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Slater’s rules

- provides estimates of the Effective nuclear charges, Zeff,
experienced by electrons in different atomic orbitals.
- based on experimental ionization energies

Zeff = Z - S
where Z = nuclear charge,
Zeff = effective nuclear charge,
S = screening (or shielding) constant

Values of S may be estimated as follows:
1. Write out the electronic configuration of the
element in the following order and groupings:
(1s), (2s, 2p), (3s, 3p), (3d ), (4s, 4p), (4d ), (4f ), (5s, 5p) etc.

2) or lower shells contributes S = 1. (iii) Each of the electrons in the (n .1) shell contributes S = 0. (ii) Each of the electrons in the (n .2. .00. Consider a particular electron in an ns or np orbital: (i) Each of the other electrons in the (ns. Electrons in any group higher in this sequence than the electron under consideration contribute nothing to S. 3.85.35. np) group contributes S = 0.

35.4.00. Consider a particular electron in an nd or nf orbital: (i) Each of the other electrons in the (nd. np is 100% effective.shielding is ns. nf ) group contributes S = 0. . 1s2 2s2 2p6 3s2 3p6 4s1. . s and p more penetrating Application of Slater’s rules Confirm that the experimentally observed electronic configuration of K. is energetically more stable than the configuration 1s2 2s2 2p6 3s2 3p6 3d1. (ii) Each of the electrons in a lower group than the one being considered contributes S = 1.

85) + (10 x 1. . Z =19 The effective nuclear charge experienced by the 4s electron for the configuration 1s2 2s2 2p6 3s2 3p6 4s1 is: Zeff = Z .00 Thus.(18 x 1.00)] = 2. more stable) that is occupied. in the ground state of potassium.[(8 x 0.00) = 1.For K. it is the 4s atomic orbital (which “feels” greater Zeff.S = 19 .20 For the configuration 1s2 2s2 2p6 3s2 3p6 3d1 is: Zeff = Z .S = 19 .

Electronic Configurations Lanthanides and Actinides of Transition Metals. Dashed lines surrounding elements designate irregularities in orbital filling. . including Solid lines surrounding elements designate filled or half-filled d or f subshells.

Ex. Cr: 4s1 3d5 not 4s2 3d4 The diagram shows that s electrons are removed before d electrons. b) A similar diagram for ions Ex.Schematic Energy Levels for Transition Elements (TE) a) Schematic interpretation of electronic configurations for TE in terms of interorbital repulsion and trend in subshell energies. The electrons with highest n are always removed first in the formation of ions from the transition elements. Sc+: 4s1 3d1 not 4s2 .

Formation of a positive ion by removal of an electron reduces the overall electron repulsion and lowers the energy of the d orbitals more than that of the s orbitals .Exercises: 1. Based on the schematic E level below. Based on Zeff values. 3d3 4s1 or 3d2 4s2. 2. Use Slater’s rules to estimate values of Zeff for (a) a 4s and (b) a 3d electron in a V atom. 3. what is the electronic configuration of Fe+ and V+. which is the possible valence configuration of the ground state of a V+ ion.

X(g) " X+(g) + e - The second ionization energy. IE2 is based on the equation - X+(g) " X+2(g) + e Apparent repeating patterns and some features of IEs: .the general increase in values of IE1 as a given period is crossed . IE1. associated with the removal of the first valence electron in the gas phase. !U(0 K). IE The first ionization energy.the high values of IE1 associated with the noble gases .the very low values of IE1 associated with the group 1 elements .Ionization energies. of an atom is the internal energy change at 0 K.

mino ma jor c h ang e r ch ang e .the rather similar values of IE1 for a given row of d-block elements.the decrease in values of IE1 on going from an element in group 2 or 12 to its neighbour in group 3 or 13 .the discontinuity in values of IE1 on going from an element in group 15 to its neighbour in group 16 ..

reduces the ionization energy. at O. At the fourth p electron. .. The new (8th) electron shares an orbital with one of the previous 2p electrons.The break in the trend at B is attributed to occupation of new p orbital that has most of its electron density farther away from the nucleus than the other electrons. or repulsion between two electrons in the same region of space. The pairing energy. a similar drop in ionization energy occurs. It’s easier to remove a 2p electron in B than 2s2 electrons of Be.

K! Consider two electrons in different orbitals. The repulsion between the electrons if they have anti parallel spins is greater than if they have parallel spins e.e. for a p2 configuration: versus The difference in energy between these two configurations is the exchange energy. K i.g. The key is actually the exchange energy. this is the extra stability that the right-hand configuration has .Filled and half-filled shells are often referred to as possessing a ‘special stability’.

Y(g) + e " Y-(g) The second electron affinity of atom Y is defined for process Y-(g) + e " Y-2(g) . #e is expressed in terms of K "e = $ N(N #1) K 2 where N = number of electrons with parallel spin ! Electron affinities The first electron affinity (EA1) is minus the internal energy change (EA = -!U) for the gain of an electron by a gaseous atom.The total exchange energy.

Repulsive interactions are dominant when an electron is added to an anion and the process is endothermic .The attachment of an electron to an atom is usually exothermic.

electron removal from a (-) ion (opposite for EA) is easier than removal from a neutral atom (IE). . but with smaller absolute numbers.The pattern of electron affinities with changing Z is similar to that of the IEs. . The noble gases have smallest EAs.

The interaction of these two effects results in a gradual decrease in atomic size across each period. more electrons are added to the atom and their mutual repulsion keeps the outer orbitals large. . the electrons are pulled in toward the center of the atom. On the other hand. as the nuclear charge increases. and the size of any particular orbital (thus the size of atom) decreases.Covalent and Ionic Radii (Size) Opposing factors: As the nuclear charge increases.


but the radius of fluoride is 37% larger) .Crystal Radii for Selected Ions Z Element Radius (pm) Alkali metal ions 3 11 19 37 55 Li+ Na+ K+ Rb+ Cs+ 90 116 152 166 181 Alkaline earth ions 4 12 20 38 56 Be2+ Mg2+ Ca2+ Sr2+ Ba2+ 59 86 114 132 149 Other cations 13 30 Al3+ Zn2+ 68 88 Halide ions 9 17 35 53 FClBrI- 119 167 182 206 Other anions 8 16 O2S2- 126 170 Anions are generally larger than cations with similar numbers of electrons (Fand Na+ differ only in nuclear charge.

for the same element. with a much larger change for the cations. . such as O2-. F-.Crystal Radius and Nuclear Charge Ion Protons Electrons Radius (pm) O2- 8 10 126 F- 9 10 119 Na+ 11 10 116 Mg2+ 12 10 86 Crystal Radius and Total Number of Electrons Ion Protons Electrons Radius (pm) O2- 8 10 126 S2- 16 18 170 Se2- 34 36 184 Te2- 52 54 207 Crystal Radius and Ionic Charge Ion Protons Electrons Radius (pm) Ti2+ 22 20 100 Ti3+ 22 19 81 Ti4+ 22 18 75 The radius decreases as nuclear charge increases for ions with the same electronic structure. Within a family. the ionic radius increases as Z increases because of the larger number of electrons in the ions and. Na+. the radius decreases with increasing charge on the cation. and Mg+2.