrac{1}{\text s}s1
start fraction, 1, divided by, start text, s, end text, end fraction.
As a consequence, the emitted electromagnetic radiation must have energies that are multiples of
hνh\nuhνh, \nu. Einstein used Planck's results to explain why a minimum frequency of light was
required to eject electrons from a metal surface in the photoelectric effect.
[Where can I learn more about the photoelectric effect?]
When something is quantized, it means that only specific values are allowed, such as when
playing a piano. Since each key of a piano is tuned to a specific note, only a certain set of notes
—which correspond to frequencies of sound waves—can be produced. As long as your piano is
properly tuned, you can play an F or F sharp, but you can't play the note that is halfway between
an F and F sharp.
Atomic line spectra
Atomic line spectra are another example of quantization. When an element or ion is heated by a
flame or excited by electric current, the excited atoms emit light of a characteristic color. The
emitted light can be refracted by a prism, producing spectra with a distinctive striped appearance
due to the emission of certain wavelengths of light.

Emission spectra of sodium, top, compared to the emission spectrum of the sun, bottom. The
dark lines in the emission spectrum of the sun, which are also called Fraunhofer lines, are from
absorption of specific wavelengths of light by elements in the sun's atmosphere. The side-by-side
comparison shows that the pair of dark lines near the middle of the sun's emission spectrum are
probably due to sodium in the sun's atmosphere. Image credit: From the Biodiversity Heritage
Library
For the relatively simple case of the hydrogen atom, the wavelengths of some emission lines
could even be fitted to mathematical equations. The equations did not explain why the hydrogen
atom emitted those particular wavelengths of light, however. Prior to Bohr's model of the
hydrogen atom, scientists were unclear of the reason behind the quantization of atomic emission
spectra.

Bohr's model of the hydrogen atom: quantization of

electronic structure
Bohr’s model of the hydrogen atom started from the planetary model, but he added one
assumption regarding the electrons. What if the electronic structure of the atom was quantized?
Bohr suggested that perhaps the electrons could only orbit the nucleus in specific orbits or shells
with a fixed radius. Only shells with a radius given by the equation below would be allowed, and
the electron could not exist in between these shells. Mathematically, we could write the allowed
values of the atomic radius

as r(n)=n2⋅r(1)r(n)=n^2\cdot r(1)r(n)=n2⋅r(1)r, left parenthesis, n, right parenthesis, equals, n,

squared, dot, r, left parenthesis, 1, right parenthesis, where nnnn is a positive integer, and
r(1)r(1)r(1)r, left parenthesis, 1, right parenthesis is the Bohr radius, the smallest allowed radius
for hydrogen.
He found that r(1)r(1)r(1)r, left parenthesis, 1, right parenthesis has the value
Bohr radius=r(1)=0.529×10−10 m\text{Bohr radius}=r(1)=0.529 \times 10^{-10}
\,\text{m}Bohr radius=r(1)=0.529×10−10mstart text, B, o, h, r, space, r, a, d, i, u, s, end text,
equals, r, left parenthesis, 1, right parenthesis, equals, 0, point, 529, times, 10, start superscript,
minus, 10, end superscript, start text, m, end text
An atom of lithium shown using the planetary model. The electrons are in circular orbits around
the nucleus. Image credit: planetary atomic model from Wikimedia Commons, CC-BY-SA 3.0
By keeping the electrons in circular, quantized orbits around the positively-charged nucleus,
Bohr was able to calculate the energy of an electron in the nnnnth energy level of hydrogen:
E(n)=−1n2⋅13.6 eVE(n)=-\dfrac{1}{n^2} \cdot 13.6\,\text{eV}E(n)=−n21⋅13.6eVE, left
parenthesis, n, right parenthesis, equals, minus, start fraction, 1, divided by, n, squared, end
fraction, dot, 13, point, 6, start text, e, V, end text, where the lowest possible energy or ground
state energy of a hydrogen electron—E(1)E(1)E(1)E, left parenthesis, 1, right parenthesis—is
−13.6 eV-13.6\,\text{eV}−13.6eVminus, 13, point, 6, start text, e, V, end text.
Note that the energy is always going to be a negative number, and the ground state, n=1n=1n=1n,
equals, 1, has the most negative value. This is because the energy of an electron in orbit is
relative to the energy of an electron that has been completely separated from its nucleus,
n=∞n=\inftyn=∞n, equals, infinity, which is defined to have an energy of 0 eV0\,\text{eV}0eV0,
start text, e, V, end text. Since an electron in orbit around the nucleus is more stable than an
electron that is infinitely far away from its nucleus, the energy of an electron in orbit is always
negative.
Absorption and emission
The energy level diagram showing transitions for Balmer series, which has the n=2 energy level
as the ground state.
The Balmer series—the spectral lines in the visible region of hydrogen's emission spectrum—
corresponds to electrons relaxing from n=3-6 energy levels to the n=2 energy level.
Bohr could now precisely describe the processes of absorption and emission in terms of
electronic structure. According to Bohr's model, an electron would absorb energy in the form of
photons to get excited to a higher energy level as long as the photon's energy was equal to the
energy difference between the initial and final energy levels. After jumping to the higher energy
level—also called the excited state—the excited electron would be in a less stable position, so it
would quickly emit a photon to relax back to a lower, more stable energy level.
The energy levels and transitions between them can be illustrated using an energy level
diagram, such as the example above showing electrons relaxing back to the n=2n=2n=2n,
equals, 2 level of hydrogen. The energy of the emitted photon is equal to the difference in energy
between the two energy levels for a particular transition. The energy difference between energy
levels nhighn_{high}nhighn, start subscript, h, i, g, h, end subscript and nlown_{low}nlown,
start subscript, l, o, w, end subscript can be calculated using the equation for E(n)E(n)E(n)E, left
parenthesis, n, right parenthesis from the previous section:
ΔE=E(nhigh)−E(nlow)=(−1nhigh2⋅13.6 eV)−(−1nlow2⋅13.6 eV)=(1nlow2−1nhigh2)⋅13.6 
eV\begin{aligned} \Delta E &= E(n_{high})-E(n_{low}) \\ \\ &=\left( -\dfrac{1}
{{n_{high}}^2} \cdot 13.6\,\text{eV} \right)-\left(-\dfrac{1}{{n_{low}}^2} \cdot
13.6\,\text{eV}\right) \\ \\ &= \left(\dfrac{1}{{n_{low}}^2}-\dfrac{1}{{n_{high}}^2}\right)
\cdot 13.6\,\text{eV} \end{aligned}ΔE=E(nhigh)−E(nlow)=(−nhigh21⋅13.6eV)−(−nlow21
⋅13.6eV)=(nlow21−nhigh21)⋅13.6eV
Since we also know the relationship between the energy of a photon and its frequency from
Planck's equation, we can solve for the frequency of the emitted photon:
hν=ΔE=(1nlow2−1nhigh2)⋅13.6 eV            Set photon energy equal to energy differenceν=(1nlo
w2−1nhigh2)⋅13.6 eVh                      Solve for frequency\begin{aligned} h\nu &=\Delta E =
\left(\dfrac{1}{{n_{low}}^2}-\dfrac{1}{{n_{high}}^2}\right) \cdot 13.6\,\text{eV}
~~~~~~~~~~~~\text{Set photon energy equal to energy difference}\\ \\ \nu &= \left(\dfrac{1}
{{n_{low}}^2}-\dfrac{1}{{n_{high}}^2}\right) \cdot \dfrac{13.6\,\text{eV}}
{h}~~~~~~~~~~~~~~~~~~~~~~\text{Solve for frequency}\end{aligned}hνν=ΔE=(nlow21
−nhigh21)⋅13.6eV            Set photon energy equal to energy difference=(nlow21−nhigh
21)⋅h13.6eV                      Solve for frequency
We can also find the equation for the wavelength of the emitted electromagnetic radiation using
the relationship between the speed of light c\text ccstart text, c, end text, frequency ν\nuν\nu, and
wavelength λ\lambdaλlambda:
c=λν                                                                  Rearrange to solve for ν.cλ=ν=(1nlow2−1nhigh2)⋅
13.6 eVh              Divide both sides by c to solve for 1λ.1λ=(1nlow2−1nhigh2)⋅13.6 
eVhc\begin{aligned}\text c &=\lambda \nu
~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~\text{R
earrange to solve for }\nu . \\\\ \dfrac{\text c}{\lambda}&=\nu=\left(\dfrac{1}
{{n_{low}}^2}-\dfrac{1}{{n_{high}}^2}\right) \cdot \dfrac{13.6\,\text{eV}}
{h}~~~~~~~~~~~~~~\text{Divide both sides by c to solve for }\dfrac{1}{\lambda}.\\\\ \\\\
\dfrac{1}{\lambda} &=\left(\dfrac{1}{{n_{low}}^2}-\dfrac{1}{{n_{high}}^2}\right) \cdot
\dfrac{13.6\,\text{eV}}{h\text c} \end{aligned}cλcλ1
=λν                                                                  Rearrange to solve for ν.=ν=(nlow21−nhigh
21)⋅h13.6eV              Divide both sides by c to solve for λ1.=(nlow21−nhigh21)⋅hc13.6eV
[What about the Rydberg constant?]
Thus, we can see that the frequency—and wavelength—of the emitted photon depends on the
energies of the initial and final shells of an electron in hydrogen.

What have we learned since Bohr proposed his model of

hydrogen?
The Bohr model worked beautifully for explaining the hydrogen atom and other single electron
systems such as He+\text{He}^+He+start text, H, e, end text, start superscript, plus, end
superscript. Unfortunately, it did not do as well when applied to the spectra of more complex
atoms. Furthermore, the Bohr model had no way of explaining why some lines are more intense
than others or why some spectral lines split into multiple lines in the presence of a magnetic field
—the Zeeman effect.
In the following decades, work by scientists such as Erwin Schrödinger showed that electrons
can be thought of as behaving like waves and behaving as particles. This means that it is not
possible to know both a given electron’s position in space and its velocity at the same time, a
concept that is more precisely stated in Heisenberg's uncertainty principle. The uncertainty
principle contradicts Bohr’s idea of electrons existing in specific orbits with a known velocity
and radius. Instead, we can only calculate probabilities of finding electrons in a particular region
of space around the nucleus.
The modern quantum mechanical model may sound like a huge leap from the Bohr model, but
the key idea is the same: classical physics is not sufficient to explain all phenomena on an atomic
level. Bohr was the first to recognize this by incorporating the idea of quantization into the
electronic structure of the hydrogen atom, and he was able to thereby explain the emission
spectra of hydrogen as well as other one-electron systems.