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The simplest atomic orbitals are those that occur in an atom with a single electron, such as the Hydrogen Atom . In this case the atomic orbitals are the Eigenstate s of the Hydrogen Hamiltonian . They can be obtained analytically (see Hydrogen Atom ). An atom of any other element Ion ized down to a single electron is very similar to hydrogen, and the orbitals take the same form.

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, numerical approximations must be used. Atomic orbitals are often expanded in a Basis Set of Slater-type Orbital s which are orbitals of hydrogen-like atoms with arbitrary nuclear charge ''Z''.

A given (hydrogen-like) atomic orbital is identified by unique values of three , ''l'' , and ''ml'' . 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 State s) of the hydrogen-like atoms are its atomic orbital. 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 Combination s) of multiple orbitals. See Linear Combination Of Atomic Orbitals Molecular Orbital Method .

The quantum number ''n'' first appeared in the Bohr Model . It determines, among other things, the distance of the electron from the nucleus; all electrons with the same value of ''n'' lay at the same distance. Modern quantum mechanics confirms that these orbitals are closely related. 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 ".


Mathematical characterization



Derivation


Atomic orbitals are solutions to the Schrödinger Equation . In this case, the Potential term is the potential given by Coulomb's Law :

:V = - rac{1}{4 \pi \epsilon_0} rac{Ze^2}{r}

where
  • The first term is a constant, usually abbreviated by the letter ''k'',

  • ''Z'' is the Atomic Number ,

  • ''e'' is the Elementary Charge ,

  • ''r'' is the magnitude of the distance from the nucleus.


The wavefunction is a function of three spatial variables, so that after removing the Time -dependence, the Schrödinger equation is a Partial Differential Equation in three variables (see Separation Of Variables ). However, since the potential is spherically Symmetric , it is profitable to write the equation in Spherical Coordinates . In this form, any individual Eigenfunction ψ can be written as a product of three single-variable functions, often denoted as follows:

:\psi(r, heta, \phi) = R(r)f( heta)g(\phi)

(where θ represents the polar angle ( Colatitude ) and φ the Azimuth al angle.) It can further be reduced to three separate equations, each in one variable.

Two separations are required, resulting in two separation constants. A third arbitrary constant results from the application of boundary conditions to ''R''. The equations given below use a form of the separation constants that seems arbitrary, but it simplifies matters later on.

: rac{1}{R(r)} rac{d}{dr} \left ( r^2 rac{dR}{dr} ight ) + rac{2 \mu r^2}{\hbar^2}(E-V(r)) = l(l+1)

: rac{1}{g(\phi)} rac{d^2 g(\phi)}{d\phi^2} = -m^2

:l(l+1)\sin ^2( heta) + rac{\sin( heta)}{f( heta)} rac{d}{d heta} \left \sin( heta) rac{df}{d heta} ight = m^2

where:


Results


In addition to \ell and ''m'', a third arbitrary integer, called ''n'', emerges from the boundary conditions placed on ''R''. The functions ''R'', ''f'' and ''g'' that solve the equations above depend on the values of these integers, called '' Quantum Number s''. As a result, it is customary to subscript the functions with the values of the quantum numbers they depend on. The forms of the functions are:

:\psi = C_{nlm}\, R_{nl}(r)\, f_{lm}( heta)\, g_m(\phi)

:R_{nl}(r) = e^{- rac{r}{a_0n}} \left ( rac{2r}{n a_0} ight )^l L_{n-l-1}^{2l+1} \left( rac{2 r}{n a_0} ight)

  <math>C {nlm}</math> Is A "http://wwwinformationdelightinfo/encyclopedia/entry/normalization_constant" class="copylinks">Normalization Constant Since the Wavefunction must be normalized ( <math> \int_^3} \Psi ^2 d^3 ec{r} = 1 </math> ), by calculating this integral we get:
  :<math>\left \mathbf L Ight \hbar \sqrt{l(l+1)}</math>