Atomic orbital

An atomic orbital is a mathematical function that describes the wave-like behavior of either one electron or a pair of electrons in an atom.^[1] This function can be used to calculate the probability of finding any electron of an atom in any specific region around the atom's nucleus. The term may also refer to the physical region where the electron can be calculated to be, as defined by the particular mathematical form of the orbital.^[2]

Atomic orbitals are the regions or volumes in space in which the probability of finding electrons is highest.They describe the wave-like nature of this electron in any energy state. They can be the hydrogen-like "orbitals" which are exact solutions to the Schrödinger equation for a hydrogen-like "atom" (i.e., the hydrogen atom or any ion formed by one electron and a nucleus). Alternatively, atomic orbitals refer to functions that depend on the coordinates of one electron (i.e. orbitals) but are used as starting points for approximating wave functions that depend on the simultaneous coordinates of all the electrons in an atom or molecule. The coordinate systems for atomic orbitals are usually spherical coordinates (r,θ,φ) in atoms and cartesians (x,y,z) in poly-atomic molecules.

Within a visual context, atomic orbitals are the basic building blocks of the introductory pedagogical electron cloud model (derived from the wave mechanics model or atomic orbital model, but using particle concepts in order to visualize the mathematical procedures used to approximate wave functions for atoms with many electrons). Thus (with particle concepts in italics), this model provides a framework for describing the placement of electrons in an atom. In this model, the atom consists of a nucleus surrounded by orbiting electrons. These electrons exist in so called atomic orbitals, which are a set of quantum states of the negatively charged electrons trapped in the electrical field generated by the positively-charged nucleus (which may be weakened by the effect of other electrons, but still remains attractive in sum). The electron cloud model can ultimately be described by quantum mechanics, in which the electrons are more accurately described as standing waves surrounding the nucleus.

Atomic orbitals are typically categorized by n, l, and m quantum numbers, which correspond to the electron's energy, angular momentum, and an angular momentum vector component, respectively. Each orbital is defined by a different set of quantum numbers and contains a maximum of two electrons. The simple names s orbital, p orbital, d orbital and f orbital refer to orbitals with angular momentum quantum number l = 0, 1, 2 and 3 respectively. These names indicate the orbital shape and are used to describe the electron configurations. They are derived from the characteristics of their spectroscopic lines: sharp, principal, diffuse, and fundamental, the rest being named in alphabetical order (omitting j).^[3][4]

The wave function for the electron cloud of a multi-electron atom may be seen as being built up (in approximation) in an electron configuration that is a product of simpler hydrogen-like atomic orbitals. Ψ_He(x₁,y₁,z₁,x₂,y₂,z₂) ≈ 1s(x₁,y₁,z₁) • 1s(x₂,y₂,z₂) = 1s². (This is read as, "The exact wave function depending on the simultaneous coordinates of the two electrons in the helium atom is approximated as a product of two one-s atomic orbitals each of which depends on the coordinates of only one electron.") In such a configuration, pairs of electrons are arranged in simple repeating patterns of increasing odd numbers (1,3,5,7..), each of which represents a set of electron pairs with a given energy and angular momentum. The repeating periodicity of the blocks of 2, 6, 10, and 14 elements within sections of the periodic table arises naturally from the total number of electrons which occupy a complete set of s, p, d and f atomic orbitals, respectively.

There are typically three mathematical forms for atomic orbitals which can be chosen as a starting point for the calculation of the properties of atoms and molecules with many electrons. They all have forms that generate s, p, d, etc. functions. Their differences are:

1. the hydrogen-like atomic orbitals are derived from the exact solution of the Schrödinger Equation for one electron and a nucleus. The part of the function that depends on the distance from the nucleus has nodes (radial nodes) and decays as e^(-distance) from the nucleus.
2. The Slater-type orbital (STO) is a form without radial nodes but decays from the nucleus as does the hydrogen-like orbital.
3. The form of the Gaussian type orbital (Gaussians) has no radial nodes and decays as e^{(-distance squared)}.

Although hydrogen-like orbitals are still used as pedagogical tools, the advent of computers has made STOs preferable for atoms and diatomic molecules since combinations of STOs can replace the nodes in hydrogen-like atomic orbital. Gaussians are typically used in molecules with three or more atoms. Although not as accurate by themselves as STOs, combinations of many Gaussians can attain the accuracy of hydrogen-like orbitals.

Introduction

With the development of quantum mechanics, it was found that the orbiting electrons around a nucleus could not be fully described as particles, but needed to be explained by the wave-particle duality. In this sense, the electrons have the following properties:

Wave-like properties

The electrons do not orbit the nucleus in the sense of a planet orbiting the sun, but instead exist as standing waves. The lowest possible energy an electron can take is therefore analogous to the fundamental frequency of a wave on a string. Higher energy states are then similar to harmonics of the fundamental frequency.

The electrons are never in a single point location, although the probability of interacting with the electron at a single point can be found from the wave function of the electron.

Particle-like properties

There is always an integer number of electrons orbiting the nucleus.

Electrons jump between orbitals in a particle-like fashion. For example, if a single photon strikes the electrons, only a single electron changes states in response to the photon.

The electrons retain particle like-properties such as: each wave state has the same electrical charge as the electron particle. Each wave state has a single discrete spin (spin up or spin down).

Visualizing atomic orbitals intuitively

Despite the obvious analogy to planets revolving around the Sun, electrons cannot be described as solid particles. In addition, atomic orbitals do not closely resemble a planet's elliptical path in ordinary atoms. A more accurate analogy might be that of a large and often oddly-shaped "atmosphere" (the electron), distributed around a relatively tiny planet (the atomic nucleus). One difference is that some of an atom's electrons, those in s orbitals, have zero angular momentum, so they cannot in any sense be thought of as moving "around" the nucleus, as a planet does. (A planet would need to fall vertically into the Sun and oscillate up and down through it, to be in an orbit with no angular momentum). Other electrons do have varying amounts of angular momentum.

Atomic orbitals exactly describe the shape of this "atmosphere" only when a single electron is present in an atom. When more electrons are added to a single atom, the additional electrons tend to more evenly fill in a volume of space around the nucleus so that the resulting collection (sometimes termed the atom’s “electron cloud” ^[5]) tends toward a generally spherical zone of probability describing where the atom’s electrons will be found.

History

The term "orbital" was coined by Robert Mulliken in 1932.^[6] However, the idea that electrons might revolve around a compact nucleus with definite angular momentum was convincingly argued at least 19 years earlier by Niels Bohr,^[7] and the Japanese physicist Hantaro Nagaoka published an orbit-based hypothesis for electronic behavior as early as 1904.^[8] Explaining the behavior of these electron "orbits" was one of the driving forces behind the development of quantum mechanics.^[9]

Early models

With J.J. Thomson's discovery of the electron in 1897,^[10] it became clear that atoms were not the smallest building blocks of nature, but were rather composite particles. The newly discovered structure within atoms tempted many to imagine how the atom's constituent parts might interact with each other. Thomson theorized that multiple electrons revolved in orbit-like rings within a positively-charged jelly-like substance,^[11] and between the electron's discovery and 1909, this "plum pudding model" was the most widely-accepted explanation of atomic structure.

Shortly after Thomson's discovery, Hantaro Nagaoka, a Japanese physicist, predicted a different model for electronic structure.^[8] Unlike the plum pudding model, the positive charge in Nagaoka's "Saturnian Model" was concentrated into a central core, pulling the electrons into circular orbits reminiscent of Saturn's rings. Few people took notice of Nagaoka's work at the time,^[12] and Nagaoka himself recognized a fundamental defect in the theory even at its conception, namely that a classical charged object cannot sustain orbital motion because it is accelerating and therefore loses energy due to electromagnetic radiation.^[13] Nevertheless, the Saturnian model turned out to have more in common with modern theory than any of its contemporaries.

Bohr atom

In 1909 Ernest Rutherford discovered that the positive half of atoms was tightly condensed into a nucleus,^[14] and it became clear from his analysis in 1911 that the plum pudding model could not explain atomic structure. Shortly after, in 1913, Rutherford's postdoctoral student Niels Bohr proposed a new model of the atom, wherein electrons orbited the nucleus with classical periods, but were only permitted to have discrete values of angular momentum, quantized in units h/2π.^[7] This constraint automatically permitted only certain values of electron energies. The Bohr model of the atom fixed the problem of energy loss from radiation from a ground state (by declaring that there was no state below this), and more importantly explained the origin of spectral lines.

After Bohr's use of Einstein's explanation of the photoelectric effect to relate energy levels in atoms with the wavelength of emitted light, the connection between the structure of electrons in atoms and the emission and absorption spectra of atoms became an increasingly useful tool in the understanding of electrons in atoms. The most prominent feature of emission and absorption spectra (known experimentally since the middle of the 19^th century), was that these atomic spectra contained discrete lines. The significance of the Bohr model was that it related the lines in emission and absorption spectra to the energy differences between the orbits that electrons could take around an atom. This was, however, not achieved by Bohr through giving the electrons some kind of wave-like properties, since the idea that electrons could behave as matter waves was not suggested until twelve years later. Still, the Bohr model's use of quantized angular momenta and therefore quantized energy levels was a significant step towards the understanding of electrons in atoms, and also a significant step towards the development of quantum mechanics in suggesting that quantized restraints must account for all discontinuous energy levels and spectra in atoms.

With de Broglie's suggestion of the existence of electron matter waves in 1924, and for a short time before the full 1926 Schrödinger equation treatment of hydrogen like atom, a Bohr electron "wavelength" could be seen to be a function of its momentum, and thus a Bohr orbiting electron was seen to orbit in a circle at a multiple of its half-wavelength (this historically incorrect Bohr model is still occasionally taught to students). The Bohr model for a short time could be seen as a classical model with an additional constraint provided by the 'wavelength' argument. However, this period was immediately superseded by the full three-dimensional wave mechanics of 1926. In our current understanding of physics, the Bohr model is called a semi-classical model because of its quantization of angular momentum, not primarily because of its relationship with electron wavelength, which appeared in hindsight a dozen years after the Bohr model was proposed.

The Bohr model was able to explain the emission and absorption spectra of hydrogen. The energies of electrons in the n=1, 2, 3, etc. states in the Bohr model match those of current physics. However, this did not explain similarities between different atoms, as expressed by the periodic table, such as the fact that helium (2 electrons), neon (10 electrons), and argon (18 electrons) exhibit similar chemical behavior. Modern physics explains this by noting that the n=1 state holds 2 electrons, the n=2 state holds 8 electrons, and the n=3 state holds 8 electrons (in argon). In the end, this was solved by the discovery of modern quantum mechanics and the Pauli Exclusion Principle.

Modern conceptions and connections to the Heisenberg Uncertainty Principle

Immediately after Heisenberg discovered his uncertainty relation,^[15] it was noted by Bohr that the existence of any sort of wave packet implies uncertainty in the wave frequency and wavelength, since a spread of frequencies is needed to create the packet itself.^[16] In quantum mechanics, where all particle momenta are associated with waves, it is the formation of such a wave packet which localizes the wave, and thus the particle, in space. In states where a quantum mechanical particle is bound, it must be localized as a wave packet, and the existence of the packet and its minimum size implies a spread and minimal value in particle wavelength, and thus also momentum and energy. In quantum mechanics, as a particle is localized to a smaller region in space, the associated compressed wave packet requires a larger and larger range of momenta, and thus larger kinetic energy. Thus, the binding energy to contain or trap a particle in a smaller region of space, increases without bound, as the region of space grows smaller. Particles cannot be restricted to a geometric point in space, since this would require an infinite particle momentum.

In chemistry, Schrödinger, Pauling, Mulliken and others noted that the consequence of Heisenberg's relation was that the electron, as a wave packet, could not be considered to have an exact location in its orbital. Max Born suggested that the electron's position needed to be described by a probability distribution which was connected with finding the electron at some point in the wave-function which described its associated wave packet. The new quantum mechanics did not give exact results, but only the probabilities for the occurrence of a variety of possible such results. Heisenberg held that the path of a moving particle has no meaning if we cannot observe it, as we cannot with electrons in an atom.

In the quantum picture of Heisenberg, Schrödinger and others, the Bohr atom number n for each orbital became known as an n-sphere in a three dimensional atom and was pictured as the mean energy of the probability cloud of the electron's wave packet which surrounded the atom.

Orbital names

Orbitals are given names in the form:

where X is the energy level corresponding to the principal quantum number n, type is a lower-case letter denoting the shape or subshell of the orbital and it corresponds to the angular quantum number l, and y is the number of electrons in that orbital.

For example, the orbital 1s² (pronounced "one ess two") has two electrons and is the lowest energy level (n = 1) and has an angular quantum number of l = 0. In X-ray notation, the principal quantum number is given a letter associated with it. For n = 1, 2, 3, 4, 5, ..., the letters associated with those numbers are K, L, M, N, O, ..., respectively.

Formal quantum mechanical definition

In quantum mechanics, the state of an atom, i.e. the eigenstates of the atomic Hamiltonian, is expanded (see configuration interaction expansion and basis set) into linear combinations of anti-symmetrized products (Slater determinants) of one-electron functions. The spatial components of these one-electron functions are called atomic orbitals. (When one considers also their spin component, one speaks of atomic spin orbitals.)

In atomic physics, the atomic spectral lines correspond to transitions (quantum leaps) between quantum states of an atom. These states are labeled by a set of quantum numbers summarized in the term symbol and usually associated with particular electron configurations, i.e., by occupation schemes of atomic orbitals (e.g., 1s² 2s² 2p⁶ for the ground state of neon -- term symbol: ¹S₀).

This notation means that the corresponding Slater determinants have a clear higher weight in the configuration interaction expansion. The atomic orbital concept is therefore a key concept for visualizing the excitation process associated with a given transition. For example, one can say for a given transition that it corresponds to the excitation of an electron from an occupied orbital to a given unoccupied orbital. Nevertheless, one has to keep in mind that electrons are fermions ruled by the Pauli exclusion principle and cannot be distinguished from the other electrons in the atom. Moreover, it sometimes happens that the configuration interaction expansion converges very slowly and that one cannot speak about simple one-determinant wave function at all. This is the case when electron correlation is large.

Fundamentally, an atomic orbital is a one-electron wave function, even though most electrons do not exist in one-electron atoms, and so the one-electron view is an approximation. When thinking about orbitals, we are often given an orbital vision which (even if it is not spelled out) is heavily influenced by this Hartree–Fock approximation, which is one way to reduce the complexities of molecular orbital theory.

Hydrogen-like atoms

The simplest atomic orbitals are those that are calculated for systems with a single electron, such as the hydrogen atom. An atom of any other element ionized down to a single electron is very similar to hydrogen, and the orbitals take the same form. In the Schrödinger equation for this system of one negative and one positive particle, the atomic orbitals are the eigenstates of the Hamiltonian operator for the energy. They can be obtained analytically, meaning that the resulting orbitals are products of a polynomial series, and exponential and trigonometric functions. (see hydrogen atom).

For atoms with two or more electrons, the governing equations can only be solved with the use of methods of iterative approximation. Orbitals of multi-electron atoms are qualitatively similar to those of hydrogen, and in the simplest models, they are taken to have the same form. For more rigorous and precise analysis, the numerical approximations must be used.

A given (hydrogen-like) atomic orbital is identified by unique values of three quantum numbers: n, l, and m_l. The rules restricting the values of the quantum numbers, and their energies (see below), explain the electron configuration of the atoms and the periodic table.

The stationary states (quantum states) of the hydrogen-like atoms are its atomic orbitals. However, in general, an electron's behavior is not fully described by a single orbital. Electron states are best represented by time-depending "mixtures" (linear combinations) of multiple orbitals. See Linear combination of atomic orbitals molecular orbital method.

The quantum number n first appeared in the Bohr model where it determines the radius of each circular electron orbit. In modern quantum mechanics however, n determines the mean distance of the electron from the nucleus; all electrons with the same value of n lie at the same average distance. For this reason, orbitals with the same value of n are said to comprise a "shell". Orbitals with the same value of n and also the same value of l are even more closely related, and are said to comprise a "subshell".

Quantum numbers

Because of the quantum mechanical nature of the electrons around a nucleus, they cannot be described by a location and momentum. Instead, they are described by a set of quantum numbers that encompasses both the particle-like nature and the wave-like nature of the electrons. An atomic orbital is uniquely identified by the values of the three quantum numbers, and each set of the three quantum numbers corresponds to exactly one orbital, but the quantum numbers only occur in certain combinations of values. The quantum numbers, together with the rules governing their possible values, are as follows:

The principal quantum number, n, describes the energy of the electron and is always a positive integer. In fact, it can be any positive integer, but for reasons discussed below, large numbers are seldom encountered. Each atom has, in general, many orbitals associated with each value of n; these orbitals together are sometimes called electron shells.

The azimuthal quantum number, , describes the orbital angular momentum of each electron and is a non-negative integer. Within a shell where n is some integer n₀, ranges across all (integer) values satisfying the relation . For instance, the n = 1 shell has only orbitals with , and the n = 2 shell has only orbitals with , and . The set of orbitals associated with a particular value of are sometimes collectively called a subshell.

The magnetic quantum number, , describes the magnetic moment of an electron in an arbitrary direction, and is also always an integer. Within a subshell where is some integer , ranges thus: .

The above results may be summarized in the following table. Each cell represents a subshell, and lists the values of available in that subshell. Empty cells represent subshells that do not exist.

	l=0	l=1	l=2	l=3	l=4	...
n=1
n=2	0	-1, 0, 1
n=3	0	-1, 0, 1	-2, -1, 0, 1, 2
n=4	0	-1, 0, 1	-2, -1, 0, 1, 2	-3, -2, -1, 0, 1, 2, 3
n=5	0	-1, 0, 1	-2, -1, 0, 1, 2	-3, -2, -1, 0, 1, 2, 3	-4, -3, -2 -1, 0, 1, 2, 3, 4
...	...	...	...	...	...	...

Subshells are usually identified by their - and -values. is represented by its numerical value, but is represented by a letter as follows: 0 is represented by 's', 1 by 'p', 2 by 'd', 3 by 'f', and 4 by 'g'. For instance, one may speak of the subshell with and as a '2s subshell'.

Each electron also has a spin quantum number, s, which describes the spin of each electron (spin up or spin down). The number s can be +¹⁄₂ or -¹⁄₂.

The Pauli exclusion principle states that no two electrons can occupy the same quantum state: every electron in an atom must have a unique combination of quantum numbers.

Shapes of orbitals

Any discussion of the shapes of electron orbitals is necessarily arbitrary since a number representing a certain probability of finding the electron must be chosen (usually from zero up to one, or from 0 up to 100%). According to the uncertainty principle and the hypotheses of Quantum Mechanics a given electron has one and only one probability of being found at any moment at a particular point (x,y,z) in space. For an atom, it is easier to calculate the probability using a distance r from the nucleus and a direction (θ,φ) using polar coordinates. If an atomic orbital is used to describe this electron, then the probability of finding an electron at point (r,θ,φ) is obtained from this orbital, which is the mathematical function ψ(r,θ,φ).

However, the electron is much more likely to be found in particular regions around the atom than in others. Given this, a boundary surface can be drawn so that the electron has a high probability to be found somewhere within the surface, and all regions outside the surface have low values. Even though the precise placement of the surface is arbitrary, any reasonably compact determination must follow a pattern specified by the behavior of |ψ(r,θ,φ)|², the square of the absolute value (also called magnitude or modulus) of the complex-valued wave function. This boundary surface is sometimes what is meant when the "shape" of an orbital is referred to. Sometimes the ψ function will be graphed to show its phases, rather than the |ψ(r,θ,φ)|² which shows probability density but has no phases (which have been lost in the process of taking the absolute value, since ψ(r,θ,φ) is a complex number). |ψ(r,θ,φ)|² orbital graphs tend to have less spherical, thinner lobes than ψ(r,θ,φ) graphs, but have the same number of lobes in the same places, and otherwise are recognizable. This article, in order to show wave function phases, shows mostly ψ(r,θ,φ) graphs.

The lobes can be viewed as interference patterns between the two counter rotating "m" and "-m" modes, with the projection of the orbital onto the xy plane having a resonant "m" wavelengths around the circumference. For each m there are two of these <m>+<-m> and <m>-<-m>. For the case where m=0 the orbital is vertical, counter rotating information is unknown, and the orbital is z-axis symmetric. For the case where l=0 there are no counter rotating modes. There are only radial modes and the shape is spherically symmetric. For any given n, the smaller l is, the more radial nodes there are. Loosely speaking n is energy, l is analogous to eccentricity, and m is orientation.

Generally speaking, the number n determines the size and energy of the orbital for a given nucleus: as n increases, the size of the orbital increases. However, in comparing different elements, the higher nuclear charge, Z, of heavier elements causes their orbitals to contract by comparison to lighter ones, so that the overall size of the whole atom remains very roughly constant, even as the number of electrons in heavier elements (higher Z) increases.

Also in general terms, determines an orbital's shape, and its orientation. However, since some orbitals are described by equations in complex numbers, the shape sometimes depends on also.

The single s-orbitals () are shaped like spheres. For n = 1 the sphere is "solid" (it is most dense at the center and fades exponentially outwardly), but for n = 2 or more, each single s-orbital is composed of spherically symmetric surfaces which are nested shells (i.e., the "wave-structure" is radial, following a sinusoidal radial component as well). See illustration of a cross-section of these nested shells, at right. The s-orbitals for all n numbers are the only orbitals with an anti-node (a region of high wave function density) at the center of the nucleus. All other orbitals (p, d, f, etc.) have angular momentum, and thus avoid the nucleus (having a wave node at the nucleus).

The three p-orbitals for n = 2 have the form of two ellipsoids with a point of tangency at the nucleus (the two-lobed shape is sometimes referred to as a "dumbbell"). The three p-orbitals in each shell are oriented at right angles to each other, as determined by their respective linear combination of values of .

Four of the five d-orbitals for n = 3 look similar, each with four pear-shaped lobes, each lobe tangent to two others, and the centers of all four lying in one plane, between a pair of axes. Three of these planes are the xy-, xz-, and yz-planes, and the fourth has the centres on the x and y axes. The fifth and final d-orbital consists of three regions of high probability density: a torus with two pear-shaped regions placed symmetrically on its z axis.

There are seven f-orbitals, each with shapes more complex than those of the d-orbitals.

For each s, p, d, f and g set of orbitals, the set of orbitals which composes it forms a spherically symmetrical set of shapes. For non-s orbitals, which have lobes, the lobes point in directions so as to fill space as symmetrically as possible for number of lobes which exist for a set of orientations. For example, the three p orbitals have six lobes which are oriented to each of the six primary directions of 3-D space; for the 5 d orbitals, there are a total of 18 lobes, in which again six point in primary directions, and the 12 additional lobes fill the 12 gaps which exist between each pairs of these 6 primary axes.

Additionally, as is the case with the s orbitals, individual p, d, f and g orbitals with n values higher than the lowest possible value, exhibit an additional radial node structure which is reminiscent of harmonic waves of the same type, as compared with the lowest (or fundamental) mode of the wave. As with s orbitals, this phenomenon provides p, d, f, and g orbitals at the next higher possible value of n (for example, 3p orbitals vs. the fundamental 2p), an additional node in each lobe. Still higher values of n further increase the number of radial nodes, for each type of orbital.

The shapes of atomic orbitals in one-electron atom are related to 3-dimensional spherical harmonics. These shapes are not unique, and any linear combination is valid, like a transformation to cubic harmonics, in fact it is possible to generate sets where all the d's are the same shape, just like the p_x, p_y, and p_z are the same shape.^[17][18]

Orbitals table

This table shows all orbital configurations for the real hydrogen-like wave functions up to 7s, and therefore covers the simple electronic configuration for all elements in the periodic table up to radium. ψ graphs are shown with - and + wave function phases shown in two different colors (arbitrarily red and blue). The p_z orbital is the same as the p₀ orbital, but the p_x and p_y are formed by taking linear combinations of the p₊₁ and p_-1 orbitals (which is why they are listed under the m=±1 label). Also, the p₊₁ and p_-1 are not the same shape as the p₀, since they are pure spherical harmonics.

Qualitative understanding of shapes

The shapes of atomic orbitals can be understood qualitatively by considering the analogous case of standing waves on a circular drum.^[19] To see the analogy, the mean vibrational displacement of each bit of drum membrane from the equilibrium point over many cycles (a measure of average drum membrane velocity and momentum at that point) must be considered relative to that point's distance from the center of the drum head. If this displacement is taken as being analogous to the probability of finding an electron at a given distance from the nucleus, then it will be seen that the many modes of the vibrating disk form patterns that trace the various shapes of atomic orbitals. The basic reason for this correspondence lies in the fact that the distribution of kinetic energy and momentum in a matter-wave is predictive of where the particle associated with the wave will be. That is, the probability of finding an electron at a given place is also a function of the electron's average momentum at that point, since high electron momentum at a given position tends to "localize" the electron in that position, via the properties of electron wave-packets (see the Heisenberg uncertainty principle for details of the mechanism).

This relationship means that certain key features can be observed in both drum membrane modes and atomic orbitals. For example, in all of the modes analogous to s orbitals (the top row in the illustration), it can be seen that the very center of the drum membrane vibrates most strongly, corresponding to the antinode in all s orbitals in an atom. This antinode means the electron is most likely to be at the physical position of the nucleus (which it passes straight through without scattering or striking it), since it is moving (on average) most rapidly at that point, giving it maximal momentum.

A mental "planetary orbit" picture closest to the behavior of electrons in s orbitals, all of which have no angular momentum, might perhaps be that of the path of an atomic-sized black hole, or some other imaginary particle which is able to fall with increasing velocity from space directly through the Earth, without stopping or being affected by any force but gravity, and in this way falls through the core and out the other side in a straight line, and off again into space, while slowing from the backwards gravitational tug. If such a particle were gravitationally bound to the Earth it would not escape, but would pursue a series of passes in which it always slowed at some maximal distance into space, but had its maximal velocity at the Earth's center (this "orbit" would have an orbital eccentricity of 1.0). If such a particle also had a wave nature, it would have the highest probability of being located where its velocity and momentum were highest, which would be at the Earth's core. In addition, rather than be confined to an infinitely narrow "orbit" which is a straight line, it would pass through the Earth from all directions, and not have a preferred one. Thus, a "long exposure" photograph of its motion over a very long period of time, would show a sphere.

In order to be stopped, such a particle would need to interact with the Earth in some way other than gravity. In a similar way, all s electrons have a finite probability of being found inside the nucleus, and this allows s electrons to occasionally participate in strictly nuclear-electron interaction processes, such as electron capture and internal conversion.

Below, a number of drum membrane vibration modes are shown. The analogous wave functions of the hydrogen atom are indicated. A correspondence can be considered where the wave functions of a vibrating drum head are for a two-coordinate system ψ(r,θ) and the wave functions for a vibrating sphere are three-coordinate ψ(r,θ,φ).

None of the other sets of modes in a drum membrane have a central antinode, and in all of them the center of the drum does not move. These correspond to a node at the nucleus for all non-s orbitals in an atom. These orbitals all have some angular momentum, and in the planetary model, they correspond to particles in orbit with eccentricity less than 1.0, so that they do not pass straight through the center of the primary body, but keep somewhat away from it.

In addition, the drum modes analogous to p and d modes in an atom show spatial irregularity along the different radial directions from the center of the drum, whereas all of the modes analogous to s modes are perfectly symmetrical in radial direction. The non radial-symmetry properties of non-s orbitals are necessary to localize a particle with angular momentum and a wave nature in an orbital where it must tend to stay away from the central attraction force, since any particle localized at the point of central attraction could have no angular momentum. For these modes, waves in the drum head tend to avoid the central point. Such features again emphasize that the shapes of atomic orbitals are a direct consequence of the wave nature of electrons.

Orbital energy

In atoms with a single electron (hydrogen-like atoms), the energy of an orbital (and, consequently, of any electrons in the orbital) is determined exclusively by . The orbital has the lowest possible energy in the atom. Each successively higher value of has a higher level of energy, but the difference decreases as increases. For high , the level of energy becomes so high that the electron can easily escape from the atom. In single electron atoms, all levels with different within a given are (to a good approximation) degenerate, and have the same energy. [This approximation is broken to a slight extent by the effect of the magnetic field of the nucleus, and by quantum electrodynamics effects. The latter induce tiny binding energy differences especially for s electrons that go nearer the nucleus, since these feel a very slightly different nuclear charge, even in one-electron atoms. See Lamb shift.]

In atoms with multiple electrons, the energy of an electron depends not only on the intrinsic properties of its orbital, but also on its interactions with the other electrons. These interactions depend on the detail of its spatial probability distribution, and so the energy levels of orbitals depend not only on but also on . Higher values of are associated with higher values of energy; for instance, the 2p state is higher than the 2s state. When = 2, the increase in energy of the orbital becomes so large as to push the energy of orbital above the energy of the s-orbital in the next higher shell; when = 3 the energy is pushed into the shell two steps higher. The filling of the 3d orbitals does not occur until the 4s orbitals have been filled.

The increase in energy for subshells of increasing angular momentum in larger atoms is due to electron-electron interaction effects, and it is specifically related to the ability of low angular momentum electrons to penetrate more effectively toward the nucleus, where they are subject to less screening from the charge of intervening electrons. Thus, in atoms of higher atomic number, the of electrons becomes more and more of a determining factor in their energy, and the principal quantum numbers of electrons becomes less and less important in their energy placement.

The energy sequence of the first 24 subshells (e.g., 1s, 2p, 3d, etc.) is given in the following table. Each cell represents a subshell with and given by its row and column indices, respectively. The number in the cell is the subshell's position in the sequence. For a linear listing of the subshells in terms of increasing energies in multielectron atoms, see the section below.

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

Note: empty cells indicate non-existent sublevels, while numbers in italics indicate sublevels that could exist, but which do not hold electrons in any element currently known.

Electron placement and the periodic table

Several rules govern the placement of electrons in orbitals (electron configuration). The first dictates that no two electrons in an atom may have the same set of values of quantum numbers (this is the Pauli exclusion principle). These quantum numbers include the three that define orbitals, as well as s, or spin quantum number. Thus, two electrons may occupy a single orbital, so long as they have different values of . However, only two electrons, because of their spin, can be associated with each orbital.

Additionally, an electron always tends to fall to the lowest possible energy state. It is possible for it to occupy any orbital so long as it does not violate the Pauli exclusion principle, but if lower-energy orbitals are available, this condition is unstable. The electron will eventually lose energy (by releasing a photon) and drop into the lower orbital. Thus, electrons fill orbitals in the order specified by the energy sequence given above.

This behavior is responsible for the structure of the periodic table. The table may be divided into several rows (called 'periods'), numbered starting with 1 at the top. The presently known elements occupy seven periods. If a certain period has number , it consists of elements whose outermost electrons fall in the th shell. Niels Bohr was the first to propose (1923) that the periodicity in the properties of the elements might be explained by the periodic filling of the electron energy levels, resulting in the electronic structure of the atom.^[20]

The periodic table may also be divided into several numbered rectangular 'blocks'. The elements belonging to a given block have this common feature: their highest-energy electrons all belong to the same -state (but the associated with that -state depends upon the period). For instance, the leftmost two columns constitute the 's-block'. The outermost electrons of Li and Be respectively belong to the 2s subshell, and those of Na and Mg to the 3s subshell.

The following is the order for filling the "subshell" orbitals, which also gives the order of the "blocks" in the periodic table:

1s, 2s, 2p, 3s, 3p, 4s, 3d, 4p, 5s, 4d, 5p, 6s, 4f, 5d, 6p, 7s, 5f, 6d, 7p

The "periodic" nature of the filling of orbitals, as well as emergence of the s, p, d and f "blocks", is more obvious if this order of filling is given in matrix form, with increasing principal quantum numbers starting the new rows ("periods") in the matrix. Then, each subshell (composed of the first two quantum numbers) is repeated as many times as required for each pair of electrons it may contain. The result is a compressed periodic table, with each entry representing two successive elements:

1s                                    
2s                          2p  2p  2p
3s                          3p  3p  3p
4s      3d  3d  3d  3d  3d  4p  4p  4p
5s      4d  4d  4d  4d  4d  5p  5p  5p
6s (4f) 5d  5d  5d  5d  5d  6p  6p  6p
7s (5f) 6d  6d  6d  6d  6d  7p  7p  7p

The number of electrons in an electrically neutral atom increases with the atomic number. The electrons in the outermost shell, or valence electrons, tend to be responsible for an element's chemical behavior. Elements that contain the same number of valence electrons can be grouped together and display similar chemical properties.

Relativistic effects

For elements with high atomic number Z, the effects of relativity become more pronounced, and especially so for s electrons, which move at relativistic velocities as they penetrate the screening electrons near the core of high Z atoms. This relativistic increase in momentum for high speed electrons causes a corresponding decrease in wavelength and contraction of 6s orbitals relative to 5d orbitals (by comparison to corresponding s and d electrons in lighter elements in the same column of the periodic table); this results in 6s valence electrons becoming lowered in energy.

Examples of significant physical outcomes of this effect include the lowered melting temperature of mercury (which results from 6s electrons not being available for metal bonding) and the golden color of gold and caesium (which results from narrowing of 6s to 5d transition energy to the point that visible light begins to be absorbed).^[21]

In the Bohr Model, an electron has a velocity given by , where Z is the atomic number, is the fine-structure constant, and c is the speed of light. In non-relativistic quantum mechanics, therefore, any atom with an atomic number greater than 137 would require its 1s electrons to be traveling faster than the speed of light. Even in the Dirac equation, which accounts for relativistic effects, the wavefunction of the electron for atoms with Z > 137 is oscillatory and unbounded. The significance of element 137, also known as untriseptium, was first pointed out by the physicist Richard Feynman. Element 137 is sometimes informally called feynmanium (symbol Fy). However, Feynman's approximation fails to predict the exact critical value of Z due to the non-point-charge nature of the nucleus and very small orbital radius of inner electrons, resulting in a potential seen by inner electrons which is effectively less than Z. The critical Z value which makes the atom unstable with regard to high-field breakdown of the vacuum and production of electron-positron pairs, does not occur until Z is about 173. These conditions are not seen except transiently in collisions of very heavy nuclei such as lead or uranium in accelerators, where such electron-positron production from these effects has been claimed to be observed. See Extension of the periodic table beyond the seventh period.

There are no nodes in relativistic orbital densities, although individual components of the wavefunction will have nodes.^[22]

Transitions between orbitals

Under quantum mechanics, each quantum state has a well-defined energy. When applied to atomic orbitals, this means that each state has a specific energy, and that if an electron is to move between states, the energy difference is also very fixed.

Consider two states of the Hydrogen atom:

State 1) n=1, l=0, m_l=0 and s=+¹⁄₂

State 2) n=2, l=0, m_l=0 and s=+¹⁄₂

By quantum theory, state 1 has a fixed energy of E₁, and state 2 has a fixed energy of E₂. Now, what would happen if an electron in state 1 were to move to state 2? For this to happen, the electron would need to gain an energy of exactly E₂ - E₁. If the electron receives energy that is less than or greater than this value, it cannot jump from state 1 to state 2. Now, suppose we irradiate the atom with a broad-spectrum of light. Photons that reach the atom that have an energy of exactly E₂ - E₁ will be absorbed by the electron in state 1, and that electron will jump to state 2. However, photons that are greater or lower in energy cannot be absorbed by the electron, because the electron can only jump to one of the orbitals, it cannot jump to a state between orbitals. The result is that only photons of a specific frequency will be absorbed by the atom. This creates a line in the spectrum, known as an absorption line, which corresponds to the energy difference between states 1 and 2.

The atomic orbital model thus predicts line spectra, which are observed experimentally. This is one of the main validations of the atomic orbital model.

The atomic orbital model is nevertheless an approximation to the full quantum theory, which only recognizes many electron states. The predictions of line spectra are qualitatively useful but are not quantitatively accurate for atoms and ions other than those containing only one electron.

See also

• Atomic electron configuration table
• Condensed matter physics
• Electron configuration
• Energy level
• List of Hund's rules
• Molecular orbital
• Quantum chemistry
• Quantum chemistry computer programs
• Solid state physics
• Orbital resonance

References

Further reading

• Tipler, Paul; Llewellyn, Ralph (2003). Modern Physics (4 ed.). New York: W. H. Freeman and Company. ISBN 0-7167-4345-0. 
• Scerri, Eric (2007). The Periodic Table, Its Story and Its Significance. New York: Oxford University Press. ISBN 978-0-19-530573-9. 
• Levine, Ira (2000). Quantum Chemistry. Upper Saddle River, New Jersey: Prentice Hall. ISBN 0-13-685512-1. 
• Griffiths, David (2000). Introduction to Quantum Mechanics (2 ed.). Benjamin Cummings. ISBN 978-0131118928. 
• Cohen, Irwin; Bustard, Thomas (1966). "Atomic Orbitals: Limitations and Variations". J. Chem. Educ. 43 (4): 187. Bibcode 1966JChEd..43..187C. doi:10.1021/ed043p187. http://pubs.acs.org/doi/pdfplus/10.1021/ed043p187. 

External links

• Guide to atomic orbitals
• Covalent Bonds and Molecular Structure
• Animation of the time evolution of an hydrogenic orbital
• The Orbitron, a visualization of all common and uncommon atomic orbitals, from 1s to 7g
• Grand table Still images of many orbitals
• David Manthey's Orbital Viewer renders orbitals with n ≤ 30
• Java orbital viewer applet
• What does an atom look like? Orbitals in 3D
• Atom Orbitals v.1.5 visualization software