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NOTE: This section does not appear in your textbook. For further understanding, consult
Miessler and Tarr.
PREMISE: We can calculate an approximate value for the effective nuclear charge
“felt” by an electron in a particular orbital of a particular atom or ion. We can do this by
focussing on a single electron and lumping all the shielding effects from the other
electrons into one shielding parameter S.
• Using Slater Type Orbitals (STO), instead of more realistic orbitals, is a reasonable
and simple approximation that makes this calculation much easier.
Q. What is a STO?
• i.e., s, p, and d orbitals all look the same and have only one node at r = 0.
• STO functions work well in approximating true radial function at distances r in the
range of covalent bonds, but fail to describe electron distribution in inner shells.
• Slater devised empirical rules to determine the values of Z* and n* (see next page).
• The effective nuclear charge Z* can then be used for such purposes as calculating
ionic radii (above equation) and electronegativities, hardness, HOMO/LUMO
energy levels, etc. of the elements (see notes to come).
• More refined calculations can be used when greater accuracy is needed, however
gross trends are nicely reproduced by this oversimplified model.
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Source: Purcell & Kotz, Inorganic Chemistry, 1977.
• For a series of elements with the same (ns,p) or (nd) group electrons, Z* regularly
increases by 0.65: Z*n+1 = Z*n + 0.65
• Application of STO’s: Ideally, Slater’s rules permit the calculation of the energy
of any electron in any atom or ion by the formula:
The ten electrons with n=1 and n=2 contribute 1.00 each to the shielding, the eight
electrons with n=3 each contribute 0.85, and the other 4s electron contributes 0.35.
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Example 2: Calculate the first ionization energy (IE) of a fluorine atom in the gas phase:
Solution:
IE = EF+ - EF0 …this is the difference in TOTAL energies…
Z = 9; n = 2
We are using a “Slater orbital assumption”. In other words, we are assuming that the
2s and 2p orbitals “look the same”…i.e., spherical electron density distribution.
We are ionizing (removing an e-) from the (2s, 2p) orbital group.
Since the electrons in the 1s orbital “see” the same nuclear charge before and after
ionization (according to this approximation), their contributions to the energies of F0
and F+ are the same and will cancel when the difference is taken…
THEREFORE:
IE = -13.6[{6(Z*/n*)22s,2p}F+ - {7(Z*/n*)22s,2p}F0]
= -13.6[{6(5.55/2)2} – {7(5.20/2)2}]
= -13.6[46.20 – 47.32]
= +15.2 eV
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Using much more complicated quantum mechanical approaches and powerful computers,
very accurate Zeff can be calculated:
The above values originate from a HF-SCF calculation using the true radial functions
as starting points for solving the Schrödinger equation with the complete Hamiltonian
of the system (see CHEM 386).
Note the difference in Z* for an electron in the 2s versus the 2p orbital…no longer
using Slater-type orbitals!
Pauli’s rule: No two electrons in the same atom/molecule can have the same set of
quantum numbers
n l ml ms
Two electrons in the same orbital must be spin correlated, i.e. have opposite spins ± ½.
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• Because of Coulomb repulsion, pairing of electrons in one orbital costs energy:
→ Charge Correlation Energy
• Consequences:
As a general rule, the most stable oxidation states are those with
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Applications:
Examples:
Phosphorus
White phosphorus is composed of P4 units. These are highly strained units and ignite (i.e.
oxidize in air) at 30 °C. White P is used as a chemical warfare agent.
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P+ [Ne] 3s23p2 very rarely observed
2,2'-Bis(diphenylphosphino)-1,1'-binaphthyl,
commonly known as BINAP, is a chiral ligand used to
design enantioselective homogeneous catalysts.
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Phosphazenes (compounds with –N=PR2–
linkages) provide a good example of stable
species in which N and P are in different
oxidation states.
Sulfur
What are the most likely oxidation states of Ga, Sn, Sr, Br, Xe ?
HOMEWORK: Use Slater’s rules to calculate Z* for highest occupied atomic orbitals of
the elements Li through F and compare the trend in Z* to the trend in electronegativity.
Textbook problems: 1.19-1.22, 1.26, 1.27, 1.29.
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