Bohr model

In atomic physics, the **Bohr model** or **Rutherford–Bohr model**, presented by Niels Bohr and Ernest Rutherford in 1913, is a system consisting of a small, dense nucleus surrounded by orbiting electrons—similar to the structure of the Solar System, but with attraction provided by electrostatic forces in place of gravity. After the cubical model (1902), the plum pudding model (1904), the Saturnian model (1904), and the Rutherford model (1911) came the *Rutherford–Bohr model* or just *Bohr model* for short (1913). The improvement over the 1911 Rutherford model mainly concerned the new quantum physical interpretation.

The model's key success lay in explaining the Rydberg formula for the spectral emission lines of atomic hydrogen. While the Rydberg formula had been known experimentally, it did not gain a theoretical underpinning until the Bohr model was introduced. Not only did the Bohr model explain the reasons for the structure of the Rydberg formula, it also provided a justification for the fundamental physical constants that make up the formula's empirical results.

The Bohr model is a relatively primitive model of the hydrogen atom, compared to the *valence shell atom* model. As a theory, it can be derived as a first-order approximation of the hydrogen atom using the broader and much more accurate quantum mechanics and thus may be considered to be an obsolete scientific theory. However, because of its simplicity, and its correct results for selected systems (see below for application), the Bohr model is still commonly taught to introduce students to quantum mechanics or energy level diagrams before moving on to the more accurate, but more complex, valence shell atom. A related model was originally proposed by Arthur Erich Haas in 1910 but was rejected. The quantum theory of the period between Planck's discovery of the quantum (1900) and the advent of a mature quantum mechanics (1925) is often referred to as the old quantum theory.

## Electron energy levels

The Bohr model gives almost exact results only for a system where two charged points orbit each other at speeds much less than that of light. This not only involves one-electron systems such as the hydrogen atom, singly ionized helium, and doubly ionized lithium, but it includes positronium and Rydberg states of any atom where one electron is far away from everything else. It can be used for K-line X-ray transition calculations if other assumptions are added (see Moseley's law below). In high energy physics, it can be used to calculate the masses of heavy quark mesons.

Calculation of the orbits requires two assumptions.

* **Classical mechanics**

The electron is held in a circular orbit by electrostatic attraction. The centripetal force is equal to the Coulomb force.

m

e

v
2

r

=

Z

k

e

e
2

r
2

{\displaystyle {m\_\mathrm{e} v^2\over r} = {Zk\_\mathrm{e} e^2 \over r^2} }

where *m*e is the electron's mass, *e* is the charge of the electron, *k*e is the Coulomb constant and *Z* is the atom's atomic number. It is assumed here that the mass of the nucleus is much larger than the electron mass (which is a good assumption). This equation determines the electron's speed at any radius:

# v

Z

k

e

e
2

m

e

r

.

{\displaystyle v = \sqrt{ Zk\_\mathrm{e} e^2 \over m\_\mathrm{e} r}. }

It also determines the electron's total energy at any radius:

# E
−

1
2

m

e

v
2

{\displaystyle E= -{1\over 2} m\_\mathrm{e} v^2
 }

The total energy is negative and inversely proportional to *r*. This means that it takes energy to pull the orbiting electron away from the proton. For infinite values of *r*, the energy is zero, corresponding to a motionless electron infinitely far from the proton. The total energy is half the potential energy, the difference being the kinetic energy of the electron. This is also true for noncircular orbits by the virial theorem.
* **A quantum rule**

The angular momentum *L* = *m*e*vr* is an integer multiple of *ħ*:

m

e

v
# r
n
ℏ

{\displaystyle m\_\mathrm{e} v r = n \hbar }

### Derivation

The angular momentum should be an integer multiple of *ħ*,

# L

n
h

2
π

=
n
ℏ

.

{\displaystyle
L = {nh \over 2\pi} = n \hbar ~ .
}

This is how Bohr arrived at his model.

Substituting the expression for the velocity gives an equation for *r* in terms of *n*:

m

e

k

e

Z

e
2

m

e

r

# r
n
ℏ

{\displaystyle m\_{\text{e}}\sqrt{\dfrac{k\_{\text{e}}Ze^2}{m\_{\text{e}}r}}r=n\hbar }

so that the allowed orbit radius at any *n* is:

r
n

=

n
2

ℏ
2

Z

k

e

e
2

m

e

{\displaystyle r\_n = {n^2\hbar^2\over Zk\_\mathrm{e} e^2 m\_\mathrm{e}} }

The smallest possible value of *r* in the hydrogen atom (*Z* = 1) is called the Bohr radius and is equal to:

r
1

=

ℏ
2

k

e

e
2

m

e

≈
0.529177
A
n
g
s
t
r
o
m
s

{\displaystyle r\_1 = {\hbar^2 \over k\_\mathrm{e} e^2 m\_\mathrm{e}} \approx 0.529177 Angstroms }

The velocity of the electron in the ground shell of hydrogen is c/137.036.
The frequency of its orbit is 1.23559 \* 1020 Hz which corresponds to 27.21 eV which is twice the kinetic energy of the electron.
The energy of the *n*-th level for any atom is determined by the radius and quantum number:

# E
−

Z

k

e

e
2

2

r
n

=
−

Z
2

(

k

e

e
2

)
2

m

e

2

ℏ
2

n
2

≈

−
13.6

Z
2

n
2

e
V

{\displaystyle E = -{Zk\_\mathrm{e} e^2 \over 2r\_n } = - { Z^2(k\_\mathrm{e} e^2)^2 m\_\mathrm{e} \over 2\hbar^2 n^2} \approx {-13.6Z^2 \over n^2}\mathrm{eV} }

An electron in the lowest energy level of hydrogen (*n* = 1) therefore has about 13.6 eV less energy than a motionless electron infinitely far from the nucleus. The next energy level (*n* = 2) is −3.4 eV. The third (*n* = 3) is −1.51 eV, and so on. For larger values of *n*, these are also the binding energies of a highly excited atom with one electron in a large circular orbit around the rest of the atom. The hydrogen formula also coincides with the Wallis product.

The combination of natural constants in the energy formula is called the Rydberg energy (*R*E):

R

E

=

(

k

e

e
2

)
2

m

e

2

ℏ
2

{\displaystyle R\_\mathrm{E} = { (k\_\mathrm{e} e^2)^2 m\_\mathrm{e} \over 2 \hbar^2} }

This expression is clarified by interpreting it in combinations that form more natural units:

m

e

c
2

{\displaystyle \, m\_\mathrm{e} c^2 }

 is the rest mass energy of the electron (511 keV)

k

e

e
2

ℏ
c

=
α
≈

1
137

{\displaystyle \, {k\_\mathrm{e} e^2 \over \hbar c} = \alpha \approx {1\over 137} }

 is the fine structure constant

R

E

=

1
2

(

m

e

c
2

)

α
2

{\displaystyle \, R\_\mathrm{E} = {1\over 2} (m\_\mathrm{e} c^2) \alpha^2}

Since this derivation is with the assumption that the nucleus is orbited by one electron, we can generalize this result by letting the nucleus have a charge *q* = *Ze*, where *Z* is the atomic number. This will now give us energy levels for hydrogenic (hydrogen-like) atoms, which can serve as a rough order-of-magnitude approximation of the actual energy levels. So for nuclei with *Z* protons, the energy levels are (to a rough approximation):

E
n

=
−

Z
2

R

E

n
2

{\displaystyle E\_n = -{Z^2 R\_\mathrm{E} \over n^2} }

The actual energy levels cannot be solved analytically for more than one electron (see *n*-body problem) because the electrons are not only affected by the nucleus but also interact with each other via the Coulomb Force.

When *Z* = 1/*α* (*Z* ≈ 137), the motion becomes highly relativistic, and *Z*2 cancels the *α*2 in *R*; the orbit energy begins to be comparable to rest energy. Sufficiently large nuclei, if they were stable, would reduce their charge by creating a bound electron from the vacuum, ejecting the positron to infinity. This is the theoretical phenomenon of electromagnetic charge screening which predicts a maximum nuclear charge. Emission of such positrons has been observed in the collisions of heavy ions to create temporary super-heavy nuclei.

The Bohr formula properly uses the reduced mass of electron and proton in all situations, instead of the mass of the electron,

m
red

=

m

e

m

p

m

e

m

p

=

m

e

1

1

m

e

/

m

p

.

{\displaystyle m\_\text{red} = \frac{m\_\mathrm{e} m\_\mathrm{p}}{m\_\mathrm{e} + m\_\mathrm{p}} = m\_\mathrm{e} ~\frac{1}{1+m\_\mathrm{e}/m\_\mathrm{p}}~.}

However, these numbers are very nearly the same, due to the much larger mass of the proton, about 1836.1 times the mass of the electron, so that the reduced mass in the system is the mass of the electron multiplied by the constant 1836.1/(1+1836.1) = 0.99946. This fact was historically important in convincing Rutherford of the importance of Bohr's model, for it explained the fact that the frequencies of lines in the spectra for singly ionized helium do not differ from those of hydrogen by a factor of exactly 4, but rather by 4 times the ratio of the reduced mass for the hydrogen vs. the helium systems, which was much closer to the experimental ratio than exactly 4.

For positronium, the formula uses the reduced mass also, but in this case, it is exactly the electron mass divided by 2. For any value of the radius, the electron and the positron are each moving at half the speed around their common center of mass, and each has only one fourth the kinetic energy. The total kinetic energy is half what it would be for a single electron moving around a heavy nucleus.

E
n

=

R

E

2

n
2

{\displaystyle E\_n = {R\_\mathrm{E} \over 2 n^2 } ~~~~~~ }

 (positronium)
## Rydberg formula

Main articles: Rydberg formula
The Rydberg formula, which was known empirically before Bohr's formula, is seen in Bohr's theory as describing the energies of transitions or quantum jumps between orbital energy levels. Bohr's formula gives the numerical value of the already-known and measured the Rydberg constant, but in terms of more fundamental constants of nature, including the electron's charge and the Planck constant.

When the electron gets moved from its original energy level to a higher one, it then jumps back each level until it comes to the original position, which results in a photon being emitted. Using the derived formula for the different energy levels of hydrogen one may determine the wavelengths of light that a hydrogen atom can emit.

The energy of a photon emitted by a hydrogen atom is given by the difference of two hydrogen energy levels:

# E

E
i

−

E
f

=

R

E

(

1

n

f

2

−

1

n
i
2

)

{\displaystyle E=E\_i-E\_f=R\_\mathrm{E} \left( \frac{1}{n\_{f}^2} - \frac{1}{n\_i^2} \right) \,}

where *n**f* is the final energy level, and *n**i* is the initial energy level.

Since the energy of a photon is

# E

h
c

λ

,

{\displaystyle E=\frac{hc}{\lambda}, \,}

the wavelength of the photon given off is given by

1
λ

=
R

(

1

n

f

2

−

1

n

i

2

)

.

{\displaystyle \frac{1}{\lambda}=R \left( \frac{1}{n\_{f}^2} - \frac{1}{n\_{i}^2} \right). \,}

This is known as the Rydberg formula, and the Rydberg constant *R* is *R*E/*hc*, or *R*E/2π in natural units. This formula was known in the nineteenth century to scientists studying spectroscopy, but there was no theoretical explanation for this form or a theoretical prediction for the value of *R*, until Bohr. In fact, Bohr's derivation of the Rydberg constant, as well as the concomitant agreement of Bohr's formula with experimentally observed spectral lines of the Lyman (*nf* =1), Balmer (*nf* =2), and Paschen (*nf* =3) series, and successful theoretical prediction of other lines not yet observed, was one reason that his model was immediately accepted.

To apply to atoms with more than one electron, the Rydberg formula can be modified by replacing *Z* with *Z* − *b* or *n* with *n* − *b* where *b* is constant representing a screening effect due to the inner-shell and other electrons (see Electron shell and the later discussion of the "Shell Model of the Atom" below). This was established empirically before Bohr presented his model.

## Shell model (heavier atoms)

Main articles: Electron shell
Bohr extended the model of hydrogen to give an approximate model for heavier atoms. This gave a physical picture that reproduced many known atomic properties for the first time.

Heavier atoms have more protons in the nucleus, and more electrons to cancel the charge. Bohr's idea was that each discrete orbit could only hold a certain number of electrons. After that orbit is full, the next level would have to be used. This gives the atom a shell structure, in which each shell corresponds to a Bohr orbit.

This model is even more approximate than the model of hydrogen, because it treats the electrons in each shell as non-interacting. But the repulsions of electrons are taken into account somewhat by the phenomenon of screening. The electrons in outer orbits do not only orbit the nucleus, but they also move around the inner electrons, so the effective charge Z that they feel is reduced by the number of the electrons in the inner orbit.

For example, the lithium atom has two electrons in the lowest 1s orbit, and these orbit at *Z* = 2. Each one sees the nuclear charge of *Z* = 3 minus the screening effect of the other, which crudely reduces the nuclear charge by 1 unit. This means that the innermost electrons orbit at approximately 1/2 the Bohr radius. The outermost electron in lithium orbits at roughly the Bohr radius, since the two inner electrons reduce the nuclear charge by 2. This outer electron should be at nearly one Bohr radius from the nucleus. Because the electrons strongly repel each other, the effective charge description is very approximate; the effective charge *Z* doesn't usually come out to be an integer. But Moseley's law experimentally probes the innermost pair of electrons, and shows that they do see a nuclear charge of approximately *Z* − 1, while the outermost electron in an atom or ion with only one electron in the outermost shell orbits a core with effective charge *Z* − *k* where *k* is the total number of electrons in the inner shells.

The shell model was able to qualitatively explain many of the mysterious properties of atoms which became codified in the late 19th century in the periodic table of the elements. One property was the size of atoms, which could be determined approximately by measuring the viscosity of gases and density of pure crystalline solids. Atoms tend to get smaller toward the right in the periodic table, and become much larger at the next line of the table. Atoms to the right of the table tend to gain electrons, while atoms to the left tend to lose them. Every element on the last column of the table is chemically inert (noble gas).

In the shell model, this phenomenon is explained by shell-filling. Successive atoms become smaller because they are filling orbits of the same size, until the orbit is full, at which point the next atom in the table has a loosely bound outer electron, causing it to expand. The first Bohr orbit is filled when it has two electrons, which explains why helium is inert. The second orbit allows eight electrons, and when it is full the atom is neon, again inert. The third orbital contains eight again, except that in the more correct Sommerfeld treatment (reproduced in modern quantum mechanics) there are extra "d" electrons. The third orbit may hold an extra 10 d electrons, but these positions are not filled until a few more orbitals from the next level are filled (filling the n=3 d orbitals produces the 10 transition elements). The irregular filling pattern is an effect of interactions between electrons, which are not taken into account in either the Bohr or Sommerfeld models and which are difficult to calculate even in the modern treatment.

## Moseley's law and calculation (K-alpha X-ray emission lines)

Niels Bohr said in 1962, "You see actually the Rutherford work was not taken seriously. We cannot understand today, but it was not taken seriously at all. There was no mention of it any place. The great change came from Moseley."

In 1913, Henry Moseley found an empirical relationship between the strongest X-ray line emitted by atoms under electron bombardment (then known as the K-alpha line), and their atomic number *Z*. Moseley's empiric formula was found to be derivable from Rydberg and Bohr's formula (Moseley actually mentions only Ernest Rutherford and Antonius Van den Broek in terms of models). The two additional assumptions that **[1]** this X-ray line came from a transition between energy levels with quantum numbers 1 and 2, and **[2]**, that the atomic number *Z* when used in the formula for atoms heavier than hydrogen, should be diminished by 1, to (*Z* − 1)2.

Moseley wrote to Bohr, puzzled about his results, but Bohr was not able to help. At that time, he thought that the postulated innermost "K" shell of electrons should have at least four electrons, not the two which would have neatly explained the result. So Moseley published his results without a theoretical explanation.

Later, people realized that the effect was caused by charge screening, with an inner shell containing only 2 electrons. In the experiment, one of the innermost electrons in the atom is knocked out, leaving a vacancy in the lowest Bohr orbit, which contains a single remaining electron. This vacancy is then filled by an electron from the next orbit, which has n=2. But the n=2 electrons see an effective charge of *Z* − 1, which is the value appropriate for the charge of the nucleus, when a single electron remains in the lowest Bohr orbit to screen the nuclear charge +*Z*, and lower it by −1 (due to the electron's negative charge screening the nuclear positive charge). The energy gained by an electron dropping from the second shell to the first gives Moseley's law for K-alpha lines,

# ν

E
i

−

E
f

=

R

E

(
Z
−
1

)
2

(

1

1
2

−

1

2
2

)

{\displaystyle E= h\nu = E\_i-E\_f=R\_\mathrm{E} (Z-1)^2 \left( \frac{1}{1^2} - \frac{1}{2^2} \right) \,}

or

# ν

R

v

(

3
4

)

(
Z
−
1

)
2

=
(
2.46
×

10

15

Hz
)
(
Z
−
1

)
2

.

{\displaystyle f = \nu = R\_\mathrm{v} \left( \frac{3}{4}\right) (Z-1)^2 = (2.46 \times 10^{15} \operatorname{Hz})(Z-1)^2.}

Here, ***R*v** = ***R*E/*h*** is the Rydberg constant, in terms of frequency equal to 3.28 x 1015 Hz. For values of Z between 11 and 31 this latter relationship had been empirically derived by Moseley, in a simple (linear) plot of the square root of X-ray frequency against atomic number (however, for silver, Z = 47, the experimentally obtained screening term should be replaced by 0.4). Notwithstanding its restricted validity, Moseley's law not only established the objective meaning of atomic number, but as Bohr noted, it also did more than the Rydberg derivation to establish the validity of the Rutherford/Van den Broek/Bohr nuclear model of the atom, with atomic number (place on the periodic table) standing for whole units of nuclear charge.

The K-alpha line of Moseley's time is now known to be a pair of close lines, written as (**Kα1** and **Kα2**) in Siegbahn notation.

## Refinements

See also: Pauli exclusion principle
Several enhancements to the Bohr model were proposed, most notably the Sommerfeld or Bohr–Sommerfeld models, which suggested that electrons travel in elliptical orbits around a nucleus instead of the Bohr model's circular orbits. This model supplemented the quantized angular momentum condition of the Bohr model with an additional radial quantization condition, the Wilson–Sommerfeld quantization condition.

∫
0
T

p
r

d

q
r

=
n
h

{\displaystyle
\int\_0^T p\_r \,dq\_r = n h
\,}

where *pr* is the radial momentum canonically conjugate to the coordinate *q* which is the radial position and *T* is one full orbital period. The integral is the action of action-angle coordinates. This condition, suggested by the correspondence principle, is the only one possible, since the quantum numbers are adiabatic invariants.

The Bohr–Sommerfeld model was fundamentally inconsistent and led to many paradoxes. The magnetic quantum number measured the tilt of the orbital plane relative to the *xy*-plane, and it could only take a few discrete values. This contradicted the obvious fact that an atom could be turned this way and that relative to the coordinates without restriction. The Sommerfeld quantization can be performed in different canonical coordinates and sometimes gives different answers. The incorporation of radiation corrections was difficult, because it required finding action-angle coordinates for a combined radiation/atom system, which is difficult when the radiation is allowed to escape. The whole theory did not extend to non-integrable motions, which meant that many systems could not be treated even in principle. In the end, the model was replaced by the modern quantum mechanical treatment of the hydrogen atom, which was first given by Wolfgang Pauli in 1925, using Heisenberg's matrix mechanics. The current picture of the hydrogen atom is based on the atomic orbitals of wave mechanics which Erwin Schrödinger developed in 1926.

However, this is not to say that the Bohr-Sommerfeld model was without its successes. Calculations based on the Bohr–Sommerfeld model were able to accurately explain a number of more complex atomic spectral effects. For example, up to first-order perturbations, the Bohr model and quantum mechanics make the same predictions for the spectral line splitting in the Stark effect. At higher-order perturbations, however, the Bohr model and quantum mechanics differ, and measurements of the Stark effect under high field strengths helped confirm the correctness of quantum mechanics over the Bohr model. The prevailing theory behind this difference lies in the shapes of the orbitals of the electrons, which vary according to the energy state of the electron.

The Bohr–Sommerfeld quantization conditions lead to questions in modern mathematics. Consistent semiclassical quantization condition requires a certain type of structure on the phase space, which places topological limitations on the types of symplectic manifolds which can be quantized. In particular, the symplectic form should be the curvature form of a connection of a Hermitian line bundle, which is called a prequantization.

Bohr also updated his model in 1922, assuming that certain numbers of electrons (for example 2, 8, and 18) correspond to stable "closed shells".

## See also

* 1913 in science
* Balmer's Constant
* The Franck–Hertz experiment provided early support for the Bohr model.Template:Nb5
* Free-fall atomic model
* The inert pair effect is adequately explained by means of the Bohr model.
* Introduction to quantum mechanics
* Theoretical and experimental justification for the Schrödinger equation