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Atomic and Molecular Electronic Structure Theory

and Chemical Bonding


Philippe Matre, Universit Paris Sud, Orsay (France).
Objective
Chemists need simple models in order to be able to represent the electronic structure of atoms
and molecules, i.e. electrons with atoms or molecules. We need simple representations or, in
other words, we need to visualize the results of Quantum Mechanics, which is the mechanics
relevant for describing atoms and molecules.
Course Description
This course starts with the description of Atomic Structure: from the discovery of sub-atomic
particles to the milestones experiments that led to the first atomic models. The first evidence
of interaction of light with matter will then be discussed (Absorption and emission spectra),
and the Bohr model of hydrogen atom will be presented.
Our current conceptions of atomic and molecular electronic structure, bonding and
spectroscopy strongly rely on quantum mechanics (QM). Only the basic principles of QM will
be given, and then the main results of quantum mechanics applied to hydrogen like atoms will
be presented. The most important and new concept which will be introduced will be the
orbital, i.e. the wavefunction of the electron of the hydrogen-like atom. A special emphasis
will be made on the representation of the atomic orbitals (one-, two- and three-dimensional
contour plots, definition of the atomic orbital radius).
Periodic trends of the physical and chemical properties of elements will be discussed in the
third chapter using the Slater model of many electron atoms. The principles (Aufbau
principle, Pauli exclusion principle, Hunds rule) for obtaining the ground state electronic
configuration of the atoms will be given. We will see that the main periodic trends can be
understood using these few principles.
A first description of the electronic structure of molecules and chemical bonding will be
given. This lecture is essentially based on the Lewis approach of chemical bonding. The rules
necessary to draw the Lewis representation of the electronic structure of molecules will be
given, and the resonance theory will also be presented. The Valence Shell Electron Pairs
Repulsion (VSEPR) theory will then be used to predict the geometry of simple molecules.
The analysis of the dipole moment of molecules will give us the opportunity to discuss the
ionic/covalent nature of the bonds, and the influence of the symmetry on physicochemical
properties of molecules.
The electronic structure of a selected set of diatomic molecules will then be discussed within
the frame of Molecular Orbital (MO) theory in the last two lectures. We will see how one can
draw a parallel between the Lewis representation and the electronic configuration using an
MO energy level diagram.

Lecture 1: Evolution of the atomic concept; First (dot and cross)
representation of atoms
Evolution of the atomic concept: Matter is not infinitely divisible (Dalton); Discovery of the first sub-
atomic particle, negatively charged, electron (Thompson); Evidence that positively charged particles
are concentrated, concept of nucleus (Rutherford, who imagined the electrons orbiting around
nucleus like planets around the sun); This planetary model was then improved by Bohr (see Lecture
2).
Atomic notation: mass and charge of subatomic constituents (proton, neutron and electron); Atomic
Symbol (atomic number Z, atomic mass A); Most of the elements have isotopes.
Dot and cross model: Periodic Table of the chemical elements (Mendeleev); Concept of shells:
definition of core and valence electrons; Electronic configuration: K, L, M notation; Examples of Dot
and Cross representations of atoms.

Lecture 2: Spectroscopy and Borhs model of Atoms
Experimental evidences for wave-particle duality of light: Decomposition of visible light into
monochromatic light (Newton); Evidences that light is a wave (diffraction, interferences); Wave
characteristics (wavelength, frequency, relationship between them); Light is an electromagnetic
wave: description of the different parts of the spectrum, orders of magnitude; light is a particle:
photoelectric experiments; Energy of a photon: numerical examples (units of , v, Energy).
Atomic spectra: Line absorption spectra; Line Emission spectra of hot gases; one-to-one match
between absorption and emission spectra.
Series of lines: Balmer (Visible), Lyman (UV), Paschen, Brackett, and Pfund (IR).
Borhs model: Postulates; Formulation of the model; Expressions for the energy and radius of the
Hydrogen Atomic orbits with derivations.
Interpretation of absorption and emission phenomena: Allowed transitions; Principle of
conservation of energy; Two representations of absorption or emission: energy diagram or orbital
scheme.
Ionization: Definition of the ionization energy; Whereas the bound states of the electron are
discrete, above the ionization limit (Energy=0), there is a continuum of states for the unbound
electron; Kinetic energy of the released electron upon ionization.

Lecture 3: Quantum model of hydrogen-like systems
Stationary states in quantum mechanics: Electron is a wave, it is described by a wavefunction; State
of the system is characterized by (E
n
, +
n
), where E
n
is the energy and +
n
the wavefunction, and n is a
set of quantum numbers; Density of probability: relationship with the wavefunction.
Ground state of hydrogen atom: Wavefunction of the ground state of hydrogen atom; for atoms,
wavefunction is called Atomic Orbital (AO); Representations of ground state 1s AO; Definition of the
radial probability density; Definition of the orbital radius as the maximum of the radial probability
density.
States of hydrogen-like systems: Wavefuntion is defined by three quantum numbers (n, l, m), +
n,l,m
;
Relationships between quantum numbers; Energy is defined by one quantum number, E
n
; Expression
of the energy (in eV) is:
2
2
6 . 13
n
Z
~
; Energy level degeneracy; Nomenclature of the AO (s(l =0), p(l
=1), d(l =2)); Hydrogen-like energy diagram; General expression of the AO.
Discussion of the s-type AO of hydrogen-like systems: When the atomic number Z increases, AO
energy decreases and AO radius decreases (AO contraction); When the principal quantum number
(n) increases, AO energy increases and AO radius (comparison with trends predicted by Bohrs
model) increases; Nodal properties of s-type AO: nodal surfaces are sphere-like, and their number
increases with n; Representation of the ns AO as sphere with a radius value increasing with n
(comparison with Borhs model); Analogy with the vibration of a drum.
Discussion of the AO of hydrogen-like systems in their first excited level (n=2): What are the four
states associated with n=2? analogy with the vibration of a drum; Representation of the 2p AO as
2p
x
, 2p
y
, and 2p
z
; Each 2p AO has a nodal plane and has a cylindrical symmetry; Energy diagram of a
hydrogen-like system: representation of the two firsts levels; the AO of the first excited level all have
a nodal surface (a sphere for the 2s, a plane for each 2p); Radius of np AO increases with n; Concept
of shell: ns and np have very similar radii.
Discussion of the AO of hydrogen-like systems in their second excited level (n=3): A third type of
AO: d OA; Mathematical expression of the 3d AO (3d
z
2, 3d
x
2
-y
2, 3d
xy
, 3d
xz
, 3d
yz
): as for the np AO, we
use hybrid coordinate (r, and Cartesian coordinates) ; Representation of the 3d AO; Energy diagram
of a hydrogen-like system: representation of the second excited states: the AO of the second excited
level all have two nodal surfaces; What are the four states associated with n=3? analogy with the
vibration of a drum.
Magnetic moment of the electron: Orbital angular momentum L: characterized by two quantum
numbers (l, m) where m is the magnetic quantum number; Why magnetic quantum number?
because a magnetic moment is associated with the orbital angular momentum, and this magnetic
moment is proportional to m; Zeeman effect: evidence of the interaction of the magnetic angular
momentum with magnetic field; Stern and Gerlach experiment: each electron has an intrinsic
angular momentum called spin; Each electron has two spin states: representations (up/down,
m
s
=; o/|); States of hydrogen like systems are labelled by 4 quantum numbers (n, l, m
l
, m
s
);
Hydrogen energy levels: experiment versus model.


Lecture 4: Electronic Structure of Many-Electron Atoms
Monoelectronic Approximation: The Schrdinger equation cannot be exactly solved for systems
containing two electrons or more: approximations have to be made; Monoelectronic approximation,
sometimes also called orbital approximation: (i) the total N-electron wavefunction is a product of
1-electron wavefunction (called AO); the total N-electron energy is the sum of the 1-electron
energies (occupied AO energies); very important: for many-electron systems, AO energy depends not
only on n (as for hydrogen-like system) but also on l; For a given n (l), the AO energy increases with l
(n); AO energy diagram of an N-electron system: the energy order up to 3p is clear (1s<2s<2p<3s<3p),
the relative energies of 3d and 4s will be discussed in more details.
Electronic configuration of many-electron systems: What is it? This is the distribution of the
electrons in the AO; Pauli exclusion principle and the (very important) concept of electron pair;
Examples of rare gas electronic configuration; Notion of shells: core and valence electron; Only the
valence electrons are shown in the dot and cross representation of the atoms.
Electronic Spin associated with an electronic configuration; Hunds rule: Examples of Li and Be:
Electronic spin of the atom; Hunds rule: for a given occupation of a degenerate level (2p, 3p, 3d for
example), the lowest energy configuration corresponds to the one with a maximum number of
singly-occupied AO with spin parallels. Examples of C and N; How to calculate the total spin S of an
atom: in the electronic ground state, it is equal to N
umpaired
* (N
umpaired
= number of unpaired
electrons); Magnetic properties of atoms are related to the spin state: diamagnetic if S=0,
paramagnetic otherwise.
Lewis representation of an atom in a given electronic configuration: Only valence electrons are
given; A doubly occupied valence AO is represented by a doublet (doublet=Lewis base); A singly
occupied AO is represented by a dot (single electron=radical); An empty valence AO is represented by
a vacant site (empty box); Examples.
Klechkowskys rule: The relative energy levels of 4s and 3d depends of the element (also charge) and
its electronic configuration; Klechkowskys rule: The ground state electronic configuration of a
neutral atom is obtained by filling the AO by (n+l) increasing order and for a given (n+l) value, by
increasing n order. Examples and exceptions confirming the rule: Chromium; Transition metal
electron configurations: special features.
Slaters model for the N-electron systems: Notion of screening effect; AO energy and radius:
Formula; How to calculate the effective charge of an electron occupying an AO? General expression
and examples; Determination of the Ionization Energy of an N-electron atom using the Slaters
model: examples (He, Ca) and comparison with experiment.
First ionization energy of an N-electron system: Trends and exception; Discussion of the trends using
the Hunds rule; Stability of filled and half-filled shells and sub-shells.
Redox phenomena: Ionization energy trends; Electron Affinity trends; Definition of the
electronegativity; Concept of oxidation state.
Atomic Orbital radius: Definition using Slaters model and trends within the periodic table.

Lecture 5: Lewis: Electronic structure of molecules
Concept of chemical bonding: Atoms in molecules are bonded through chemical bonds; a chemical
bond consists of the sharing of a pair of electrons by two atoms; Example of H-H bond; Quantification
of the chemical bond: bonding energy and equilibrium distance; Order of magnitude of chemical
bonds.
Octet rule: it has been observed that in stable molecules (especially for organic molecules, i.e.
containing C, N, O and H), atoms are bound to each other in such a way that they formally have the
electronic configuration of a rare gas atom. This is called the octet rule (4 electron pairs = 8 valence
electrons), duet rule (1 electron pair = 2 e
-
) for H.
Example of Lewis structures: Simple examples (H
2
, HF, H
2
O, NH
3
, CH
4
). Two types of electron pairs:
bonding pairs and lone pairs.
Electron count: based on equal sharing of bonded electron pairs: for each bonding pair, one electron
is formally assigned to each bonded atom; number of electrons assigned to an atom in a molecule =
2*(number of lone pairs)+1*(number of bonds involving the atom); number of electrons formally
surrounding an atom in a molecule= 2*(number of lone pairs)+2*(number of bonds involving the
atom); in these stable molecules, H is formally surrounded by 2 e
-
, and X=C, N, O, or F is surrounded
by 8 e
-
(octet rule).
Dative bond: The prototype of dative bond is between B and N in H
3
BNH
3
where the two bonded BN
electrons are provided by N.
Single and multiple bonds: Example of N
2
: triple bond. Evolution of the bond strength and bond
length of C
2
H
6
, C
2
H
4
, and C
2
H
2
: the bond order concept is meaningful.
Partial charge, oxidation number, of an atom in a molecule: Number of valence electrons Number
of electrons assigned to the atom in the Lewis structure; In other words: Number of valence
electrons Number of bonds Number of unshared electrons. Examples: H
3
O
+
, NH
4
+
, BH
4
-
, BF
4
-
.
What is the best Lewis structure: If possible, try to minimize the number of partial charges, and
have the octet rule respected for all atoms. A typical difficult case: CO. A method: (1) Make the
choice of the connectivity (arrangement of the atoms in space); (2) Count the total number of
valence electrons; (3) Connect each pair of neighbor atoms by a bond represented by a dash; (4)
Count the electrons left; (5) Distribute these electrons as lone pair (start with the most
electronegative atoms) and/or draw multiple bond so that the octet rule is respected for as many
atoms as possible; (6) If an atom A lacks an electron pair, use a lone pair of an adjacent atom B to
form a multiple AB bond; (7) Calculate the partial charges.
Hypervalent molecules: Stable molecules (PF
5
, SF
4
, ) that contain an atom (typically 3
rd
row)
formally bearing more than 8 valence electrons. Lewis representationS of oxides such as Cl
3
PO, SO
4
-
.
Constitutional isomers: Isomers=compounds that have the same molecular formula. Constitutional
(or structural) isomers= isomers that differ by the atom connectivity. Famous example: ammonium
cyanate and urea. Examples: C
n
H
2n+2
(Alkane), C
n
H
2n
(Alkene or cyclic alkane), C
n
H
2n+2
O (alcohol or
ether). Some typical functional groups of organic compounds will be given.
Limitations of the Lewis model: The paramagnetic property of the dioxygen molecule in its ground
state cannot be predicted with the Lewis model; How can we represent excited electronic states?
What is the influence of multiple bonds on geometry (see also Lecture 6: VSEPR)?

Lecture 6: VSEPR: geometry of molecules
Valence shell electron pair repulsion (VSEPR): The working principle is that the valence electron
pairs surrounding an atom mutually repel each other. The VSEPR (or Gillepsie) model assumes that
the shape of molecules derives from the minimization of valence electron pairs electrostatic
repulsion.
VSEPR notations: The notation AX
n
E
m
means that the atom A is surrounded by n bonding pairs (X)
and m lone pairs (E).
Predicted structures for atoms surrounded by 2, 3 or 4 electron pairs (n+m=2, 3, or 4): Ideal
structures are: linear (n+m=2), trigonal planar (3), and tetrahedral (4). Examples of CH
4
, NH
3
, H
2
O:
experimental versus ideal VSEPR structures suggest the increasing electrostatic repulsion strength
X-X<X-E<E-E.
VSEPR in practice: (1) draw up a Lewis structure; (2) Identify the numbers n of bonding electron
pairs (important: multiple A-X bonds count as one X) and m of lone pairs surrounding the central A
atom; (3) Determine the ideal geometry about the A atom using the AX
n
E
m
; (4) then you may want to
use the relative electrostatic repulsion strength (X-X<X-E<E-E) to refine your answer.
Predicted structures for atoms surrounded by more than 5 or 6 electron pairs: Important ideal
structures are: trigonal bipyramid, noted TBP, (n+m=5), and octahedral (6); Discussion of some stable
hypervalent molecules and S
N
2 transition state.
Dipole moment of a polyatomic molecule: Simple examples (H
2
O, ) will be used to illustrate the
estimation of the polarity of the bonds; More important: effect of symmetry on dipole moment (and
other physico-chemical properties).





Lecture 7: Molecular Orbital (MO) Theory; Simple homonuclear diatomics
Scope and limitations of the MO model: Different types of strong bonds (covalent, ionic, and
metallic): the simple MO model presented in this lecture can only be used to describe strong
covalent (ionic) bonds. Other (weaker) bonding interactions: hydrogen bonds and van der Walls
interactions.
Electronic states of H
2
+
: Both experiments and theory show that molecules have two kinds of
electronic state: Bound or repulsive; illustration with H
2
+
; One possible representation of the
molecular states: two resonance structures.
Molecular 1-electron wavefunction = Molecular Orbital (MO) of H
2
+
: Symmetry is used to label the
states: o, t, o notation and definition of the o
g
and o
u
states. In practice, MO are written as Linear
Combinations of Atomic Orbitals (LCAO); Drawing of the 1o
g
and 1o
u
of H
2
+
; Discussion of the
concept of bonding and antibonding MOs and their relative energies: Analysis of the electron density
and of the nodal properties of the 1o
g
and 1o
u
MOs.
MO Diagram: Important feature of the relative energies of bonding and antibonding MOs: with
respect to the AO energy, the destabilization of the antibonding MO is greater than the stabilization
of the bonding MO; Evolution of MO energies with interatomic distance: concept of AO overlap.
MO electronic configuration and concept of bond order: examples of H
2
+
, H
2
, H
2
-
, He
2
+
, He
2
; MO
theory provides a more refined picture of the bonding scheme than Lewis theory; One can conclude
that the order of magnitude of the energy stabilization (destabilization) of the bonding (antibonding)
MO is few eV, i.e. the order of magnitude of a chemical bond.
Description of excited electronic states: examples of H
2
and He
2
+
; MO provides a comprehensive
understanding of electronic states; It is a powerful tool for understanding photochemical processes.

Lecture 8: Molecular Orbital (MO) of 2
nd
row homonuclear diatomics
Dioxygen molecule: O
2
is paramagnetic: experimental evidence; cannot be predicted using Lewis
theory.
Valence MO of O
2
: LCAO and symmetry: Valence MO are linear combination of valence AO 2s and
2p; Two types of MO: o and t; Relative o and t bonding strength: discussion using the o and t
overlaps; Symmetry adapted MOs can be built as linear combination of 2s and 2p AO; Tools for
discussion the relative energies of these symmetry adapted MOs: 2s/2p relative energy (large for O,
~20eV), o versus t overlaps, common bonding strength (few eV).
MO electronic configuration of O
2
: Using Hunds rule, paramagnetic ground state of O
2
is predicted:
the spin state is S=1, it is a triplet; Bond order is 2; Diamagnetic (S=0, singlet state) excited electronic
states of O
2
are known: they can be easily predicted using the MO diagram.
Analysis of electron count: Evolution of the bond length, bonding strength, and magnetic properties
of O
2
2+
, O
2
+
, O
2
, O
2
-
, O
2
2-
analyzed using the MO diagram: another success of MO theory; Examples of
F
2
and Ne
2
+
.
Evidence (magnetic properties) for another MO diagram for X
2
(X=Li-N): Electronic ground state of
B
2
is paramagnetic (S=1), the one of C
2
is diamagnetic (S=0): evidence for o
u
/t
u
energy inversion; This
MO energy inversion can be rationalized: when 2s/2p energy gap is small, 2s-2p interactions cannot
be neglected (the symmetry adapted LCAO can no longer be considered as good approximations of
MOs as for O
2
); Discussion of B
2
, C
2
, and N
2
; C
2
has one low energy excited state: coherent with the
MO picture.