Chemistry Lesson 4 2016-2017

Chemistry Politecnico di Torino A.A.
2016-2017
The atomic orbitals

Federico Carosio
Department of Applied Science and Technology
Tel.: +39 0131 229303

E-mail: federico.carosio@polito.it
A Theory that Explains
Chemistry Politecnico di Torino A.A.2016-2017
Electron Behavior
• the quantum-mechanical model explains the manner electrons
exist and behave in atoms
• helps us understand and predict the properties of atoms that are
directly related to the behavior of the electrons
 why some elements are metals while others are nonmetals
 why some elements gain 1 electron when forming an anion,
while others gain 2
 why some elements are very reactive while others are
practically inert
 and other Periodic patterns we see in the properties of the
elements
The Behavior of
the Very Small

• Electrons are incredibly small
 a single speck of dust has more electrons than the
number of people who have ever lived on earth
• Electron behavior determines much of the behavior of

atoms
• Directly observing electrons in the atom is impossible, the

electron is so small that observing it changes its behavior
The Nature of Light
its Wave Nature
• light is a form of electromagnetic radiation
 composed of perpendicular oscillating waves, one for the
electric field and one for the magnetic field
 an electric field is a region where an electrically charged particle
experiences a force
 a magnetic field is a region where an magnetized particle
experiences a force
• all electromagnetic waves move through space at
the same, constant speed
 3.00 x 108 m/s in a vacuum = the speed of light, c
Electromagnetic
Radiation
Electromagnetic waves (1/3)
 the amplitude is the height of the wave

 the distance from node to crest
 or node to trough
 the amplitude is a measure of how intense the light is –
the larger the amplitude, the brighter the light
 the wavelength, (l) is a measure of the distance
covered by the wave
 the distance from one crest to the next
 or the distance from one trough to the next, or the
distance between alternate nodes
 the frequency, (n) is the number of

waves that pass a point in a given
period of time
 the number of waves = number of cycles
 units are hertz, (Hz) or cycles/s = s-1
 1 Hz = 1 s-1
 the total energy is proportional to the
amplitude and frequency of the waves
 the larger the wave amplitude, the more
force it has
 the more frequently the waves strike, the
more total force there is

n s  
m
-1
c s
l m 
 the color of light is determined by its wavelength
 or frequency
 white light is a mixture of all the colors of visible light
 a spectrum
 RedOrangeYellowGreenBlueViolet
 when an object absorbs some of the wavelengths of white light while
reflecting others, it appears colored
 the observed color is predominantly the colors reflected
 The basic!
Visible light
Visible light
 visible light comprises only a small
fraction of all the wavelengths of light
– called the electromagnetic
spectrum
 short wavelength (high frequency)
light has high energy
 radiowave light has the lowest energy
 gamma ray light has the highest energy
 high energy electromagnetic radiation
can potentially damage biological
molecules
 ionizing radiation
Waves and particles
Diffraction patterns
 When traveling waves encounter an  the diffraction of light through

obstacle or opening in a barrier that two slits separated by a distance
is about the same size as the comparable to the wavelength
wavelength, they bend around it – results in an interference
this is called diffraction pattern of the diffracted waves
 traveling particles do not diffract
Diffraction patterns
 the interaction between waves is called interference

 when waves interact so that they add to make a larger wave it is called
constructive interference
 waves are in-phase
 when waves interact so they cancel each other it is called destructive
interference
 waves are out-of-phase
Emission spectra of atoms
 when atoms or molecules absorb energy, that energy is often
released as light energy
 fireworks, neon lights, etc.
 when that light is passed through a prism, a pattern is seen that is

unique to that type of atom or molecule – the pattern is called an
emission spectrum
 non-continuous
 can be used to identify the material
 flame tests
Barium Calcium Litium Potassium Copper

Emission spectra of
atoms
(1787-1826)
Emission spectra of
How we measure it today… atoms
Emission
Spectra of Mercury
vs.
Absorption Spectra
Emission spectrum of hydrogen
 Rydberg analyzed the spectrum of hydrogen

and found that it could be described with an
equation that involved an inverse square of
integers
1 -1  1 1 
 1.097  10 m  2  2 
7
l  n1 n 2 
RH= Rydberg constant
Black body emission spectrum
Black body:
A substance capable of absorbing and emitting in the entire wavelength spectrum.
Classical theory cannot explain the

wavelenght dependence of the
intensity (I) of the light that is emitted
from a simple heated object (an
idealized “black body” that absorbs all
light)!
I (Intensity) proportional to n and l
I (Intensity)goes to infinity as l goes to

zero!
Experiment: A Maximum is observed!
• The distribution is asymmetric

• The maximum intensity is shifted towards higher frequencies (lower wavelengths) as
temperature rises.
How to explain this?
The classical theories do not explain:
• the emission/absorption at specific wavelengths
• the spectrum of the black body
Planck explains the if E can be anything

ultraviolet catastrophe
by quantizing the
energy of light.
Light can only have if E = hn
energies given by hn
Quantum of energy E=hν

h=6,626*10-34Js
Photoelectric effect
 It was observed that many metals emit electrons
when a light shines on their surface
 this is called the Photoelectric Effect
 Classic wave theory attributed this effect to the

light energy (a function of l) being transferred to
the electron
 if a dim light was used there would be a lag time
before electrons were emitted
However….
 In experiments with the photoelectric effect, it was
observed that there was a maximum wavelength for
electrons to be emitted
 called the threshold frequency
 regardless of the intensity
 It was also observed that high frequency light with a dim source caused electron
emission without any lag time
http://www.youtube.com/watch?v=kcSYV8bJox8
Einstein’s Explanation
 Einstein proposed that the light energy was delivered

to the atoms in packets, called quanta or photons
 the energy of a photon of light was directly
proportional to its frequency
 inversely proportional to it wavelength
 the proportionality constant is called Planck’s
Constant, (h) and has the value 6.626 x 10-34 J∙s
Albert Einstein
Blue light kicks out Nobel Prize 1921
electrons!
Red light
is “inert”
to kicking hc
out electrons E  hn 
l
 1 photon at the threshold frequency has just enough energy for an electron to
escape the atom binding energy, f
 for higher frequencies, the electron absorbs more energy than is necessary to
escape
 this excess energy becomes kinetic energy of the ejected electron
Kinetic Energy = Ephoton – Ebinding
KE = hn - f
The Bohr explanation of atomic spectra
Niels Bohr
Nobel Prize 1922
“the structure of atoms
and the radiation
 Neils Bohr proposed that the electrons could only have very emanating from them”
specific amounts of energy (quantized)
 the electrons traveled in orbits that were a fixed distance from the nucleus
 stationary states
 therefore the energy of the electron was proportional the distance the orbital was from the
nucleus
 electrons emitted radiation when they “jumped” from an orbit with higher energy
down to an orbit with lower energy
Absorption and emission spectra
E4 E2 - E1 = hn
E3 E4
E3
E5 E2 E5 E2
E1 E1
5
4
3 Photon Photon
Absorbed Emitted
2
1
410.1 434.0 486.1 656.3
nm nm nm nm
Bohr atom: Light absorption occurs when an Bohr atom: Light emission occurs when an
electron absorbs a photon and makes a electron makes a transition from a higher
transition for a lower energy orbital to a higher energy orbital to a lower energy orbital and a
energy orbital. Absorption spectra appear as photon is emitted. Emission spectra
sharp lines. appear as sharp lines.
Absorption and emission spectra
E4 E2 - E1 = hn
E3 E4
E3
E5 E2 E5 E2
E1 E1
5
4
3 Photon Photon
Absorbed Emitted
2
1
410.1 434.0 486.1 656.3
nm nm nm nm
Bohr atom: Light absorption occurs when an Bohr atom: Light emission occurs when an
electron absorbs a photon and makes a electron makes a transition from a higher
transition for a lower energy orbital to a higher energy orbital to a lower energy orbital and a
energy orbital. Absorption spectra appear as photon is emitted. Emission spectra
sharp lines. appear as sharp lines.
The Bohr explanation of hydrogen
Possible electron transitions

for the hydrogen atom
r = n2a0 a0=0,53Å
Wave Behavior of Electrons
 de Broglie (1924) proposed that particles could have
wave-like character
 because it is so small, the wave character of electrons

is significant  proof: electron beams shot at slits
show an interference pattern
 the electron interferes with its own wave
 de Broglie predicted that the wavelength of a particle

was inversely proportional to its momentum
h 
kg m 2
h h Planck constant
l m  s2

mass (kg)  velocity(m  s -1 ) mv mv momentum ot the particle
Electron Diffraction
if electrons behave like

particles, there should only be
two bright spots on the target
Electron Diffraction
however, electrons actually present an

interference pattern, demonstrating
the behave like waves
Tro, Chemistry: A Molecular
Approach 30
Particles as waves,
waves as particles (1/2)
Particles as waves,
waves as particles (2/2)
l = h/mv
Uncertainty principle
 Heisenberg stated that the product of the uncertainties in both the position and
speed of a particle was inversely proportional to its mass
 x = position, Dx = uncertainty in position
 v = velocity, Dv = uncertainty in velocity
 m = mass
 the means that the more accurately you know the position of a small particle, like
an electron, the less you know about its speed “vice-versa”
Determinacy vs.
Indeterminacy
 according to classical physics, particles move in a path
determined by the particle’s velocity, position, and forces
acting on it
 determinacy = definite, predictable future
 because we cannot know both the position and velocity of an

electron, we cannot predict the path it will follow
 indeterminacy = indefinite future, can only predict probability
 the best we can do is to describe the probability an electron will

be found in a particular region using statistical functions
Trajectory vs. Probability
35
Schrödinger equation
Schroedinger: If electrons are waves, their
postion and motion in space must obey a wave
equation.
Schrödinger equation (1933): concerns a wave
function whose square value mesures the probability
to find an electron in the space around the origin, where
the nucleus is located.
wave mass of potential energy

function electron at x,y,z
d 2Y d 2Y d 2Y 8p2mQ
+ + + (E-V (x,y,z)Y(x,y,z)) = 0
dx 2 dy 2 dz2 h2
how y changes in space total quantized energy of

the atomic system
Probability & Radial
Distribution Functions
 y2 is the probability density
 the probability of finding an electron at a particular point in space
 for s orbital maximum at the nucleus
 decreases as you move away from the nucleus
 the Radial Distribution function represents the total probability
at a certain distance from the nucleus
 maximum at most probable radius
 nodes in the functions are where the probability drops to 0
37
Probability & Radial
Distribution Functions
 The probability density tells us

the probability of finding the
electron in a small volume dV at dV
a particular location
 The Radial Distribution
function tells us the probability
of finding the electron in a shell
between r and r+dr
The Hydrogen Atom
The only atom that can be solved exactly.
The results become the basis for understanding all other atoms and
molecules.
Nucleus charge +Ze The electron is

(+e for H atom) confined by the pull of
the nucleus, only
certain energies are
Electron charge –e allowed (and certain
wave functions)
The potential arises from the

Coulomb interaction between the
charged particles.
The Hydrogen Atom
Schroedinger managed to solve the equation finding that:
Z e 2 4
Energy levels of the hydrogen atom. En   2 2 2
8 0 h n
This can be rewritten as
RH expressed in terms of fundamental

values, the triumph of Schroedinger.
 The energies are negative the lower the n value the lower the energy
(n=1 ground state)
 The more proton there are the more tight the electron is bond to the
nucleus
Schrödinger equation
The detailed solutions of the Schrödinger equation are three-dimensional and
characterised by three parameters, the quantum numbers.
n the principal quantum number - a positive integer
l the angular momentum quantum number - an integer from 0 to n-1
ml the magnetic moment quantum number - an integer from -l to +l
The wave functions of electrons in atoms are called atomic orbitals

Principal Quantum Number, n
 characterizes the energy of the electron in a particular orbital
 corresponds to Bohr’s energy level
 n can be any integer  1
 the larger the value of n, the more energy the orbital has
 energies are defined as being negative
 an electron would have E = 0 when it just escapes the atom
 the larger the value of n, the larger the orbital
 as n gets larger, the amount of energy between orbitals gets
smaller
 1 
E n  -2.18  10 -18
J 2  for an electron in H
n 
Quantum Numbers, l and ml
 the l quantum number primarily determines the shape

of the orbital
 l can have integer values from 0 to (n – 1)
 each value of l is called by a particular letter that
designates the shape of the orbital
 s orbitals are spherical
 p orbitals are like two balloons tied at the knots
 d orbitals are mainly like 4 balloons tied at the knot
 f orbitals are mainly like 8 balloons tied at the knot
 the ml quantum number primarily determines the

orientation of the orbital
 ml can have integer values from –l,…,0,…+l
Quantum number
Name,
variations
Symbol
(Property) Allowed Values Quantum Numbers
Principal, n Positive integer

1 2 3
(size, energy) (1, 2, 3, ...)
Angular
momentum, l 0 to n-1 0 0 1 0 1 2
(shape)
0 0 0
Magnetic, ml
-l,…,0,…,+l -1 0 +1 -1 0 +1
(orientation)
-2 -1 0 +1 +2
Orbitals
The orbitals represent a portion of space outside of which
the probability to find an electron is negligible
QUANTUM NUMBER COMMON ORBITAL TOTAL NUMBER OF
NAME ORBITALS
(dimension) (shape) (orientation)

l = 0, the s orbital
 each principal energy state has
1 s orbital
 lowest energy orbital in a
principal energy state
 spherical
 number of nodes = (n – 1)
2s and 3s
2s 3s
n = 2, n = 3,
l=0 l=0
2s and 3s
2s 3s
n = 2, n = 3,
l=0 l=0
l = 1, p orbitals
 each principal energy state above n = 1 has 3 p

orbitals
 ml = -1, 0, +1
 each of the 3 orbitals point along a different axis
 px, py, pz
 2nd lowest energy orbitals in a principal energy
state
 two-lobed
 node at the nucleus, total of n nodes
p orbitals
l = 2, d orbitals
 each principal energy state above n = 2 has 5 d
orbitals
 ml = -2, -1, 0, +1, +2
 4 of the 5 orbitals are aligned in a different plane
 the fifth is aligned with the z axis, dz squared
 dxy, dyz, dxz, dx squared – y squared
 3rd lowest energy orbitals in a principal energy
state
 mainly 4-lobed
 one is two-lobed with a toroid
 planar nodes
 higher principal levels also have spherical nodes
d orbitals
l = 3, f orbitals
 each principal energy state above n = 3 has 7 d

orbitals
 ml = -3, -2, -1, 0, +1, +2, +3
 4th lowest energy orbitals in a principal energy
state
 mainly 8-lobed
 some 2-lobed with a toroid
 planar nodes
 higher principal levels also have spherical nodes
f orbitals
Electron Spin
 experiments by Stern and Gerlach showed a beam of silver atoms is split in
two by a magnetic field
 the experiment reveals that the electrons spin on their axis
 as they spin, they generate a magnetic field
 spinning charged particles
generate a magnetic field
http://www.youtube.com/watch?v=rg4Fnag4V-E
Spin Quantum
Number, ms
 spin quantum number describes how the electron spins
on its axis
 clockwise or counterclockwise
 spin up or spin down
 spins must cancel in an orbital
 paired
 ms can have values of ±½
Each orbital describes the behaviour of two electrons identified by

the described quantum numbers
ms
Electron distribution in
orbitals
The maximum number of electrons that can be hosted at a n
level is limited to 2n2.
n=1 maximum population = 2(1)2 = 2
• Examples (…as Bohr would have conceived!)
Hydrogen Helium Neon Na

Z=1 Z=2 Z = 10 Z = 11
Effective nuclear charge
ZEFF=(Z-S)
Where Z is the atomic number

and S is a shield constant. The
lower the S the easier for
electrons to get closer to the
nucleus.
Orbital energy 1/2
The hydrogen atom
4s 4p 4d 4f
3s 3p 3d
 the sublevels in each principal energy
Energy
2s 2p level of Hydrogen all have the same

energy – we call orbitals with the same
energy degenerate
 or other single electron systems (e.g. He+1)
 for multielectron atoms, the energies of

1s the sublevels are split
 caused by electron-electron repulsion
Orbital energy 2/2
7s 6d
6p 5f
5d
6s 4f
5p
4d
5s
4p
4s 3d
Energy
3p
Notice the following:
3s 1. sublevels within an energy level are not
2p degenerate
2. penetration of the 4th and higher energy
2s levels is so strong that their s sublevel is
lower in energy than the d sublevel of the
previous energy level
1s
Electronic configuration:
Rules for its definition
AUFBAU method
The orbitals with lower energy get
occupied first.
Pauli principle 1s
A maximum of two electrons can
be hosted in a single orbital. They 2s 2p
have opposed spin value.
3s 3p 3d
Hund rule
If more than one configuration is
4s 4p 4d 4f
possible the one that enables the 5s 5p 5d 5f
maximum spin multiplicity (i.e.
maximum number of unpaired 6s 6p 6d
electrons) is favoured.
7s
The effect of the atomic
number
The atomic
number has PRINCIPAL QUANTUM NUMBER
an effect on
the order of
orbital filling.
ATOMIC NUMBER
Electron configuration:
examples (1/4)
 The electron configuration represents how the electrons are
distributed in the various orbitals.
 Energy minimisation is a general principle
H (1 electron) 1s1 semi saturation
He (2 electrons) 1s2 saturation
Li (3 electrons) 1s2 2s1
Be (4 electrons) 1s2 2s2

examples (2/4)
B (5 electrons) 1s2 2s2 2p1
C (6 electrons)
* 1s2 2s2 2p2 * Here the
Hund rule
intervenes
N (7 electrons) 1s2 2s2 2p3
*
Ne (10 electrons) 1s2 2s2 2p6
Al (13 electrons) [Ne] 3s2 3p1
Ar (18 electrons) 1s2, 2s2, 2p6, 3s2,3p6
Kr (36 electrons) 1s2, 2s2, 2p6, 3s2,3p6, 3d10,4s2,4p6

examples (3/4)
Electron Electron
Z Element configuration Z Element configuration
examples (4/4)
Electron Electron
Z Element configuration Z Element configuration
exercise
Write the Ground State Electron
Configuration and Orbital Diagram and of
Magnesium.
1. Determine the atomic number of the element from
the Periodic Table
 This gives the number of protons and electrons in the
atom
Mg Z = 12, so Mg has 12 protons and 12 electrons

Magnesium.
2. Draw 9 boxes to represent the first 3 energy levels s
and p orbitals
a) since there are only 12 electrons, 9 should be plenty
1s 2s 2p 3s 3p

Magnesium.
3. Add one electron to each box in a set, then pair the
electrons before going to the next set until you use
all the electrons
 When pair, put in opposite arrows
     
1s 2s 2p 3s 3p

Magnesium.
4. Use the diagram to write the electron configuration
 Write the number of electrons in each set as a
superscript next to the name of the orbital set
1s22s22p63s2 = [Ne]3s2
     
1s 2s 2p 3s 3p
Refelxes on the periodic table
representation (1/2)
The periodic table can be divided into sector depending on the types of
valence orbitals.
Internal electrons: those belonging to the noble gas with the closest
lower mass. These electrons fill in the lower energy levels of an atom.
External electrons: Those with the highest energy (highest n value).
Valence electrons: Those that are taking part in bonds. In transition
metals sometimes also inner electrons become valence ones. The valence
electrons are equal in the elements of a given column.
Reflexes on the periodic table
representation (2/2)
Lewis representation of
valence electrons (1910)
ELEMENT s ORBITAL p ORBITAL ORBITAL LEWIS
CONFIGURATION CONFIGURATION
First period
octet
(peculiar
stability)
period
Formation of ions
Ions formed by the elements

close to noble gases.
Oxidation number
General rules
1. For an atom in its elemental form (Na, O2, Cl2, etc.): O.N. = 0
2. For a monoatomic ion: O.N. = ion charge
3. The sum of O.N. values for the atoms in a compound equals zero. The
sum of O.N. values for the atoms in a polyatomic ion equals the ion’s charge.
Rules for specific atoms or periodic table groups

1. For Group 1A(1): O.N. = +1 in all compounds
2. For Group 2A(2): O.N. = +2 in all compounds
3. For hydrogen: O.N. = +1 in combination with nonmetals
4. For fluorine: O.N. = -1 in combination with metals and boron
5. For oxygen: O.N. = -1 in peroxides
O.N. = -2 in all other compounds(except with F)
6. For Group 7A(17): O.N. = -1 in combination with metals, nonmetals
(except O), and other halogens lower in the group

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Chemistry Politecnico di Torino A.A.

The atomic orbitals

Department of Applied Science and Technology

Tel.: +39 0131 229303

the Very Small

• Electron behavior determines much of the behavior of

• Directly observing electrons in the atom is impossible, the

 the amplitude is the height of the wave

 the frequency, (n) is the number of

 When traveling waves encounter an  the diffraction of light through

 the interaction between waves is called interference

 when that light is passed through a prism, a pattern is seen that is

Barium Calcium Litium Potassium Copper

 Rydberg analyzed the spectrum of hydrogen

Classical theory cannot explain the

I (Intensity) proportional to n and l

I (Intensity)goes to infinity as l goes to

Experiment: A Maximum is observed!

• The distribution is asymmetric

Planck explains the if E can be anything

Quantum of energy E=hν

 Classic wave theory attributed this effect to the

 Einstein proposed that the light energy was delivered

Possible electron transitions

 because it is so small, the wave character of electrons

 de Broglie predicted that the wavelength of a particle

if electrons behave like

however, electrons actually present an

 because we cannot know both the position and velocity of an

 the best we can do is to describe the probability an electron will

Trajectory vs. Probability

wave mass of potential energy

how y changes in space total quantized energy of

 The probability density tells us

Nucleus charge +Ze The electron is

The potential arises from the

This can be rewritten as

RH expressed in terms of fundamental

n the principal quantum number - a positive integer

l the angular momentum quantum number - an integer from 0 to n-1

ml the magnetic moment quantum number - an integer from -l to +l

The wave functions of electrons in atoms are called atomic orbitals

 the l quantum number primarily determines the shape

 the ml quantum number primarily determines the

Principal, n Positive integer

(dimension) (shape) (orientation)

 each principal energy state above n = 1 has 3 p

 each principal energy state above n = 3 has 7 d

 as they spin, they generate a magnetic field

 spinning charged particles

generate a magnetic field

Each orbital describes the behaviour of two electrons identified by

• Examples (…as Bohr would have conceived!)

Hydrogen Helium Neon Na

Where Z is the atomic number

2s 2p level of Hydrogen all have the same

 for multielectron atoms, the energies of

H (1 electron) 1s1 semi saturation

He (2 electrons) 1s2 saturation

Li (3 electrons) 1s2 2s1

Be (4 electrons) 1s2 2s2

Al (13 electrons) [Ne] 3s2 3p1