Electron Shell - Wikipedia

In 1913, Niels Bohr proposed a model of the atom, giving the arrangement of electrons in their sequential orbits. At that time, Bohr allowed the capacity of the inner orbit of the atom to increase to eight electrons as the atoms got larger, and "in the scheme given below the number of electrons in this [outer] ring is arbitrary put equal to the normal valency of the corresponding element". Using these and other constraints, he proposed configurations that are in accord with those now known only for the first six elements. "From the above we are led to the following possible scheme for the arrangement of the electrons in light atoms:"[3][4]

Bohr's 1913 proposed configurations

Element	Electrons per shell	Element	Electrons per shell	Element	Electrons per shell
1	1	9	4, 4, 1	17	8, 4, 4, 1
2	2	10	8, 2	18	8, 8, 2
3	2, 1	11	8, 2, 1	19	8, 8, 2, 1
4	2, 2	12	8, 2, 2	20	8, 8, 2, 2
5	2, 3	13	8, 2, 3	21	8, 8, 2, 3
6	2, 4	14	8, 2, 4	22	8, 8, 2, 4
7	4, 3	15	8, 4, 3	23	8, 8, 4, 3
8	4, 2, 2	16	8, 4, 2, 2	24	8, 8, 4, 2, 2

The shell terminology comes from Arnold Sommerfeld's modification of the 1913 Bohr model. During this period Bohr was working with Walther Kossel, whose papers in 1914 and in 1916 called the orbits "shells".[5][6] Sommerfeld retained Bohr's planetary model, but added mildly elliptical orbits (characterized by additional quantum numbers ℓ and m) to explain the fine spectroscopic structure of some elements.[7] The multiple electrons with the same principal quantum number (n) had close orbits that formed a "shell" of positive thickness instead of the circular orbit of Bohr's model which orbits called "rings" were described by a plane.[8]

The existence of electron shells was first observed experimentally in Charles Barkla's and Henry Moseley's X-ray absorption studies. Moseley's work did not directly concern the study of electron shells, because he was trying to prove that the periodic table was not arranged by weight, but by the charge of the protons in the nucleus.[9] However, because the number of electrons in an electrically neutral atom equals the number of protons, this work was extremely important to Niels Bohr who mentioned Moseley's work several times in his 1962 interview.[10] Moseley was part of Rutherford's group, as was Niels Bohr. Moseley measured the frequencies of X-rays emitted by every element between calcium and zinc and found that the frequencies became greater as the elements got heavier. This led to the theory that electrons were emitting X-rays when they were shifted to lower shells.[11] This led to the conclusion that the electrons were in Kossel's shells with a definite limit per shell, labeling them with the letters K, L, M, N, O, P, and Q.[4][12] The origin of this terminology was alphabetic. Barkla, who worked independently from Moseley as an X-ray spectrometry experimentalist, first noticed two distinct types of scattering from shooting X-rays at elements in 1909 and named them "A" and "B". Barkla described these two types of X-ray diffraction: the first was unconnected with the type of material used in the experiment and could be polarized. The second diffraction beam he called "fluorescent" because it depended on the irradiated material.[13] It was not known what these lines meant at the time, but in 1911 Barkla decided there might be scattering lines previous to "A", so he began at "K".[14] However, later experiments indicated that the K absorption lines are produced by the innermost electrons. These letters were later found to correspond to the n values 1, 2, 3, etc. that were used in the Bohr model. They are used in the spectroscopic Siegbahn notation.

The work of assigning electrons to shells was continued from 1913 to 1925 by many chemists and a few physicists. Niels Bohr was one of the few physicists who followed the chemist's work[15] of defining the periodic table, while Arnold Sommerfeld worked more on trying to make a relativistic working model of the atom that would explain the fine structure of the spectra from a classical orbital physics standpoint through the Atombau approach.[4] Einstein and Rutherford, who did not follow chemistry, were unaware of the chemists who were developing electron shell theories of the periodic table from a chemistry point of view, such as Irving Langmuir, Charles Bury, J.J. Thomson, and Gilbert Lewis, who all introduced corrections to Bohr's model such as a maximum of two electrons in the first shell, eight in the next and so on, and were responsible for explaining valency in the outer electron shells, and the building up of atoms by adding electrons to the outer shells.[16][4] So when Bohr outlined his electron shell atomic theory in 1922, there was no mathematical formula for the theory. So Rutherford said he was hard put "to form an idea of how you arrive at your conclusions".[17][18] Einstein said of Bohr's 1922 paper that his "electron-shells of the atoms together with their significance for chemistry appeared to me like a miracle – and appears to me as a miracle even today".[19] Arnold Sommerfeld, who had followed the Atombau structure of electrons instead of Bohr who was familiar with the chemists' views of electron structure, spoke of Bohr's 1921 lecture and 1922 article on the shell model as "the greatest advance in atomic structure since 1913".[4][20][17] However, the electron shell development of Niels Bohr was basically the same theory as that of the chemist Charles Rugeley Bury in his 1921 paper.[21][4][22]

As work continued on the electron shell structure of the Sommerfeld-Bohr Model, Sommerfeld had introduced three "quantum numbers n, k, and m, that described the size of the orbit, the shape of the orbit, and the direction in which the orbit was pointing."[23] Because we use k for the Boltzmann constant, the azimuthal quantum number was changed to ℓ. When the modern quantum mechanics theory was put forward based on Heisenberg's matrix mechanics and Schrödinger's wave equation, these quantum numbers were kept in the current quantum theory but were changed to n being the principal quantum number, and m being the magnetic quantum number.

However, the final form of the electron shell model still in use today for the number of electrons in shells was discovered in 1923 by Edmund Stoner, who introduced the principle that the nth shell was described by 2(n2). Seeing this in 1925, Wolfgang Pauli added a fourth quantum number, "spin", during the old quantum theory period of the Sommerfeld-Bohr Solar System atom to complete the modern electron shell theory.[4]