Chapter 9

Atomic Structure &The Periodic Table

The atomic spectrum of hydrogen
The Bohr Model
Wave-Particle Duality
The uncertainty principle
Quantum numbers
Multielectron atoms
Electron configurations
Periodic table
 The Discovery of Atomic Structure

1803 Dalton - the atom is a indivisible,

indestructible, tiny ball
1850 Evidence is accumulating that the atom is
itself composed of smaller particles
The current model...
The strength of attraction between electrons and protons in the
nuclei for different atoms is the basis of many of the unique
properties of different atoms. The electrons play a major role
in chemical reactions. In atomic models, the electrons are
represented as a diffuse electron cloud
 The spectrum of white light

(a) Dispersion of light through a prism

(b) Rainbow near a waterfall

Continuous spectrum is a spectrum containing light of all

wavelengths.

Line spectrum of hydrogen

Line spectrum is a spectrum showing only certain colors or specific
wavelengths of light.
Bohr's Model

Where RH is a constant called the Rydberg constant and

has the value
2.18 x 10-18 J
n is an integer, called the principle quantum number
and corresponds to the different allowed orbits for the
electron.
 -RH
E= 2
n
RH = 2.179 10-18 J
Energy-Level Diagram

-RH -RH
E = Ef Ei = 2
2
nf ni

1 1
= RH ( 2 2 ) = h = hc/
ni nf
Emission

Absorption
 Inadequacies of the Bohr Model

The theory cannot explain the emission spectra

of atoms and ions with more than one electron.
The theory cannot explain the effect of
magnetic fields on emission spectra.
Bohr theory is an uneasy mixture of classical
and nonclassical physics.
The Bohr theory gave the paradigm shift
the quantum leap from classical physics to
the new quantum physics.
Two Ideas Leading to a New Quantum Mechanics

Wave-Particle Duality.
Einstein suggested particle-like properties of
light could explain the photoelectric effect.
But diffraction patterns suggest photons are
wave-like.

de Broglie, 1924
Small particles of matter may at times display
wavelike properties.
 E = mc2
= c/

Albert Einstein (The Nobel Prize in Physics 1921

"for his services to theoretical physics, and
especially for his discovery of the law of the
photoelectric effect")
de Broglie and Matter Waves

E = mc2
h = mc2
h/c = mc = p
p = h/

= h/p = h/m
 X-Ray Diffraction

X-rays are highly energetic photos with an associated

wavelength of about 1
A photon of light strikes and electron and is
reflected. In the collision, the photon
transfers momentum to the electron. The
reflected photon is seen through the
microscope, but the electron is out of focus.
Its exact position cannot be determined.
 The Uncertainty Principle

We cannot measure position and momentum with great precision

simultaneously.

Werner Heisenberg

h
x px
4
 It is only when wavelengths are comparable
to atomic or nuclear dimensions that wave-
particle duality is important. The concept
has little meaning when applied to large
(macroscopic) objects, such as baseballs
and automobiles because their wavelengths
are too small to measure.

For these macroscopic objects, the laws of

classical physics are quite adequate.
 Schrdinger Equation

Kinetic energy Force

2 2 2 8 2m
( E V ) 0
2 2 2 2
x y z h

xyz axes
Wave function
 Solution of Schrdinger
equation gives:
(1) allowed energy values
(2) wave function

Erwin Schrdinger and Paul Dirac (The

Nobel Prize in Physics 1933
"for the discovery of new productive forms of
atomic theory")
 The wave function () is obtained by solving
Schrdinger equation. These wave functions are
called orbitals to distinguish them from the orbitals
of the Bohr theory.
psi /psi:

It square, | |2 , gives the probability density of

finding particle within a region of space.

The distribution of electrons within a region of

space is represented by electron cloud .
 n,l,m(r,,) = R n, l (r) Yl, m (, )

Radial wave function

depends only on r

Angular wave functiondepends

on and

In the spherical polar system the orbitals can be expressed in

terms of one function R that depends only on r and a second
function Y that depends on and
 Principle Shells and Subshells

Principle electronic shell,

n = 1, 2, 3
Angular momentum quantum number,
l = 0, 1, 2(n-1)

l = 0, s Magnetic quantum number, ml =

l = 1, p - l -2, -1, 0, 1, 2+l
l = 2, d
l = 3, f
 Applying relationships among Quantum
Numbers. Can an orbital have the quantum
numbers n = 2, l =2 and ml =2?

Solution: No.
The l quantum number cannot be greater than
n-1. Thus, if n =2, l can be only 0 or 1. And if l
can be only 0 or 1, ml cannot be 2; ml must be 0
if l= 0 and may be -1, 0 or +1 if l = 1.
n : As n increases the electron density is further away
from the nucleus . As n increases the electron has a higher
energy and is less tightly bound to the nucleus

l :Defines the shape of the orbital the energy of an

orbital also depends somewhat on the l quantum number
(except for the H atom). For a given n, the energy of an
orbital increases with l.

m : Describes the orientation of the orbital in space

 For Example,

The symbol 1s designates the s subshell in

the first principal shell, but 1s also the
designation for the s orbital in the first
principal shell.
Orbital Energies
Electron Spin: A Fourth Quantum Number

An electron, because of its spin, generates a magnetic field.

A pair of electrons with opposing spins has no net

magnetic field.
Experimental arrangement for demonstrating the spinning motion of
electrons. A beam of atoms is directed through a magnetic field. For
example, when a hydrogen atom with a single electron passes through
the field, it is deflected in one direction or the other, depending on the
direction of the spin. In a stream consisting of many atoms, there will
be equal distributions of the two kinds of spins, so that two spots of
equal intensity are detected on the screen.
s orbitals
p Orbitals
p Orbitals
d Orbitals
Shape and size of orbitals:
(i) provide the foundation for chemical
bonding
(ii) determine the shape of molecule
 Example:
State whether each of the following sets of
quantum numbers is permissible for an
electron in an atom.
A n =1, l =1, ml =0, ms = +1/2
B n=3, l =1, ml =-2, ms = -1/2
C n=2, l =1, ml =0, ms = +1/2
D n=2, l =0, ml =0, ms = 1
Solution:
A. Not permissible. The l must be less than n.
B Not permissible. The magnitude of the ml
quantum number must not be greater than l.
C Permissible
D Not permissible. The ms quantum number
can be only +1/2 or -1/2
 Screen and Penetration

Electrons in orbitals closer to the nucleus screen or shield

the nucleus from electrons father away.

The ability of electrons in s orbitals that allows them to get

close to the nucleus is called penetration.

The quantity 42 R2(r) provides a different insight into

the behavior of the electron.
Screening and Penetration
Penetration
 Radial probability distributions 42 R2(r)

The smaller its orbital angular momentum quantum number,

the more closely an electron approaches the nucleus.
 In comparing 2s and 2p orbitals, a 2s electron has
a greater chance of being close to the nucleus than
a 2p electron. The 2s electron exhibits greater
penetration than the 2p electron.

Electrons having a high degree of penetration

effectively block the view of an electron in an
outer orbital looking for the nucleus.
The energy level of many-electron atoms

Schrdinger equation was for only one e-.

Electron-electron repulsion in multi-
electron atoms.
Hydrogen-like orbitals (by approximation).
Effective Nuclear Charge

In a many-electron atom, each electron is

simultaneously:
attracted to the protons in the nucleus
repelled by other electrons (like-charge
repulsion)
 Electrons in orbitals closer to the nucleus screen
or shield the nucleus from electrons farther
away.

The net positive charge attracting the electron is

called the effective nuclear charge

Z = Z - ( screening constant )

(Z )2
Ei 2.18 1018 J
n2
 Thus, the energy level of a principal shell is split
into separate levels for its subshells. There is no
further splitting of energies within a subshell.

As a results, Ens<Enp<End<Enf. And all three p

orbitals of a principal shell have the same energy;
all five d orbitals have the same energy; and so on.
Because of the extra penetration of a 4s electron over that of a 3d
electron, the 4s energy level is below the 3d level despite its higher
principal quantum number n.
Portrayal of Pauling
approximation energy
level
Electron Configurations

No two electrons in an atom may have all four quantum

numbers alike---The Pauli Exclusion principle.

Another way to state this result is that

only two electrons may occupy the same orbital and
these electrons must have opposing spins.
 Electrons occupy orbitals in a way that minimizes
the energy of the atom.
---Aufau principle ( German aufbauen, to build up)

When orbitals of identical energy (degenerate

orbitals) are available, electrons initially
occupy these orbitals singly. ----Hunds rule, an
atoms tends to have as many unpaired electrons as
possible.
 Representing Electron Configurations

spdf notation (condensed)

N 1s22s22p3
spdf notation (expanded) N
N 1s22s22px12py12pz1
Orbital diagram
2p

1s 2s
completely filledp6 d10 f14
Half-filledp3 d5 f7
emptyp0 d0 f0
Filling the d Orbitals
Zr
1s22s22p63s23p64s23d104p65s24d2
( filling s orbital firstly, penetrate)
1s22s22p63s23p63d104s24p64d25s2
( d orbital screens)
Zr [Kr] 4d25s2

26Fe 1s2 2s2 2p6 3s2 3p6 3d6 4s2 atomic kernel
[Ar] 3d6 4s2
Fe2+
26 1s2 2s2 2p6 3s2 3p6 3d6 4s0
 Not all electrons present in an atom participate in
chemical bond formation

Electrons occupy a set of shells around the nucleus

inner shell = core shell (core electrons) and outer shell =
valence shell (valence electrons)

Valence electrons participate in the bond formation,

while core electrons do not

Number of electrons in the valence shell = the main group

number
 Magnetic Properties

Diamagnetic atoms or ions:

All e- are paired.
Weakly repelled by a magnetic field.

Paramagnetic atoms or ions:

Unpaired e-.
Attracted to an external magnetic field.
Paramagnetism
Which of the following quantum numbers (n, l, m, ms) are allowed to
describe 3P1: 3, 2, -1, +1/2
3, 1, -1, +1/2
3, 0, 0, -1/2

Concerning the electrons in the shells, subshells,

and orbitals of an atom, how many can have : 18
n=3 6
n=2, l=1 1
n=2, l=0, m=0, ms= +1/2

Which elements are represented by the following electron

configuration:
1s22s22p63s23p64s2 Ca
1s22s22p63s23p63d104s24p5 Br
[Ar]3d34s2 V
 The Periodic Law and the Periodic Table

1869, Dimitri Mendeleev

Lother Meyer

When the elements are arranged in order

of increasing atomic mass, certain sets of
properties recur periodically.
Alkali Metals The Periodic table Noble Gases

Alkaline Earths Main Group

Halogens

Transition Metals

Main Group Lanthanides and Actinides

 p block ns2p 1~6
s block: ns 1~2
ds block (n-1)d10ns1~2 He
H
Li Be d block (n-1)d1~8ns2 B C N O F Ne

Na Mg Al Si P S Cl Ar

K Ca Sc Ti V Cr Mn Fe Co Ni Cu Zn Ga Ge As Se Br Kr

Rb Sr Y Zr Nb Mo Tc Ru Rh Pd Ag Cd In Sn Sb Te I Xe

Cs Ba La Hf Ta W Re Os Ir Pt Au Hg Tl Pb Bi Po At Rn

Fr Ra Ac Rf Db Sg Bh Hs Mt
f block (n-2)f 1~14

La Ce Pr Nd Pm Sm Eu Gd Tb Dy Ho Er Tm Yb

La Ce Pr Nd Pm Sm Eu Gd Tb Dy Ho Er Tm Yb
Periodic Law
 Electronegativity

Defined electronegativity: the measure of the tendency of

an atom to draw to itself electrons in a chemical bond.

is a measure of the ability of an atom in a molecule to

draw bonding electrons to itself.

In general, electronegativity increases from left to right

and decreases from top to bottom in the periodic table.
Metals are the least electronegative elements (they are
electropositive) and nonmetals the most electronegative.
Nonmetals Tend to Gain Electrons
Metals Tend to Lose Electrons