Slater's rules

In quantum chemistry, Slater's rules provide numerical values for the effective nuclear charge concept. In a many-electron atom, each electron is said to experience less than the actual nuclear charge owning to shielding or screening by the other electrons. For each electron in an atom, Slater's rules provide a value for the screening constant, denoted by s, S, or , which relates the effective and actual nuclear charges as The rules were devised semi-empirically by John C. Slater and published in 1930.[1]

[edit] Rules
Firstly,[1][2] the electrons are arranged in to a sequence of groups that keep s- and p- orbitals with the same principal quantum number together, but otherwise progresses with the orbital ordering of the periodic table (ignoring filling irregularities): [1s] [2s,2p] [3s,3p] [3d] [4s,4p] [4d] [4f] [5s, 5p] [5d] etc. Each group is given a different shielding constant which depends upon the number and types of electrons in those groups preceding it. The shielding constant for each group is formed as the sum of the following contributions: 1. An amount of 0.35 from each other electron within the same group except for the [1s] group, where the other electron contributes only 0.30. (electrons_in_group - 1) 2. If the group is of the [s p] type, an amount of 0.85 from each electron with principal quantum number one less and an amount of 1.00 for each electron with an even smaller principal quantum number 3. If the group is of the [d] or [f], type, an amount of 1.00 for each electron with a smaller principal quantum number In tabular form, the rules are summarized as: Electrons in group(s) with Other electrons in Electrons in all group(s) with principal quantum number nthe same group principal quantum number < n-1 1 0.3 0.35 N/A 0.85 1 N/A 1 1

Group

[1s] [ns,np]

[nd] or [nf] 0.35

[edit] Example
An example provided in Slater's original paper is for the iron atom which has nuclear charge 26 and electronic configuration 1s22s22p63s23p63d64s2. The screening constant, and subsequently the effective nuclear charge for each electron is deduced as:[1]

[edit] Motivation
The rules were developed by John C. Slater in an attempt to construct simple analytic expressions for the atomic orbital of any electron in an atom. Specifically, for each electron in an atom, Slater wished to determine shielding constants (s) and radial quantum numbers (n*) such that provides a reasonable approximation to a single-electron wavefunction. Such a form was inspired by the known wavefunction spectrum of hydrogen-like atoms which have the radial component where n is the principal quantum number, l the azimuthal quantum number, and fnl(r) is an oscillatory polynomial with n - l - 1 nodes.[3] Slater argued on the basis of previous calculations by Clarence Zener[4] that the presence of radial nodes was not required to obtain a reasonable approximation. He also noted that in the asymptotic limit (far away from the nucleus), his approximate form coincides with the exact hydrogen-like wavefunction in the presence of a nuclear charge of Z-s and in the state of principal quantum number n*. Slater then argued, again based on the work of Zener, that the total energy of a N-electron atom with a wavefunction constructed from orbitals of his form should be well approximated as Using this expression for the total energy of an atom (or ion) as a function of the shielding constants and radial quantum numbers, Slater was able to compose rules such that spectral energies calculated agree reasonably well with experimental values for a wide range of atoms. Using the values in the iron example above, the total energy of a neutral iron atom using this method is -2497.2 Ry, while the energy of an iron cation lacking a single 1s electron is -1964.6 Ry. The difference, 532.6 Ry, can be compared to the experimental (circa 1930) K absorption limit of 524.0 Ry.[1]

[edit] References
1. ^ a b c d Slater, J. C. (1930). "Atomic Shielding Constants". Phys. Rev. 36 (1): 5764.
doi:10.1103/PhysRev.36.57.

2. ^ Miessler, Gary L.; Tarr, Donald A. (2003). Inorganic Chemistry. Prentice Hall. pp. 38. ISBN
9780130354716. 3. ^ Robinett, Richard W. (2006). Quantum Mechanics Classical Results, Modern Systems, and Visualized Examples. New York: Oxford University Press. pp. 503. ISBN 978-0-13-120198-9. 4. ^ Zener, Clarence (1930). "Analytic Atomic Wave Functions". Phys. Rev. 36 (1): 5156. doi:10.1103/PhysRev.36.51.