Electron orbital

In quantum chemistry, an electron orbital (or more often just orbital) is a synonym for a quadratically integrable one-electron wave function. Here "orbital" is used as a noun. In quantum mechanics, the adjective orbital is often used as a synonym of "spatial", in contradistinction to spin.

Types of orbitals

Several kinds of orbitals can be distinguished.

Atomic orbital

The basic kind of orbital is the atomic orbital (AO). This is a function depending on a single 3-dimensional vector r_A1, which is a vector pointing from point A to electron 1. Generally there is a nucleus at A. The following notation for an AO is frequently used,

$\chi _{i}(\mathbf {r} _{A1}),$

but other notations can be found in the literature. Sometimes the center A is added as an index: χ_{A i}. We say that χ_{A i} (or, as the case may be, χ _i) is centered at A. In numerical computations AOs are either taken as Slater type orbitals (STOs) or Gaussian type orbitals (GTOs). Hydrogen-like orbitals are rarely applied in numerical calculations, but form the basis of many qualitative arguments in chemical bonding and atomic spectroscopy.

The orbital is quadratically integrable, which means that the following integral is finite,

$0\leq \int _{-\infty }^{\infty }\int _{-\infty }^{\infty }\int _{-\infty }^{\infty }\chi _{i}(\mathbf {r} _{A1})^{*}\chi _{i}(\mathbf {r} _{A1})\;dx_{A1}\,dy_{A1}\,dz_{A1}\ <\infty .$

Its integrand being real and non-negative, the integral is real and non-negative. The integral is zero if and only if χ _i is the zero function.

Molecular orbital

The second kind of orbital is the molecular orbital (MO). Such a one-electron function depends on several vectors: r_A1, r_B1, r_C1, ... where A, B, C, ... are different points in space (usually nuclear positions). The oldest example of an MO (without use of the name MO yet) is in the work of Burrau (1927) on the single-electron ion H₂⁺. Burrau introduced spheroidal coordinates (a bipolar coordinate system) to describe the wavefunction of the electron of H₂⁺.

Lennard-Jones introduced the following linear combination of atomic orbitals (LCAO) way of writing an MO φ:

$\phi (\mathbf {r} _{1})=\sum _{A=1}^{N_{\mathrm {nuc} }}\sum _{i=1}^{n_{A}}c_{iA}\chi _{i}(\mathbf {r} _{A1}),\qquad c_{iA}\in \mathbb {C} ,$

where A runs over N_nuc different points in space (usually A runs over all the nuclei of a molecule, hence the name molecular orbital), and i runs over the n_A different AOs centered at A. The complex coefficients c _iA can be calculated by any of the existing effective one-electron quantum chemical methods. Examples of such methods are the Hückel method and the Hartree-Fock method.

Spinorbitals

The AOs and MOs defined so far depend only on the spatial coordinates r_A1 of electron 1. In addition, an electron has a spin coordinate μ, which can have two values: spin-up or spin-down. A complete set of functions of μ consists of two functions only, traditionally these are denoted by α(μ) and β(μ). These functions are eigenfunctions of the z-component s_z of the spin angular momentum operator with eigenvalues ±½.

Spin atomic orbital

The most general spin atomic orbital of electron 1 is of the form

$\chi _{i}^{+}(\mathbf {r} _{A1})\alpha (\mu _{1})+\chi _{i}^{-}(\mathbf {r} _{A1})\beta (\mu _{1})$

which in general is not an eigenfunction of s_z. More common is the use of either

$\chi _{i}(\mathbf {r} _{A1})\alpha (\mu _{1})\quad {\hbox{or}}\quad \chi _{i}(\mathbf {r} _{A1})\beta (\mu _{1}),$

which are eigenfunctions of s_z. Since it is rare that different AOs are used for spin-up and spin-down electrons, we dropped the superscripts + and −.

Spin molecular orbital

A spin molecular orbital is usually either

$\phi ^{+}(\mathbf {r} _{1})\alpha (\mu _{1})\quad {\hbox{or}}\quad \phi ^{-}(\mathbf {r} _{1})\beta (\mu _{1}).$

Here the superscripts + and − might be necessary, because some quantum chemical methods distinguish the spatial wave functions of electrons with different spins. These are the so-called different orbitals for different spins (DODS) (or spin-unrestricted) methods. However, many quantum chemical methods apply the spin-restriction:

$\phi ^{+}(\mathbf {r} _{1})=\phi ^{-}(\mathbf {r} _{1})=\phi (\mathbf {r} _{1}).$

Chemists express this spin restriction by stating that two electrons, one with spin up (α) and one with spin down (β), are placed in the same spatial orbital φ. This means that the total N-electron wave function contains a factor of the type φ(k)α(k)φ(k+1)β(k+1), with 1 ≤ k < N.

History of term

Orbit is an old noun (1548), initially indicating the path of the Moon and later the paths of other heavenly bodies as well. The adjective "orbital" had (and still has) the meaning "relating to an orbit". When Ernest Rutherford in 1911 postulated his planetary model of the atom (the nucleus as the Sun, and the electrons as the planets) it was natural to call the paths of the electrons "orbits". Bohr, although he was the first to recognize (1913) orbits as stationary states of the hydrogen atom, used the word as well. However, after Schrödinger (1926) had solved his wave equation for the hydrogen atom (see this article for details), it became clear that the electronic "orbits" did not resemble planetary orbits at all. The wave functions of the hydrogen electron are time-independent and smeared out. They are more like unmoving clouds than like planetary orbits. As a matter of fact, the angular parts of the hydrogen wave functions are spherical harmonics and hence they have the same appearance as spherical harmonics. (See spherical harmonics for a few graphical illustrations).

In the 1920s electron spin was discovered, where upon the adjective "orbital" started to be used in the meaning of "non-spin", that is, as a synonym of "spatial". In scientific papers of around 1930 one finds discussions about "orbital degeneracy", meaning that the spatial (non-spin) parts of several one-electron wave functions have the same energy. Also the terms orbital- and spin-angular momentum date form these days.

In 1932 Robert S. Mulliken coined the noun "orbital". He wrote: From here on, one-electron orbital wave functions will be referred to for brevity as orbitals. Then he went on to distinguish atomic and molecular orbitals.

Later the somewhat unfortunate term "spinorbital" was introduced for the product functions φ(r₁)α(1) and φ(r₁)β(1) in which φ(r₁) has the tautological name "spatial orbital" and α(1) and β(1) are called "one-electron spin functions". The term "spinorbital" is unfortunate because it ignores the contradistinction between spin and space and may lead to confusement. For instance, one of the pioneers of theoretical chemistry, Walter Heitler, correctly contraposes two-electron spin functions and two-electron orbital functions. In the phrase two-electron orbital function, Heitler uses orbital as an adjective synonymous with spatial, and does not refer to a "two-electron orbital", (there is no such thing as a two-electron orbital!), as an inexperienced reader may erroneously interpret it.

References and notes

(To be continued)