Electron Configuration &

Chemical Periodicity
Part I
Prepared by: Michael Angelo R. Circulado
Characteristics of Many-Electron Atoms
§ The Schrödinger equation does not give exact solutions for the energy levels of many-
electron atoms.
§ The three quantum numbers n, l, ml describe the size, shape, and orientation in space,
respectively, of an atomic orbital.
§ A fourth quantum number describes a property called spin, which is a property of the
electron and not the orbital.
§ Spin quantum number, ms - has 2 possible values, +½ or -½.
§ Thus, each electron in an atom is described completely by a set
of four quantum numbers: the first three describe its orbital, and
the fourth describes its spin.
§ For the lone electron of H, it has the following quantum numbers:
n = 1, l = 0, ml = 0, ms = +½
Characteristics of Many-Electron Atoms
Pauli’s Exclusion Principle
§ Austrian physicist Wolfgang Pauli formulated the exclusion principle: no two electrons
in the same atom can have the same four quantum numbers.
§ Therefore, the second He electrons has similar quantum numbers with the first electron,
except the spin: n = 1, l = 0, ml = 0, ms = -1/2
§ The major consequence of the exclusion principle is that an atomic orbital can hold a
maximum of two electrons, which must have opposing spins.
Electrostatic Effects and Energy-Level Splitting
§ The first energy-level splitting occurs with Li (Z = 3). The first 2
electrons fills its 1s orbital, so the 3rd electron must go into the n
= 2 level.
§ But, this level has 2s and 2p subshells: which does the 3rd
electron enter?
§ Since 2s is lower in energy than 2p, the 3rd electron goes into
that subshell.

§ Effect of Nuclear Charge (Z) on Subshell Energy

§ A higher nuclear charge (more protons in the nucleus) increases
nucleus-electron attractions and, thus, lowers subshell energy
(stabilizes the atom)
Electrostatic Effects and Energy-Level Splitting
§ Shielding: Effect of Electron Repulsions on Subshell Energy
§ In many-electron atoms, each electron “feels” not only the attraction to the nucleus but
also repulsions from other electrons.
§ Hence, each electron “shield” other electrons to some extent from the nuclear charge.
§ Shielding (or screening) reduces the full nuclear charge to an effective nuclear charge
(Zeff), the nuclear charge an electron actually experiences, and this lower nuclear charge
makes the electron easier to remove.
1. Electrons in the same energy level
shield each other somewhat.
2. Electrons in inner energy levels
effectively shield those in outer
energy levels. They cause a much
lower Zeff.
Electrostatic Effects and Energy-Level Splitting
§ Penetration: Effect of Orbital Shape on Subshell Energy
§ To see why the 3rd Li electron occupies the 2s subshell rather than the 2p, the orbital
shapes should be considered, that is their radial probability distributions.
§ A 2p orbital (orange curve) is slightly closer to the nucleus,
on average, than the major portion of the 2s orbital (blue
curve).
§ But a small portion of the 2s radial probability distribution
peaks within the 1s region.
§ Thus, an electron in the 2s orbital spends part of its time
“penetrating” very close to the nucleus.

§ Penetration has two effects:

§ It increases the nuclear attraction for a 2s electron over that for a 2p electron.
§ It decreases the shielding of a 2s electron by the 1s electrons.
Electrostatic Effects and Energy-Level Splitting
§ Splitting of Levels into Subshells
§ In general, penetration and the resulting effects on shielding split an energy level into
subshells of differing energy.
§ The lower the l value of a subshell, the more its electrons penetrate, and so the greater
their attraction to the nucleus.
Order of subshell energies: s < p < d < f
Periodic Table & Electron Configurations
§ Electron configurations found in the periodic table refer to the ground-state electron
configuration of each element－the lowest energy distribution of electrons in the
subshells of its atoms.
§ There is a recurring pattern in electron configurations, which is the basis for recurring
patterns in chemical behavior.
§ Aufbau principle - states that electrons fill subshells of lowest energy level first, then
the subshells of higher energy levels
§ Two ways to indicate the distribution of electrons in subshells:
§ Electron configuration

§ Orbital diagram
Periodic Table & Electron Configurations
§ Building Up Period 1
§ Hydrogen

§ Helium

§ Pauli’s exclusion principle states than an orbital can hold no more than 2 electrons.
Therefore, in He, the n = 1 level is filled

§ Building Up Period 2
§ Lithium

§ Beryllium

§ Boron
Periodic Table & Electron Configurations
§ To minimize electron-electron repulsions, the 6th electron of carbon enters one of the
unoccupied 2p orbitals rather than the 2p orbital that already holds 1 electron.
§ This exemplifies Hund’s rule: when orbitals of equal energy (degenerate) are available,
the electron configuration of lowest energy has the maximum number of unpaired
electrons with parallel spins.

§ Carbon

§ Nitrogen

§ Oxygen

§ Fluorine

§ Neon
Periodic Table & Electron Configurations
§ Elements in the same group have similar outer electron configurations and similar
patterns of reactivity.
§ For example, He and Ne in Groups 8A both have filled outer subshells and neither
element forms compounds.
Periodic Table & Electron Configurations
§ Building Up Period 3
§ The 3rd energy level splits into 3s, 3p and 3d subshells.
§ Condensed electron configurations have the element symbol of the previous noble gas
to represent its configuration, followed by that of the energy level being filled.
Periodic Table & Electron Configurations
§ Building Up Period 4
§ Period 4 contains the first series of transition elements, those in which d orbitals are
being filled. Three factors affect the filling pattern in periods with transition series.

1. Effects of shielding and penetration on subshell energy

• The 4s subshell is filled before the 3d subshell. This switch in filling order is due to
shielding and penetration effects.
• 3d electrons are shielded very effectively from the nuclear charge; on the other hand,
4s electrons penetrates close to the nucleus at times, so it is subject to greater
attraction.
• As a result, the 4s orbital is slightly lower in energy than the 3d and fills first.
• In any period, the ns subshell fills before the (n-1)d subshell.
Periodic Table & Electron Configurations
2. Filling the 4s and 3d subshells
Periodic Table & Electron Configurations
3. Stability of half-filled and filled subshells
• There are some transition elements that do not follow the aufbau principle. Examples
are Cr and Cu.
• For Cr, both 4s and 3d subshells are half-filled instead of having a [Ar]4s23d4
configuration.

• For Cu, it prefers to have a filled 3d subshell and half-filled 4s subshell instead of the
expected configuration ([Ar]4s23d9).

• From these exceptions, it can be concluded that half-filled and filled subshells are
unexpectedly stable (low in energy).
General Principles of Electron Configurations
General Principles of Electron Configurations
• Orbital filling order

• Categories of electrons
1. Inner (core) electrons - fill all the lower energy levels of an atom, includes any
completed transition series

2. Outer electrons - those in the highest energy level

General Principles of Electron Configurations
3. Valence electrons - outermost electrons involved in forming compounds:
• For main-group elements, the valence electrons are the outer electrons
• For transition elements, in addition to the outer ns electrons, the (n-1)d electrons are
also valence electrons

• Group and Period Numbers

• Among the main-group elements (A groups), the group number equals the number of
outer electrons.
• The period number is the n value of the outermost s and p subshells.
• The period number - 1 is the n value of the outermost d subshell (Periods 4 - 7).
• The period number - 2 is the n value of the outermost f subshell (Periods 6 - 7).
• For an energy level, the n2 value is the number of orbitals, and 2n2 is the maximum
number of electrons (or elements).
Intervening Series: Inner Transition Elements
• Period 6 contains the first of two series of inner transition elements, those in which f
orbitals are being filled.
• There are seven f orbitals and thus can hold a maximum of 14 electrons.
• The Period 6 inner transition series, called the lanthanides (or rare earths), occurs
after La and in it the 4f orbitals are filled.
• The Period 7 inner transition series, called the actinides, occurs after Ac, and in it the
5f orbitals are filled.
• Thus, in Periods 6 and 7, the filling sequence is ns, first of the (n-1)d, all (n-2)f,
remainder of the (n-1)d, and np. Period 6 ends with the 6p subshell, and Period 7 ends
with the 7p subshell.
Similar Electron Configurations Within Groups
• Electron configurations of elements in a group are similar, especially among the main-
group elements (s-block and p-block).
• Similar outer electron configurations correlate with similar chemical behavior.
Examples:
• Group 1A elements (alkali metals): Li, Na, K, Rb, Cs & Fr all have the outer electron
configuration ns1. All are highly reactive metals which tend to lose their valence
electrons.
• Group 7A elements (halogens): F, Cl, Br, I & At all have the outer electron configuration
ns2np5. All are reactive nonmetals that occur as diatomic molecules.