Electronic Structure

The Wave -Particle Nature of Electromagnetic (E.M.) Radiation

Greek letter “lambda” à wavelength

λ

speed of light (c) c = 3.0 x 108 ms-1

frequency (ν; Greek “nu”) – the number of peaks or troughs that pass a
given point per second; units of s-1 (Hertz)

E.M. radiation has both wave-like and particle -like properties (de Broglie, 1925). A “particle” of E.M. radiation is called a
photon.
Important relationships for E.M. radiation

λν = c E = hν h is Planck’s constant; h = 6.626 x 10-34 Js

Example Problem (using the important relationships): What is the minimum wavelength of light necessary to remove an
electron from an atom on the surface of solid gold? The
ionization energy of gold is 492 kJ/mol

The Original Model of Electronic Structure (Niels Bohr, 1913) – proposed as an explanation of the discrete line
spectrum of hydrogen

In Bohr's model, electrons orbit the nucleus in discrete, or quantized, energy levels (shells)

etc. Shells are label by a value of n, called the principal energy level

n=3 Important points: 1) As n goes up, so does energy and distance from nucleus
n=2 2) The maximum number of electrons per level is 2n2
n=1

The Problem with Bohr’s Model

Good News – Bohr model allows derivation of equations that can calculate the wavelengths of spectral lines for the
hydrogen atom

Bad News – Bohr model calculations apply only to one-electron systems, like the H atom or the He+1 ion

The Schrödinger Equation – The Quantum Mechanical Description of Electronic Structure

Erwin Schrödinger (1926) – using brilliant mathematical intuition, applied the behavior of waves to electrons in the atom

Schrödinger equation – a wave equation with many solutions

Orbitals – mathematical regions of space where electrons are found with ~90% probability; orbitals are essentially the
solutions of the Schrödinger equation
Quantum Numbers

Each distinct orbital in an atom is described by 3 interrelated quantum numbers (n, L, mL) which appear in the solution of
the Schrödinger equation.

1) n à a) principal quantum number; can take integer values n = 1, 2, 3, ….

b) determines size of orbital (distance from nucleus) and denotes energy level (shell number)
c) as n increases, size and energy increase

2) L à angular momentum quantum number; takes values L = 0, 1, 2,… n 1

L = 0 à s orbital (spherical shape) L = 1 à p orbital (dumbbell shape)

L = 2 à d orbital (cloverleaf, expect for one) L = 3 à f orbital (weird shape)

3) mL à magnetic quantum number; takes integer values mL = −L to +L, zero included

How are Orbitals Arranged in Atoms and How are Quantum Numbers Assigned to Orbitals?

energy
levels etc.
(shells)

mLà 0 -1 0 +1 -2 -1 0 +1 +2 -3 -2 -1 0 +1 +2 +3
L=0 L=1 L=1 L=1 L=2 L=2 L=2 L=2 L=2 L=3 L=3 L=3 L=3 L=3 L=3 L=3
n=4 n=4 n=4 n=4 n=4 n=4 n=4 n=4 n=4 n=4 n=4 n=4 n=4 n=4 n=4 n=4
n=4 ___ ___ ___ ___ ___ ___ ___ ___ ___ ___ ___ ___ ___ ___ ___ ___
4s three 4p’s five 4d’s seven 4f’s

mLà 0 -1 0 +1 -2 -1 0 +1 +2
L=0 L=1 L=1 L=1 L=2 L=2 L=2 L=2 L=2
n=3 n=3 n=3 n=3 n=3 n=3 n=3 n=3 n=3
n=3 ___ ___ ___ ___ ___ ___ ___ ___ ___
3s three 3p’s five 3d’s

mLà 0 -1 0 +1
L=0 L=1 L=1 L=1
n=2 n=2 n=2 n=2
n=2 ___ ___ ___ ___
2s three 2p’s

mL = 0
L=0
n=1
n=1 ___
1s

Nucleus
Electron Spin and the “fourth quantum number”

A spinning electron generates a magnetic field; the field direction (up or down) depends on the direction in which the
electron is spinning. Up-spin and down-spin electrons are distinguished by ms , which is, for convenience, referred to as
the spin quantum number, even though it does not come from the Schrödinger equation, but rather from experiment.
There are two possible values for ms: ms= +1/2 and ms = -1/2

Pauli Exclusion Principle – no 2 electrons in an atom can have the same 4 quantum numbers (n, L, mL, ms)
A direct consequence of the Exclusion Principle à an individual orbital can hold a maximum of 2 electrons

Subshell Maximum Number of Electrons in Subshell

s 2x1= 2
p 2x3=6 (3 distinct orbitals in p subshell, and each orbital can hold 2 e-)
d 2 x 5 = 10 (5 distinct orbitals in d subshell, and each orbital can hold 2 e-)
f 2 x 7 = 14 (7 distinct orbitals in f subshell, and each orbital can hold 2 e-)

Aufbau (“building up”) Principle the process of building up electrons configurations by adding electrons to successive
orbitals

Basic guiding principle à orbitals get filled in order of increasing energy

Important Considerations: 1) In a given shell, orbital energy increases in the order s < p < d < f
(lower energy orbitals have higher penetrating power, and are closer to the nucleus)
2) All orbitals in a given subshell (p, d, or f) are degenerate – they have the same energy

Examples and Notes

Element Orbital Diagram Electron Configuration

H ____ _____ _____ _____ _____ 1s1

1s 2s 2p

He 1s2
____ _____ _____ _____ _____
1s 2s 2p

Li 1s22s1
____ _____ _____ _____ _____
1s 2s 2p

C ____ _____ _____ _____ _____ 1s22s2 2p2

1s 2s 2p
Note: Hund’s Rule – the lowest energy configuration is the one with the
most unpaired electrons in a particular subshell
(i.e. only pair electrons in an orbital when necessary)

O ____ _____ _____ _____ _____ 1s2 2s22p4

1s 2s 2p

Ne 1s22s2 2p6
____ _____ _____ _____ _____
(completely filled n =1 and n = 2 shells)
1s 2s 2p
Continuing on…..

Na à 1s22s2 2p63s1 or [Ne] 3s 1 (noble gas shorthand notation)

Class example : What would the e- configuration of Cl, in both full and noble gas shorthand notation?

Jump to Period 4….

K is [Ar] 4s 1 , Ca is [Ar] 4s 2 . What about Sc, the first transition metal? Sc à [Ar] 4s 1 3d1

** The 3d subshell gets filled after the 4s subshell (because the 3d energy is slightly higher than the 4s energy)**

Continuing in Period 4: Ti à 1s2 2s22p63s23p64s2 3d2 V à [Ar] 4s 23d3

We would expect Cr to be [Ar] 4s 2 3d4 , but it is actually [Ar] 4s 13d5.

Two trends are present here: 1) Half-filled and fully-filled subshells are conditions of relative stability
2) For Cr and Mo, the s and d subshells are close enough in energy that promotion of
an s electron to a d electron is favored by Hund’s rule

** Trend 1 is evident for Cu, Ag, and Au, all of which end their configurations with s1 d10 **

Practice Examples

Ru Sn Ag

When do the 4f orbitals show up? Not until Period 6, after the 6s subshell has been filled

More practice examples

Yb Ir Bi

**** Super Important ******

The valence shell in an atom is the outermost (i.e. highest value of n) occupied or partially occupied shell.
Electrons that are in any subshell within the valence shell are called valence electrons

Electrons in shells with n less than the valence value are called core or inner-shell electrons

** elements in the same Group on the periodic table have the same valence electron configuration, and therefore show
similar chemical behavior ***

Lewis Dot Structures à a convenient way of representing valence electrons for the Group A elements; the element
symbol is surrounded by one dot for each valence electron.

Li Be B C N O F Ne
Ion Formation
*** A completely filled outer shell gives the noble gases (Group 8A) exceptional chemical stability ***
(i.e. an octet of electrons)

Look at the electron configuration for S à 1s22s22p6 3s23p 4

If S gains 2 electrons to form S-2 à 1s22s22p63s23p6 = Ar! S2- has the same electron configuration as Ar!
Important principle : Group A nonmetals tend to gain enough electrons to become isoelectronic with a noble gas
(i.e. group A nonmetals gain electrons to attain a stable noble gas configuration)

Look at the electron configuration for K à 1s22s22p63s23p 64s1

If K loses 1 electron to form K+1 à 1s22s22p63s23p6 = Ar! K +1 has the same electron configuration as Ar!
Important princ iple : Group A metals tend to lose enough electrons to become isoelectronic with a noble gas
(i.e. group A metals lose electrons to reveal the underlying noble gas configuration)

What about the variable charge Group A cations? (e.g. Sn, Pb, In, Ga, Sb, etc.)
General principle à electrons can be lost from the valence p subshell or the valence s and p subshells

Example Ga can form 2 different cations: Ga +1 and Ga 3+

The electron configuration of Ga is [Ar]4s 23d104p1
When Ga forms Ga+1 the electron is lost from the p subshell à Ga+1 = [Ar]4s 23d10
When Ga forms Ga +3 the electrons are lost from the s and p subshells à Ga+3 = [Ar]3d10

Ionization Energy -- the minimum energy required to remove an electron from a gaseous atom in it ground (lowest
energy) state.
Important notes:
1) Ionization energy increases for each successive electron removed (i.e. 1st I.E. < 2nd I.E. < 3rd I.E. etc.)
2) Ionization energy for core electrons is much greater than for valence electrons

Electron Affinity -- the energy change when an electron is accepted by an atom in the gaseous state

Effective Nuclear Charge

Effective nuclear charge refers to the charge that electrons in an atom actually feel from the positive nucleus. The
element He, for example, has 2 electrons in a 1s orbital about a nucleus with charge +2. As far as each electron is
concerned, however, the nuclear charge appears to be less than +2 because this charge is partially offset by the mutual
repulsion of the electrons.
Important points: 1) electrons in a given shell are shielded (screened) by electrons in inner shells but not by electrons
in outer shells
2) inner filled shells shield (screen) outer electrons more effectively than ele ctrons in the same
subshell shield (screen) one another
 Periodic Trends
Atomic Size

Across a period, atomic size decreases from left to right. The reason for this is that electrons, which are added to
the same shell when moving across a period, do not shield each other sufficiently to counterbalance the increasing nuclear
charge. As a result, effective nuclear charge increases, and the atomic size decreases as electrons are pulled toward the
nucleus
Moving down a group, atomic size increases. One reason for this is that orbital size increases as electrons are
added to the next higher energy level (shell) for each subsequent element. Furthermore, effective nuclear charge remains
approximately constant, since inner filled shells shield outermost electrons from the increasing nuclear charge.

Ionic Size

Cations are smaller than their corresponding neutral atoms, since removal of one or more electrons decreases
electron-electron repulsion and slightly increases effective nuclear charge, allowing the ele ctron cloud to shrink. For the
opposite reasons, anions are larger than their corresponding neutral atoms.
Moving down a group, ionic size parallels atomic size. Across a period from left to right, ionic size decreases for both
cations and anions, which also parallels atomic size. When a cation and an anion are isoelectronic, the cation is always
smaller than the anion. In a series of isoelectronic cations and anions, cations with higher positive charge are smaller than
cations with lower charge; likewise anions with greater negative charge are larger than those with lesser charge.

Example: smallest Ca2+ K+1 Ar Cl-1 S-2 P -3 largest (all the ions and Ar have 18 electrons)

Ionization Energy

Moving down a group, ionization energy decreases with increasing atomic number, since atomic size and the
distance of the valence electrons from the nucleus both increase.
Across a period from left to right, the general trend is that ionization energy increases as atomic size decreases, with
two irregularities. In Group 3A elements, the lone p orbital electron is shielded just enough from the nucleus by the
electron pair in the corresponding s orbital that their ionization energies are lower than those for Group 2A elements. The
other exception occurs in Group 6A elements, which have lower ionization energies than for Group 5A elements. This is
because Group 5A elements have three unpaired electrons in their p orbitals (according to Hund's rule), so the fourth p
electron (added in 6A) must be paired with one of the other p electrons, creating a slightly unfavorable repulsive situation
that makes it easier to take an electron from the Group 6A element, despite its higher nuclear charge. Another way to
remember this exception is to keep in mind that half-filled and fully-filled shells (or subshells) are conditions of
relative stability, so anything that perturbs such a condition is probably unfavorable.

Electron Affinity

Electron affinities are negative (i.e. favorable) for all Groups except the noble gases and the alkaline earths. The alkaline
earths have positive (unfavorable) electron affinity because they have a filled s subshell, which effectively screens from
the nuclear charge an electron entering one of the empty p orbitals.