Bohr model

Bohr model showing maximum electrons per shell with shells labeled in X-ray notation

In the early 20th century, experiments by Ernest Rutherford established that atoms consisted of a diffuse cloud of negatively charged electrons surrounding a small, dense, positively charged nucleus.[2] Given this experimental data, Rutherford naturally considered a planetary model of the atom, the Rutherford model of 1911. This had electrons orbiting a solar nucleus, but involved a technical difficulty: the laws of classical mechanics (i.e. the Larmor formula) predict that the electron will release electromagnetic radiation while orbiting a nucleus. Because the electron would lose energy, it would rapidly spiral inwards, collapsing into the nucleus on a timescale of around 16 picoseconds.[3] This atom model is disastrous because it predicts that all atoms are unstable.[4] Also, as the electron spirals inward, the emission would rapidly increase in frequency as the orbit got smaller and faster. This would cause a continuous stream of electromagnetic radiation. However, late 19th-century experiments with electric discharges had shown that atoms will only emit light (that is, electromagnetic radiation) at certain discrete frequencies.

To overcome the problems of Rutherford's atom, in 1913 Niels Bohr put forth three postulates that sum up most of his model:

1. The electron is able to revolve in certain stable orbits around the nucleus without radiating any energy, contrary to what classical electromagnetism suggests. These stable orbits are called stationary orbits and are attained at certain discrete distances from the nucleus. The electron cannot have any other orbit in between the discrete ones.
2. The stationary orbits are attained at distances for which the angular momentum of the revolving electron is an integer multiple of the reduced Planck constant: ${\displaystyle m_{\mathrm {e} }vr=n\hbar }$, where n = 1, 2, 3, ... is called the principal quantum number, and ħ = h/2π. The lowest value of n is 1; this gives the smallest possible orbital radius of 0.0529 nm known as the Bohr radius. Once an electron is in this lowest orbit, it can get no closer to the proton. Starting from the angular momentum quantum rule, Bohr[2] was able to calculate the energies of the allowed orbits of the hydrogen atom and other hydrogen-like atoms and ions. These orbits are associated with definite energies and are also called energy shells or energy levels. In these orbits, the electron's acceleration does not result in radiation and energy loss. The Bohr model of an atom was based upon Planck's quantum theory of radiation.
3. Electrons can only gain and lose energy by jumping from one allowed orbit to another, absorbing or emitting electromagnetic radiation with a frequency ν determined by the energy difference of the levels according to the Planck relation: ${\displaystyle \Delta E=E_{2}-E_{1}=h\nu }$, where h is Planck's constant.

Other points are:

1. Like Einstein's theory of the photoelectric effect, Bohr's formula assumes that during a quantum jump a discrete amount of energy is radiated. However, unlike Einstein, Bohr stuck to the classical Maxwell theory of the electromagnetic field. Quantization of the electromagnetic field was explained by the discreteness of the atomic energy levels; Bohr did not believe in the existence of photons.[5][6]
2. According to the Maxwell theory the frequency ν of classical radiation is equal to the rotation frequency ν_rot of the electron in its orbit, with harmonics at integer multiples of this frequency. This result is obtained from the Bohr model for jumps between energy levels E_n and E_n−k when k is much smaller than n. These jumps reproduce the frequency of the k-th harmonic of orbit n. For sufficiently large values of n (so-called Rydberg states), the two orbits involved in the emission process have nearly the same rotation frequency, so that the classical orbital frequency is not ambiguous. But for small n (or large k), the radiation frequency has no unambiguous classical interpretation. This marks the birth of the correspondence principle, requiring quantum theory to agree with the classical theory only in the limit of large quantum numbers.
3. The Bohr–Kramers–Slater theory (BKS theory) is a failed attempt to extend the Bohr model, which violates the conservation of energy and momentum in quantum jumps, with the conservation laws only holding on average.

Bohr's condition, that the angular momentum is an integer multiple of ħ was later reinterpreted in 1924 by de Broglie as a standing wave condition: the electron is described by a wave and a whole number of wavelengths must fit along the circumference of the electron's orbit:

${\displaystyle n\lambda =2\pi r.}$

According to de Broglie hypothesis, matter particles such as the electron behaves as waves. So, de Broglie wavelength of electron is:

${\displaystyle \lambda ={\frac {h}{mv}}}$.

which implies that,

${\displaystyle {\frac {nh}{mv}}=2\pi r}$

or

${\displaystyle {\frac {nh}{2\pi }}=mvr}$

where ${\displaystyle mvr}$ is the angular momentum ${\displaystyle \ell }$ of the orbiting electron.

${\displaystyle \ell ={\frac {nh}{2\pi }}}$

which is the Bohr's second postulate.

Bohr described angular momentum of the electron orbit as 1/2h while de Broglie's wavelength of λ = h/p described h divided by the electron momentum. In 1913, however, Bohr justified his rule by appealing to the correspondence principle, without providing any sort of wave interpretation. In 1913, the wave behavior of matter particles such as the electron was not suspected.

In 1925, a new kind of mechanics was proposed, quantum mechanics, in which Bohr's model of electrons traveling in quantized orbits was extended into a more accurate model of electron motion. The new theory was proposed by Werner Heisenberg. Another form of the same theory, wave mechanics, was discovered by the Austrian physicist Erwin Schrödinger independently, and by different reasoning. Schrödinger employed de Broglie's matter waves, but sought wave solutions of a three-dimensional wave equation describing electrons that were constrained to move about the nucleus of a hydrogen-like atom, by being trapped by the potential of the positive nuclear charge.

Models depicting electron energy levels in hydrogen, helium, lithium, and neon

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.

${\displaystyle {m_{\mathrm {e} }v^{2} \over r}={Zk_{\mathrm {e} }e^{2} \over r^{2}}}$

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:

${\displaystyle v={\sqrt {Zk_{\mathrm {e} }e^{2} \over m_{\mathrm {e} }r}}.}$

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

${\displaystyle E=-{1 \over 2}m_{\mathrm {e} }v^{2}}$

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_evr is an integer multiple of ħ:

${\displaystyle m_{\mathrm {e} }vr=n\hbar }$

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:

${\displaystyle E=E_{i}-E_{f}=R_{\mathrm {E} }\left({\frac {1}{n_{f}^{2}}}-{\frac {1}{n_{i}^{2}}}\right)\,}$

where n_f is the final energy level, and n_i is the initial energy level.

Since the energy of a photon is

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

the wavelength of the photon given off is given by

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

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 (n_f =1), Balmer (n_f =2), and Paschen (n_f =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.

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.

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."[9]

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,

${\displaystyle E=h\nu =E_{i}-E_{f}=R_{\mathrm {E} }(Z-1)^{2}\left({\frac {1}{1^{2}}}-{\frac {1}{2^{2}}}\right)\,}$

or

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

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,[10] 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.

The Bohr model gives an incorrect value L=ħ for the ground state orbital angular momentum: The angular momentum in the true ground state is known to be zero from experiment.[11] Although mental pictures fail somewhat at these levels of scale, an electron in the lowest modern "orbital" with no orbital momentum, may be thought of as not to rotate "around" the nucleus at all, but merely to go tightly around it in an ellipse with zero area (this may be pictured as "back and forth", without striking or interacting with the nucleus). This is only reproduced in a more sophisticated semiclassical treatment like Sommerfeld's. Still, even the most sophisticated semiclassical model fails to explain the fact that the lowest energy state is spherically symmetric – it doesn't point in any particular direction.

Nevertheless, in the modern fully quantum treatment in phase space, the proper deformation (careful full extension) of the semi-classical result adjusts the angular momentum value to the correct effective one. As a consequence, the physical ground state expression is obtained through a shift of the vanishing quantum angular momentum expression, which corresponds to spherical symmetry.

In modern quantum mechanics, the electron in hydrogen is a spherical cloud of probability that grows denser near the nucleus. The rate-constant of probability-decay in hydrogen is equal to the inverse of the Bohr radius, but since Bohr worked with circular orbits, not zero area ellipses, the fact that these two numbers exactly agree is considered a "coincidence". (However, many such coincidental agreements are found between the semiclassical vs. full quantum mechanical treatment of the atom; these include identical energy levels in the hydrogen atom and the derivation of a fine structure constant, which arises from the relativistic Bohr–Sommerfeld model (see below) and which happens to be equal to an entirely different concept, in full modern quantum mechanics).

The Bohr model also has difficulty with, or else fails to explain:

• Much of the spectra of larger atoms. At best, it can make predictions about the K-alpha and some L-alpha X-ray emission spectra for larger atoms, if two additional ad hoc assumptions are made. Emission spectra for atoms with a single outer-shell electron (atoms in the lithium group) can also be approximately predicted. Also, if the empiric electron–nuclear screening factors for many atoms are known, many other spectral lines can be deduced from the information, in similar atoms of differing elements, via the Ritz–Rydberg combination principles (see Rydberg formula). All these techniques essentially make use of Bohr's Newtonian energy-potential picture of the atom.
• the relative intensities of spectral lines; although in some simple cases, Bohr's formula or modifications of it, was able to provide reasonable estimates (for example, calculations by Kramers for the Stark effect).
• The existence of fine structure and hyperfine structure in spectral lines, which are known to be due to a variety of relativistic and subtle effects, as well as complications from electron spin.
• The Zeeman effect – changes in spectral lines due to external magnetic fields; these are also due to more complicated quantum principles interacting with electron spin and orbital magnetic fields.
• The model also violates the uncertainty principle in that it considers electrons to have known orbits and locations, two things which cannot be measured simultaneously.
• Doublets and triplets appear in the spectra of some atoms as very close pairs of lines. Bohr's model cannot say why some energy levels should be very close together.
• Multi-electron atoms do not have energy levels predicted by the model. It does not work for (neutral) helium.

Elliptical orbits with the same energy and quantized angular momentum

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.[1] This model supplemented the quantized angular momentum condition of the Bohr model with an additional radial quantization condition, the Wilson–Sommerfeld quantization condition.[12][13]

${\displaystyle \int _{0}^{T}p_{r}\,dq_{r}=nh\,}$

where p_r 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".[14]

Niels Bohr proposed a model of the atom and a model of the chemical bond. According to his model for a diatomic molecule, the electrons of the atoms of the molecule form a rotating ring whose plane is perpendicular to the axis of the molecule and equidistant from the atomic nuclei. The dynamic equilibrium of the molecular system is achieved through the balance of forces between the forces of attraction of nuclei to the plane of the ring of electrons and the forces of mutual repulsion of the nuclei. The Bohr model of the chemical bond took into account the Coulomb repulsion – the electrons in the ring are at the maximum distance from each other.[15][16]

• Linus Carl Pauling (1970). "Chapter 5-1". General Chemistry (3rd ed.). San Francisco: W.H. Freeman & Co.
  • Reprint: Linus Pauling (1988). General Chemistry. New York: Dover Publications. ISBN 0-486-65622-5.
• George Gamow (1985). "Chapter 2". Thirty Years That Shook Physics. Dover Publications.
• Walter J. Lehmann (1972). "Chapter 18". Atomic and Molecular Structure: the development of our concepts. John Wiley and Sons. ISBN 0-471-52440-9.
• Paul Tipler and Ralph Llewellyn (2002). Modern Physics (4th ed.). W. H. Freeman. ISBN 0-7167-4345-0.
• Klaus Hentschel: Elektronenbahnen, Quantensprünge und Spektren, in: Charlotte Bigg & Jochen Hennig (eds.) Atombilder. Ikonografien des Atoms in Wissenschaft und Öffentlichkeit des 20. Jahrhunderts, Göttingen: Wallstein-Verlag 2009, pp. 51–61
• Steven and Susan Zumdahl (2010). "Chapter 7.4". Chemistry (8th ed.). Brooks/Cole. ISBN 978-0-495-82992-8.
• Helge Kragh (2011). "Conceptual objections to the Bohr atomic theory — do electrons have a "free will" ?". European Physical Journal H. 36 (3): 327–352. Bibcode:2011EPJH...36..327K. doi:10.1140/epjh/e2011-20031-x. S2CID 120859582.

• Standing waves in Bohr’s atomic model An interactive simulation to intuitively explain the quantization condition of standing waves in Bohr's atomic mode

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