MadSci Network: Chemistry |
Why do electron shells have set limits ?
As we know electron shells or energy levels can only contain a
certain number of electrons ie 2,8,18,32,32,18,8 which match
nicely to the first four quadratic numbers. We know what the
individual shell configuration for each atom is. We use this
information to explain the bonding between atoms, why gases are
inert and it all fits very nicely into groups in the periodic
table. What I would like to know is. Why does each particular
shell have a set number of electrons that match the first four
quadratic numbers. Doesn't this hint that there is a mathematical
law that denotes why this is so, and therefore describes the
nature of all matter ?
The more complex mathematics behind what I am going to tell you can be found in textbooks (such as MacQuarrie's Quantum Chemistry), or you might check out my modest collection of computational chemistry links. Some of the sites have extensive lectures available on molecular and atomic quantum mechanics.The quantum mechanical description of many-electron atoms is based on the Schrödinger equation for the hydrogen atom, which is exactly soluble.[*] The solution tells us that an electron in an atom is fully described by four quantum numbers, labeled n, l, m and s. These quantum numbers have particular allowed values:
Thus, we see that
The first shell contains one orbital.This is a quadratic sequence, but "by accident." There is no underlying mathematics which forces the sequence to be quadratic, it is merely an accident of the properties of the first three quantum numbers associated with an electron in the hydrogen atom.
The second shell contains four (1+3) orbitals.
The third shell contains nine (1+3+5) orbitals.
The fourth shell contains sixteen (1+3+5+7) orbitals.
...
The nth shell contains n2 (1+3+5+7+...+2n-1) orbitals.
All we have left is the Pauli Exclusion Principle, which says that no two electrons in the same atom can share all four quantum numbers; it is often stated as "an atomic orbital can hold a maximum of two electrons."
It is the maximum occupancy of two electrons per orbital which leads to the nice quadratic sequence: each shell 1,2,3,4,...,n can hold 2,8,18,32,...,2n2 electrons.
The obvious next question is, "Why don't the orbitals fill in a logical manner, one shell at a time, instead of skipping around?" But that's another question and anoth er answer!
Dan Berger | |
Bluffton College | |
http://cs.bluffton.edu/~berger |
Schrödinger equations for many-electron atoms involve more than two interacting bodies (the nucleus counts as one, but the electrons must be considered individually). The general many-body problem has not been solved and so we must use approximate methods, based on the solution for the hydrogen atom, to describe all other atoms.
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