Electron shell
In atomic physics and chemistry, an electron shell refers to a group of atomic orbitals that share the same principal quantum number, n, which defines the energy level and average distance of electrons from the nucleus in an atom.[1] These shells organize the electrons surrounding the positively charged nucleus, with electrons filling lower-energy shells first according to the Aufbau principle.[2] The concept originated in the Bohr model of the atom but is now understood through quantum mechanics, where shells correspond to discrete energy states rather than fixed circular orbits.[3] Electron shells are traditionally labeled with letters starting from the innermost: K (n=1), L (n=2), M (n=3), and so on, up to the seventh shell for known elements.[4] Each shell can hold a maximum of 2n² electrons, allowing the first shell to accommodate 2 electrons, the second up to 8, the third up to 18, and higher shells even more, though outer shells in most elements are not fully occupied.[5] This capacity arises from the subshells (s, p, d, f) within each shell, each with specific orbital angular momentum quantum numbers that determine their electron-holding limits.[2] The arrangement of electrons in shells governs an atom's chemical behavior, particularly through the valence shell—the outermost shell—which contains the valence electrons responsible for bonding and reactivity.[6] Full valence shells, as in noble gases, confer stability, while incomplete ones drive elements to form ions or compounds to achieve a stable octet configuration in the valence shell.[7] This shell structure underpins the periodic table's organization, where periods correspond to the filling of successive shells, explaining trends in atomic size, ionization energy, and electronegativity across elements.[8]Fundamentals
Definition and Basic Properties
In atomic physics, electron shells represent discrete energy levels within an atom, conceptualized as concentric spherical regions surrounding the nucleus where electrons are most likely to be found according to quantum mechanical probability distributions.[2] These shells are defined by the principal quantum number n, a positive integer that specifies the shell's designation, with n = 1 for the innermost shell and increasing sequentially outward as n = 2, 3, 4, \dots.[9] The value of n indicates the shell's average distance from the nucleus and its associated energy, with higher n corresponding to larger, higher-energy shells.[10] Electron shells are conventionally labeled using spectroscopic notation: the K shell for n=1, L shell for n=2, M shell for n=3, N for n=4, and so forth. A key property is that shell radius and electron binding energy both increase with n, meaning electrons in outer shells are less tightly bound to the nucleus and require less energy to remove.[11] Consequently, the electrons occupying the outermost shell—termed valence electrons—predominantly govern an atom's chemical behavior, including its reactivity and bonding tendencies with other atoms.[4] For conceptual clarity, electron shells can be intuitively compared to the discrete orbits in a simplified planetary model of the atom, akin to planets revolving around the sun at fixed distances; this analogy, however, oversimplifies the quantum reality, where electrons do not follow definite paths but exist in probabilistic clouds.[12] Each shell is subdivided into subshells based on the orbital angular momentum quantum number.[2]Role in Atomic and Molecular Structure
Electron shells play a crucial role in determining the stability of atoms by organizing electrons into energy levels that minimize overall energy. Atoms with completely filled inner shells, such as the noble gases, exhibit exceptional stability due to their closed-shell configurations, where the valence shell is fully occupied, leading to low reactivity and high ionization energies.[13] For instance, helium achieves this stability with its two electrons filling the 1s shell completely, resulting in a configuration that resists chemical interactions under normal conditions.[14] In chemical bonding, electron shells govern how atoms interact to achieve more stable configurations, primarily through the sharing or transfer of valence electrons from the outermost shell. The octet rule describes the tendency of atoms to gain, lose, or share electrons to fill their outer shell with eight electrons, mimicking the stable noble gas arrangement and lowering potential energy.[15] This leads to ionic bonding, where electrons are transferred—as in sodium, which loses its single 3s valence electron to form Na⁺ with a neon-like configuration—creating oppositely charged ions attracted by electrostatic forces.[16] In covalent bonding, atoms share pairs of valence electrons to satisfy the octet rule, forming molecules where the shared electrons are counted toward both atoms' outer shells. The arrangement of electrons in outer shells also influences molecular structure by dictating bond angles and geometries through interactions of valence electrons. In molecular formation, these valence electrons participate in hybridization, where atomic orbitals from the outer shell combine to form hybrid orbitals that overlap effectively, enabling specific molecular shapes like the tetrahedral geometry in methane.[17] This shell-driven hybridization and repulsion among electron pairs in the valence shell determine overall molecular architecture, affecting properties such as polarity and reactivity.[18]Historical Context
Pre-Quantum Models
In the early 20th century, J.J. Thomson proposed the "plum pudding" model of the atom in 1904, envisioning it as a uniform sphere of positive charge with negatively charged electrons embedded throughout like plums in a pudding, ensuring overall electrical neutrality without any discrete shell structure.[19] This model accounted for the discovery of the electron but lacked a concept of organized electron layers, treating electrons as distributed within a diffuse positive medium.[19] Ernest Rutherford's nuclear model, introduced in 1911 based on the gold foil scattering experiments conducted by Hans Geiger and Ernest Marsden, depicted the atom as a tiny, dense, positively charged nucleus surrounded by electrons orbiting in planetary-like paths, much like planets around the sun.[20] However, this classical picture was inherently unstable, as accelerating electrons in circular orbits would, according to Maxwell's electromagnetic theory, continuously radiate energy and spiral inward toward the nucleus, leading to atomic collapse.[21] Niels Bohr addressed these issues in his 1913 model, postulating that electrons occupy discrete, quantized orbits around the nucleus—serving as precursors to modern electron shells—where they do not radiate energy while in these stable "stationary states."[22] Bohr introduced angular momentum quantization, with the electron's orbital angular momentum given by L = n \hbar, where n is a positive integer and \hbar = h / 2\pi (with h as Planck's constant), preventing continuous energy loss.[23] This framework successfully explained the discrete spectral lines of hydrogen, attributing them to electrons transitioning between quantized energy levels and emitting photons of specific wavelengths corresponding to the energy differences.[24] Despite its successes, Bohr's model had significant limitations, particularly its inability to accurately describe multi-electron atoms, where electron-electron interactions were not accounted for, leading to incorrect predictions of energy levels and spectra for elements beyond hydrogen.[25] This shortfall highlighted the need for a more comprehensive quantum mechanical treatment to incorporate wave-like electron behavior and full atomic complexity.Development of Quantum Theory
The development of quantum theory marked a pivotal shift in understanding electron behavior within atoms, building upon the limitations of earlier atomic models such as Niels Bohr's 1913 planetary model, which posited quantized electron orbits but failed to fully explain spectral complexities. A key milestone in this evolution came from Arnold Sommerfeld in 1916, who extended Bohr's model by incorporating relativistic effects and allowing for elliptical orbits rather than strictly circular ones. This introduction of an additional quantum condition for the radial motion, alongside angular quantization, provided a precursor to the concept of subshells by accounting for fine structure splittings in atomic spectra, such as the hydrogen fine structure lines observed experimentally. Sommerfeld's relativistic treatment predicted energy level shifts dependent on orbital eccentricity, laying groundwork for more nuanced electron groupings in multi-electron atoms. Further advancements arose from Louis de Broglie's 1924 hypothesis, which proposed wave-particle duality for electrons, asserting that particles like electrons exhibit wave-like properties with a wavelength given by \lambda = h / p, where h is Planck's constant and p is the electron's momentum. This idea suggested that electrons in atoms could be standing waves confined to discrete paths, providing a conceptual bridge from classical orbits to wave mechanics and motivating the quantization of electron shells. Building on this, Erwin Schrödinger formulated the time-independent Schrödinger equation in 1926 for the hydrogen atom, expressed as \hat{H} \psi = E \psi, where \hat{H} is the Hamiltonian operator, \psi is the wave function, and E is the energy eigenvalue. Solving this equation yielded quantized energy levels E_n = -13.6 \, \text{eV} / n^2, where n is a positive integer, confirming discrete shells and resolving inconsistencies in Bohr's non-relativistic energies.[26] Complementing these developments, Werner Heisenberg's uncertainty principle, articulated in 1927, introduced fundamental indeterminacy in quantum measurements, stating that the product of uncertainties in position \Delta x and momentum \Delta p satisfies \Delta x \Delta p \geq \hbar / 2, where \hbar = h / 2\pi. This principle prohibited the precise definition of fixed electron orbits, as simultaneous knowledge of position and momentum becomes impossible, thereby necessitating a probabilistic wave description for electron shells rather than deterministic paths. Finally, Wolfgang Pauli's exclusion principle, proposed in 1925, stipulated that no two electrons in an atom can occupy the same quantum state, meaning they cannot share all quantum numbers simultaneously. This rule was essential for establishing the shell structure, as it enforced distinct occupancy limits within energy levels, preventing collapse of electrons into the lowest state and enabling the layered configuration observed in atomic spectra.Quantum Mechanical Framework
Principal Quantum Number and Shells
In quantum mechanics, the principal quantum number n is a positive integer (n = 1, 2, 3, \dots, \infty) that primarily determines the energy level and size of an electron shell in an atom.[10] It labels the discrete energy shells, with n = 1 corresponding to the innermost K shell, n = 2 to the L shell, n = 3 to the M shell, and so on, following spectroscopic notation established in early atomic physics.[27] The energy of an electron in a shell depends on n. For hydrogen-like atoms (single-electron systems such as H or He⁺), the energy levels are given by E_n = -\frac{13.6 \, Z^2}{n^2} \, \text{eV}, where Z is the atomic number; this formula arises from solving the Schrödinger equation for the Coulomb potential.[28] In multi-electron atoms, inner electrons screen the nuclear charge, reducing the effective nuclear charge Z_{\text{eff}} experienced by outer electrons, which modifies the energy to approximately E_n \approx -\frac{13.6 \, Z_{\text{eff}}^2}{n^2} \, \text{eV} and results in less negative (higher) energies compared to hydrogen-like cases. Spatially, the electron shell's extent is characterized by the radial probability distribution, where the probability density for finding the electron peaks at an average distance from the nucleus scaling as \sim n^2 a_0, with a_0 = 0.529 \, \text{Å} being the Bohr radius (the most probable radius for the ground state of hydrogen).[29] This quadratic dependence on n reflects the increasing orbital size with higher shells, as derived from the radial wavefunctions in the hydrogen atom solution.[28] Electron shells are denoted using spectroscopic notation, such as 1s or 2p, where the numeral specifies n and the letter indicates the subshell (an angular subdivision within the shell); this ties the overall shell structure directly to the principal quantum number.[27]Subshells and Angular Momentum
Within each electron shell defined by the principal quantum number n, subshells arise as subdivisions characterized by the azimuthal quantum number l, which quantifies the orbital angular momentum of the electron. The value of l ranges from 0 to n-1 in integer steps, with this range constrained by n.[2] Subshells are conventionally labeled using letters: s for l = 0, p for l = 1, d for l = 2, and f for l = 3, with higher values of l assigned subsequent letters in alphabetical order (g, h, etc.).[2][30] The orbital angular momentum associated with a subshell has a magnitude given by \sqrt{l(l+1)} \hbar, where \hbar = h / 2\pi and h is Planck's constant; this formula emerges from the quantum mechanical solution to the angular part of the Schrödinger equation for the hydrogen atom.[31] The distinct values of l also determine the shapes of the atomic orbitals within each subshell. For instance, s orbitals (l = 0) are spherically symmetric around the nucleus, p orbitals (l = 1) exhibit a dumbbell shape with two lobes along a principal axis, d orbitals (l = 2) possess more intricate cloverleaf-like patterns with four lobes in the equatorial plane or double dumbbells, and f orbitals (l = 3) display even more complex geometries involving multiple lobes and nodal planes.[2] These shapes reflect the probability distribution of finding the electron in space, derived from the angular dependence of the wave function.[10] Further subdivision within a subshell is provided by the magnetic quantum number m_l, which specifies the orientation of the orbital in a magnetic field and takes integer values from -l to +l, inclusive.[9] This yields $2l + 1 possible values for m_l, corresponding to the number of distinct orbitals in the subshell; each orbital represents a unique spatial orientation.[9] For example, the p subshell (l = 1) has three orbitals (m_l = -1, 0, +1), oriented along the x, y, and z axes, while the d subshell (l = 2) contains five orbitals.[2]Orbital Energies and Electron Filling
In the hydrogen atom, the energy levels of orbitals depend solely on the principal quantum number n, resulting in degeneracy where all subshells within the same shell (e.g., 2s and 2p) have identical energies.[32] However, in multi-electron atoms, this degeneracy is lifted primarily by electron-electron repulsion, which introduces additional energy contributions that differentiate orbitals based on both n and the azimuthal quantum number l.[33] As a result, orbital energies increase with increasing n due to the larger average distance from the nucleus, but within a given n, energies also rise with l because higher-l orbitals experience less penetration toward the nucleus and thus weaker attraction.[30] For example, the 2s orbital has lower energy than the 2p orbital in atoms like carbon, as the 2s wavefunction penetrates closer to the nucleus, allowing better shielding from inner electrons and a stronger effective nuclear pull.[34] This variation in orbital energies arises from the effective nuclear charge Z_{\text{eff}} experienced by an electron, defined as Z_{\text{eff}} = Z - \sigma, where [Z](/page/Z) is the atomic number (nuclear charge) and \sigma is the screening constant accounting for the shielding effect of inner electrons.[35] The screening constant \sigma quantifies how much the net positive charge is reduced by electron-electron repulsions and the spatial distribution of other electrons, with values estimated via methods like Slater's rules, which assign contributions based on the electron's shell and subshell grouping.[35] Electrons in penetrating orbitals (lower l) experience a higher Z_{\text{eff}} because they are less effectively screened, lowering their energy relative to non-penetrating ones in the same shell.[36] When filling orbitals with electrons, the Pauli exclusion principle limits each orbital to a maximum of two electrons, distinguished by their spin quantum number m_s, which can take values of +\frac{1}{2} (spin up) or -\frac{1}{2} (spin down).[37] These opposite spins allow the two electrons to occupy the same orbital without violating the principle that no two electrons can have identical sets of quantum numbers.[37] In degenerate orbitals (those of equal energy within a subshell), Hund's rule dictates that electrons occupy orbitals singly with parallel spins to maximize the total spin multiplicity, minimizing electron-electron repulsion through greater spatial separation before pairing occurs.[38] This configuration achieves the lowest energy state by favoring higher total spin S, where the multiplicity $2S + 1 is maximized for the subshell.[38]Configuration Rules
Maximum Occupancy per Shell and Subshell
In quantum mechanics, the maximum number of electrons that can occupy a subshell is determined by the azimuthal quantum number \ell, given by the formula $2(2\ell + 1). This capacity arises from the $2\ell + 1 possible values of the magnetic quantum number m_\ell (ranging from -\ell to +\ell), each defining a distinct orbital that can accommodate up to two electrons with opposite spins.[1] For the common subshells, this yields specific limits: the s subshell (\ell = 0) holds 2 electrons, the p subshell (\ell = 1) holds 6 electrons, the d subshell (\ell = 2) holds 10 electrons, and the f subshell (\ell = 3) holds 14 electrons. These limits are enforced by the Pauli exclusion principle, which prohibits more than two electrons from sharing the same set of quantum numbers in an orbital.[1] The total maximum occupancy of an electron shell, defined by the principal quantum number n, is $2n^2. This formula is derived by summing the capacities of all subshells within the shell, from \ell = 0 to \ell = n-1: \sum_{\ell=0}^{n-1} 2(2\ell + 1) = 2 \sum_{\ell=0}^{n-1} (2\ell + 1) = 2 \left[ 2 \cdot \frac{(n-1)n}{2} + n \right] = 2n^2. The summation reflects the total number of orbitals in the shell, which equals n^2, with each orbital holding 2 electrons. Examples of shell capacities include the K shell (n=1): 2 electrons; L shell (n=2): 8 electrons; and M shell (n=3): 18 electrons. In multi-electron atoms, shells generally fill from inner to outer due to decreasing electron-nucleus attraction with distance, though energy overlaps in transition metals can result in incomplete filling of inner d subshells before outer s subshells.[39]| Principal Quantum Number (n) | Shell Designation | Maximum Electrons ($2n^2) | Subshells Included | Subshell Capacities |
|---|---|---|---|---|
| 1 | K | 2 | 1s | 2 |
| 2 | L | 8 | 2s, 2p | 2, 6 |
| 3 | M | 18 | 3s, 3p, 3d | 2, 6, 10 |
| 4 | N | 32 | 4s, 4p, 4d, 4f | 2, 6, 10, 14 |
Aufbau Principle and Madelung Rule
The Aufbau principle, also known as the building-up principle, dictates that electrons in the ground state of an atom occupy atomic orbitals in a sequence of increasing energy levels, starting from the lowest available energy orbital.[40] This principle provides a systematic framework for constructing electron configurations by progressively adding electrons to orbitals as atomic number increases.[40] To determine the specific order of orbital filling under the Aufbau principle, the Madelung rule—also called the n + ℓ rule—is applied, where orbitals are filled in ascending order of the sum of the principal quantum number n and the azimuthal quantum number ℓ (n + ℓ), and for orbitals with equal n + ℓ values, the one with the lower n is filled first. For example, the 1s orbital (n=1, ℓ=0; n+ℓ=1) is filled before the 2s orbital (n=2, ℓ=0; n+ℓ=2), which precedes the 2p orbitals (n=2, ℓ=1; n+ℓ=3), followed by 3s (n=3, ℓ=0; n+ℓ=3), 3p (n=3, ℓ=1; n+ℓ=4), 4s (n=4, ℓ=0; n+ℓ=4), and then 3d (n=3, ℓ=2; n+ℓ=5). While the Madelung rule accurately predicts the filling order for most elements, notable exceptions occur due to the enhanced stability of half-filled or fully filled subshells, which lower the overall energy compared to the predicted configuration.[41] For instance, chromium (atomic number 24) adopts the configuration [Ar] 3d⁵ 4s¹ instead of the expected [Ar] 3d⁴ 4s², achieving a half-filled 3d subshell; similarly, copper (atomic number 29) has [Ar] 3d¹⁰ 4s¹ rather than [Ar] 3d⁹ 4s², resulting in a fully filled 3d subshell.[41] In heavier elements following the lanthanide series, the lanthanide contraction—caused by the poor shielding of 4f electrons—further complicates the filling order by raising the energy of 5d and 4f orbitals relative to 6s, leading to irregularities in configurations for elements such as Hf and beyond.[42] This diagonal arrangement, often depicted with arrows indicating the Aufbau path (1s → 2s → 2p → 3s → 3p → 4s → 3d → 4p), reflects the Madelung ordering and holds for most configurations up to krypton, with the noted exceptions for stability.Periodic Implications
Electron Distribution Across Elements
The periodic table is divided into four main blocks—s, p, d, and f—each corresponding to the subshell being filled by valence electrons in the ground state configuration of atoms. The s-block includes groups 1 and 2 (alkali and alkaline earth metals), where the ns subshell accommodates up to two electrons. The p-block encompasses groups 13 through 18 (main group elements), filling the np subshell with up to six electrons. The d-block, spanning groups 3 through 12 (transition metals), involves sequential filling of the (n-1)d subshell, which holds up to 10 electrons. The f-block consists of the lanthanides and actinides, where the (n-2)f subshell is filled, accommodating up to 14 electrons. This block organization reflects the progressive addition of electrons to specific subshells as atomic number increases, providing a structural basis for periodic properties.[43][6] Shell filling trends vary across the blocks, influencing chemical behavior. In main group elements of the s- and p-blocks, electrons fill the outermost shell sequentially, leading to predictable valence electron counts that dictate reactivity. Transition metals in the d-block exhibit more complex filling, where the (n-1)d subshell is populated after the ns subshell but before completing the np subshell in subsequent periods, often resulting in variable oxidation states due to partial d-subshell occupancy. The f-block elements show similar intricacies, with f-subshell filling occurring within the inner shells, contributing to the contraction of atomic radii in these series. These trends are guided by the Aufbau principle, which orders orbital filling by increasing energy.[6][43] The valence shell, comprising the outermost occupied shell and any partially filled subshell, determines an element's group number and thus its position in the periodic table. For representative elements, the number of valence electrons corresponds directly to the group number; for example, group 17 elements (halogens) possess seven valence electrons in the configuration ns²np⁵. This valence electron count governs bonding tendencies, with s- and p-block elements typically achieving octet stability through electron transfer or sharing.[44][45] Ionization processes primarily affect the outer electron shells, as valence electrons are removed first to form cations, reflecting the relative stability of inner shells. Inner shells exhibit greater stability due to stronger nuclear attraction and shielding effects, making subsequent ionizations progressively more energy-intensive. Across the periodic table, first ionization energy increases from left to right within a period as effective nuclear charge rises and outer shells fill, while it decreases down a group with the addition of new shells that increase electron-nucleus distance. These shell-related effects underscore the periodic trends in reactivity and metallic character.[46][47]Notation and Examples for Key Elements
Electron configurations are expressed in spectroscopic notation, where the principal quantum number n precedes the subshell designation (s for l=0, p for l=1, d for l=2, f for l=3), followed by a superscript indicating the number of electrons in that subshell.[48] For elements beyond helium, configurations often use noble gas core notation, enclosing the symbol of the preceding noble gas in brackets to represent its filled shells; for instance, neon's full configuration is $1s^2 2s^2 2p^6, while sodium's is abbreviated as [Ne] $3s^1.[49] Representative examples demonstrate the progression of shell filling. Hydrogen has the simplest configuration: $1s^1.[50] Carbon, in the second period, fills the 2p subshell partially: $1s^2 2s^2 2p^2.[50] Iron, a transition metal, involves d-orbital filling: $1s^2 2s^2 2p^6 3s^2 3p^6 4s^2 3d^6 or [Ar] $4s^2 3d^6.[50] Gold exhibits a complex configuration with f- and d-block involvement: [Xe] $4f^{14} 5d^{10} 6s^1.[50] Exceptions to expected filling orders arise for enhanced stability. Chromium adopts [Ar] $4s^1 3d^5 rather than [Ar] $4s^2 3d^4, as the half-filled 3d subshell lowers energy through increased electron exchange interactions.[51] Copper follows suit with [Ar] $4s^1 3d^{10} instead of [Ar] $4s^2 3d^9, prioritizing the fully filled 3d subshell for similar stability gains.[51] The table below lists configurations for elements 1–20, revealing the sequential filling of K (n=1), L (n=2), M (n=3), and initial N (n=4) shells, with s subshells filling before p and the onset of 4s before 3d.| Atomic Number | Element | Electron Configuration |
|---|---|---|
| 1 | H | $1s^1 |
| 2 | He | $1s^2 |
| 3 | Li | $1s^2 2s^1 |
| 4 | Be | $1s^2 2s^2 |
| 5 | B | $1s^2 2s^2 2p^1 |
| 6 | C | $1s^2 2s^2 2p^2 |
| 7 | N | $1s^2 2s^2 2p^3 |
| 8 | O | $1s^2 2s^2 2p^4 |
| 9 | F | $1s^2 2s^2 2p^5 |
| 10 | Ne | $1s^2 2s^2 2p^6 |
| 11 | Na | $1s^2 2s^2 2p^6 3s^1 |
| 12 | Mg | $1s^2 2s^2 2p^6 3s^2 |
| 13 | Al | $1s^2 2s^2 2p^6 3s^2 3p^1 |
| 14 | Si | $1s^2 2s^2 2p^6 3s^2 3p^2 |
| 15 | P | $1s^2 2s^2 2p^6 3s^2 3p^3 |
| 16 | S | $1s^2 2s^2 2p^6 3s^2 3p^4 |
| 17 | Cl | $1s^2 2s^2 2p^6 3s^2 3p^5 |
| 18 | Ar | $1s^2 2s^2 2p^6 3s^2 3p^6 |
| 19 | K | $1s^2 2s^2 2p^6 3s^2 3p^6 4s^1 |
| 20 | Ca | $1s^2 2s^2 2p^6 3s^2 3p^6 4s^2 |