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4 Estimating the effective nuclear charge: Slater Type Orbitals (STO)

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?

• A STO assumes radial functions of the general form:

Nr = normalization constant for different orbitals, Nr = f(Z*,n*)

• These orbitals do not depend on the quantum numbers n, l, etc.

• 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 be calculated as (Z – S).

• 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:

E = -13.6 (Z*/n*)2 (Q. Where does 13.6 eV come from?)

Example 1: Predict the energy of a 4s electron in Ca.

Solution: The electron configuration for Ca is 1s22s22p63s23p64s2.

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.

S = 10(1.00) + 8(0.85) + 1(0.35) = 17.15 and Z* = 20 – 17.15 = 2.85

E4s = -13.6[(2.85)2 / (3.7)2] = -8.07 eV

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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

F0 (1s2)(2s22p5) → Z* for one e- in (2s, 2p) = 9 - 6(0.35) - 2(0.85) = 5.20

F+ (1s2)(2s22p4) → Z* for one e- in (2s, 2p) = 9 - 5(0.35) - 2(0.85) = 5.55

 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

Compare to experimental +17 eV.

Q. How do you define electron affinity (EA)?

HOMEWORK: Find the EA of a fluorine atom in the gas phase.

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Using much more complicated quantum mechanical approaches and powerful computers,
very accurate Zeff can be calculated:

Source: Shriver & Atkins, Inorganic Chemistry, 3rd Edition.

 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!

1.5 Atomic configurations

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

• Exchange energy: Electrons of like spin in energy degenerate orbitals can


“exchange” leading to an overall lower energy (quantum mechanical resonance
phenomenon.)

• Another way of looking at this is to consider a diagram of


the px and py orbitals of an atom. Although these orbitals are
orthogonal (zero overlap integral), there is nevertheless a
region of actual orbital overlap in space (shown in red).

• Consider one electron in each orbital. If they have opposite


spin, their spatial wave function can put them in exactly the same space at the same
time (high electrostatic repulsion). If they have the same spin, there must be a
constraint on their spatial wave function so as to not put them in exactly the same
space at the same time (therefore lower electrostatic repulsion if spin is the same)

• Leads to Hund’s Rule of maximum multiplicity:


Energy degenerate orbitals are filled with electrons in such a way that the maximum
possible total spin is realized.

• Consequences:

As a general rule, the most stable oxidation states are those with

- completely filled/empty (sub)shells → octet rule

- exactly half-filled (sub)shells → maximizes exchange energy

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Applications:

• Using these concepts we can qualitatively/empirically predict the stability of


oxidation states!

Examples:

Phosphorus

P0 [Ne] 3s23p3 stable in at least three different allotropic forms

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.

Red phosphorus can be amorphous or can be crystalline. In


its crystalline form it forms chains that can be described as
P4 units joined by breaking one bond of the tetrahedron and
making a bond with the adjacent tetrahedron. Red P does
not readily ignite in air but it thermally decomposes to white
P upon heating to 260 °C. This is what happens when you
strike a match.

Black phosphorus is thermally stable. It is a flaky solid that


resembles carbon. In the crystal structure of black P is
shown.

CONCLUSION: Relative stability also depends on other


factors such as structure and bonding.

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P+ [Ne] 3s23p2 very rarely observed

P2+ [Ne] 3s23p1 very rarely observed

P3+ [Ne] 3s23p0 very common: e.g., organophosphines PR3

2,2'-Bis(diphenylphosphino)-1,1'-binaphthyl,
commonly known as BINAP, is a chiral ligand used to
design enantioselective homogeneous catalysts.

Ryoji Noyori won the Nobel Prize in Chemistry in


2001 for asymmetric hydrogenation catalysis,
primarily using Rh and Ru complexes of BINAP as
catalysts.

P4+ [Ne] 3s13p0 very rarely observed

P5+ [Ne] 3s03p0 very common: phosphates (e.g. P2O5)

Phosphorus pentoxide is an anhydride of phosphoric acid. As such, it


is a powerful desiccant (drying agent). We use it to dry acetonitrile in
our laboratory stills. **Caution: P2O5 reacts violently with water.

Phosphates are very common in biological chemistry (ADP,


ATP, DNA, hydroxyapatite, etc.)

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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.

The electronegativity difference (χN = 3.04;


χP = 2.19) is less than in the siloxane link,
but some multiple bond character
strengthens the framework.

Phosphazene polymers can be biodegradable


with harmless decomposition products.

Here are two figures from an article


describing the use of a tube made of PEIP as
a prosthetic nerve guide for repairing nerve
damage in a living organism.

Ref: F. Langone, S. Lora, et al., Biomaterials, 16 (1995) 347-353.

Sulfur

S2- [Ne]3s23p6 sulfides (e.g. H2S)

S0 [Ne]3s23p4 S4+ [Ne]3s23p0 sulfites (e.g. Na2SO3)

S6+ [Ne]3s03p0 sulfates (e.g. Na2SO4)

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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