This action might not be possible to undo. Are you sure you want to continue?

BooksAudiobooksComicsSheet Music### Categories

### Categories

### Categories

Editors' Picks Books

Hand-picked favorites from

our editors

our editors

Editors' Picks Audiobooks

Hand-picked favorites from

our editors

our editors

Editors' Picks Comics

Hand-picked favorites from

our editors

our editors

Editors' Picks Sheet Music

Hand-picked favorites from

our editors

our editors

Top Books

What's trending, bestsellers,

award-winners & more

award-winners & more

Top Audiobooks

What's trending, bestsellers,

award-winners & more

award-winners & more

Top Comics

What's trending, bestsellers,

award-winners & more

award-winners & more

Top Sheet Music

What's trending, bestsellers,

award-winners & more

award-winners & more

Welcome to Scribd! Start your free trial and access books, documents and more.Find out more

**and Atomic structure
**

CM1502

Chapter 1

1 CM1502 Sem2-2013-14

2

Light and Matter

• All matter is made up of charged particles.

• Accelerating charges emit and absorb

electromagnetic radiation (EMR).

• EMR is characterized by its frequency, ν, and its

wavelength, λ.

• Light (EMR) travels at a fixed speed, c.

• There is a relationship between c, λ and ν.

νλ = c

(1.1)

CM1502 Sem2-2013-14

3

The Wave

nature

of light

CM1502 Sem2-2013-14

4

• Amplitude is the height

of the crest or the depth

of the trough of each

wave.

• Amplitude is related to

the intensity of the

radiation which we

perceive as brightness in

the case of visible light.

The Wave nature of light

CM1502 Sem2-2013-14

5

Classical Distinction between

Wave and Particle

CM1502 Sem2-2013-14

6

Electromagnetic Spectrum

CM1502 Sem2-2013-14

7

Continuous Spectra

• A warm solid, liquid and plasma will radiate at

all wavelengths thus producing a continuous

EM spectrum.

CM1502 Sem2-2013-14

8

Discrete Spectra 1

• A warm gas emits EMR, but at certain specific

wavelengths thus producing a discrete EM

spectrum.

CM1502 Sem2-2013-14

9

Discrete Spectra 2

• A gas can also absorb EMR and does so at

discrete wavelengths.

CM1502 Sem2-2013-14

10

Examples: Spectra of Stars

CM1502 Sem2-2013-14

11

Examples: Gas clouds in space 1

CM1502 Sem2-2013-14

12

Line spectra of Atoms…

CM1502 Sem2-2013-14

13

Hydrogen Atom Spectrum 1

CM1502 Sem2-2013-14

14

Hydrogen Atom Spectrum 2

• A high school maths teacher, Balmer, in 1885

noticed that the wavelengths of the visible lines of

H’s spectrum could be represented by the formula:

... 5 , 4 , 3 ,

1

4

1 1

2

H

=

− = n

n

R

λ

where R

H

is a constant.

CM1502 Sem2-2013-14

15

Hydrogen Atom Spectrum 3

• Later Rydberg showed that all the H atom’s absorption

and emission lines (not just those seen in the visible,

i.e., the Balmer series) could be represented by the

formula

where R

H

is, as before, a constant now known as the

Rydberg constant, 1/R

H

= 91.1763 nm.

... 3 , 2 , 1 ..., 3 , 2 , 1 ,

1 1 1

1 1 1 2 1

2

2

2

1

H

+ + + = =

− = n n n n n

n n

R

λ

(1.2)

The Rydberg equation and the value of the constant are

based on data rather than theory

CM1502 Sem2-2013-14

16

The Unexplained

• Why do the spectral lines of Hydrogen appear in a

pattern?

• Is there any importance about this experimental

observation?

• Over a wide range of wavelengths, light is only

observed at certain discrete wavelengths

• Light is quantized (?)

• It was taught before that light behaves as wave

only…

CM1502 Sem2-2013-14

17

Explaining Rydberg’s Formula –

Quantization of Light

• Max Planck first proposed that light could be

quantized into little packets of energy.

• The packets of energy, called photons, have an

energy value of,

ν h E =

(1.3)

where h is Planck’s constant.

CM1502 Sem2-2013-14

Bohr’s H atom 1

• Bohr postulated that an atom could only exist in certain

allowed states of specific total energy E which he called

stationary states. Atoms do not leak energy while in one

of its stationary states.

• If an atom was not in its lowest energy state (ground

state), then it could make a downward transition, to a

state of lower energy and in the process, emit a photon.

• High energy atomic state = E

u

Low energy atomic state = E

l

.

E

u

̴ E

l

= ∆E = a photon energy = hѵ.

• Bohr’s postulated fixed atomic states and energy levels

and this leads naturally to discrete spectra.

18 CM1502 Sem2-2013-14

19

The energy levels of hydrogenic

atoms/ions

E

n

=-2.18 x 10

-18

J Z

2

/n

2

The negative sign for the energy appears

because we define the zero point of the atom’s

energy when the electron is completely

removed from the attraction of the nucleus

A table top analogy for defining the

energy of a system.

If you define the zero point of your

textbook’s potential energy when the

book is on the table, the energy is

negative when it is on the floor.

2

2

2

0

4 2

1

8

n

h

e Z

E

n

ε

µ

− =

(1.4)

CM1502 Sem2-2013-14

• The lowest energy state of hydrogen atom n=1 has

the energy of -13.6eV or -1312 KJ/mole.

• The amount of energy needed to promote an atom

from the ground state to a given excited state is

called excitation energy.

• The amount of energy needed to remove an electron

from an atom in ground state is called the ionization

energy.

• The separation energy is energy needed to remove

an electron from an atom in any excited state.

H Atom Energy States

20 CM1502 Sem2-2013-14

21

n=1

n=∞

n=5

n=4

n=3

n=2

-13.6/2

2

= -3.4 eV

-13.6/3

2

= -1.51eV

-13.6/4

2

=0.85eV

-13.6/5

2

=-0.54eV

0

-13.6eV

1

st

excited state

2

nd

excited state

Ground state

a

b

a: Ionization energy = +13.6eV

b: Excitation energy

c,d:Separation energies

Energy level diagram for hydrogen atom

c

d

CM1502 Sem2-2013-14

22

Applications of Bohr’s equation for

energy levels of an atom

• We can find the

-difference in energy between two levels.

-energy needed to ionize the H atom

-wavelength of the spectral line.

CM1502 Sem2-2013-14

Figure 7.11

The Bohr explanation of the three series of spectral lines.

• E of emitted photon: UV series > VIS series > IR series

n in Rydberg equation

23

A spectral line results because a photon of specific energy is emitted.

23 CM1502 Sem2-2013-14

24

Limitations of Bohr’s Model

• Works only for hydrogenic species (one electron

species) such as H, He

+

, Li

2+

etc

• Fails for atoms with more than one electron

because the e-e repulsions and additional nucleus

electron attractions create more complex

interactions.

• He assumed that an atom has only certain energy

levels in order to explain line spectra. However he

has no theoretical base for the assumption.

CM1502 Sem2-2013-14

• Louis de Broglie

considered other

systems that display

only certain allowed

motions such as the

vibrations of a plucked

guitar string.

• He proposed that if

energy is particle-like,

perhaps matter is wave

like.

• If electrons have

wavelike motion in

orbits of fixed radii, they

would have only certain

allowable frequencies

and energies.

de Broglie and Standing Waves

25 CM1502 Sem2-2013-14

26

Fundamental or 1

st

Harmonic

2

nd

Harmonic or 1

st

Overtone 3

rd

Harmonic or 2

nd

Overtone

Animations of standing waves

CM1502 Sem2-2013-14

27

• Perhaps the electrons, fixed to occupy specific orbits,

behaved like standing waves?

• Took the formulae E = mc

2

and set it equal to E = hc/λ

to obtain for a photon λ = h/mc, m is “equivalent”

mass (not actual) of a photon.

• For a particle, he substituted v (velocity of the particle)

for c.

de Broglie’s Matter Waves

mv

h

=

particle

λ

(1.5)

CM1502 Sem2-2013-14

28

• Electrons were shown by G.P. Thomson

to diffract!

• Only waves diffract!

• de Broglie proposed that the circular

orbits of electrons were actually

standing-waves.

• Bohr’s orbits were the paths around

which the wave may vibrate.

• Only certain orbits fulfill the standing-

wave condition, i.e., that an integral

number of wavelengths “fit” into the

circumference of the orbit.

• That is, 2πr = nλ

electron

• a major application of electron travelling

in waves is the electron microscope

Particles Act Like Waves!

28

x-ray diffraction of

aluminum foil

electron diffraction of

aluminum foil

CM1502 Sem2-2013-14

29

• Light and matter can interact.

– Light can be absorbed and emitted by matter.

– The absorption and emission can be continuous or

discrete.

• Light is quantized, E = hν.

• The energy states of atoms (and molecules) are

quantized.

• Discrete spectra can be explained by atoms

undergoing a transition and emitting or absorbing a

photon of energy.

• Matter has wave properties.

• The energy stationary-states of hydrogenic atoms

(only) can be explained by electrons existing in

standing-waves that surround the nucleus.

Summary

CM1502 Sem2-2013-14

30

Here is all about the

new postulate of de

Broglie regarding

matter-waves

Matter waves…..

If they are

waves, they

must obey a

wave-equation!

Prof., Erwin Schrödinger

physical chemist Peter Debye

CM1502 Sem2-2013-14

31

The Schrödinger Wave Equation

• Schrödinger eventually came up with the famous equation:

• Ĥ is the total energy operator or Hamiltonian operator. It

represents a set of mathematical operations that when

carried out with a particular wave function, yields one of the

allowed energy states of the atom. Thus each solution of

the equation gives an energy state associated with a given

atomic orbital.

• ψ is the wave function – also a mathematical function.

• E is the total energy of the system under consideration – it

is simply a number with units of J .

n n n

E H ψ ψ =

(1.6)

CM1502 Sem2-2013-14

32

The Wave Function, ψ

• ψ is just a function, like x

2

, or sin x, or e

x

.

– This function depends on the positions of all the

particles in the system under consideration.

– For the hydrogen atom, it is a mathematical function of

the position of the electron and proton.

– If we were looking at H

2

O instead, then ψ is a function

of the positions of the two H nuclei, and the O nucleus

and the positions of each and every one of the 10

electrons.

• For each value of n we have, we will have a different ψ

n

.

• That is, ψ

1

, ψ

2

, ψ

3

etc.

• Later we will see that these are the 1s, 2s, 3s, 2p and 3d etc. atomic

orbitals.

CM1502 Sem2-2013-14

33

Solving the Schrödinger Equation

• Solving the Schrödinger, therefore, involves finding the

correct mathematical function such that when we operate on

that function with Ĥ we get a constant times the original

function back again.

• If we can do this then the constant is the energy of the

system.

• Upon solving the Schrödinger equation it was found

that…three integers, denoted as n, l, m

l

fully characterized

the functions that solved the Schrödinger equation.

(According to Bohr, only n was needed)

( ) ( ) ( ) φ θ φ θ ψ , , ,

, , , ,

l l

m l l n m l n

Y r R r =

CM1502 Sem2-2013-14

34

The Total Energy, E

n

• Interestingly, the formula for the energies was the same as derived

from the Bohr and Bohr-de Broglie models, and did not depend on l,

nor m

l

.

• Recall that E

n

represented the energy of the H atom when its electron

was in orbit number n.

• Thus the n here reminds us that our system, here the H atom, could

exist in any number of energy states.

• Each energy state being labeled by n, with the lowest being n = 1.

2

2

2

0

4 2

1

8

n

h

e Z

E

n

ε

µ

− =

CM1502 Sem2-2013-14

35

one electron

system

CM1502 Sem2-2013-14

36

Quantum Numbers n, l, and m

l

• n – the principal quantum number (QN). The energy of

hydrogenic atoms depends only on this quantum

number.

– Can take the values 1, 2, 3, …

• l – azimuthal QN, or orbital angular momentum QN. Is

associated with the allowed angular momentum of an

electron in an orbital.

– Can take the values, 0, 1, 2, …, (n - 1)

• m

l

– magnetic QN, or orbital angular momentum

projection QN. Is associated with the orientation of the

orbital angular momentum

– Can take the values, -l, -(l-1), -(l-2), …, 0, 1, 2, …, l, i.e., m

l

goes

from –l to l in steps of one.

CM1502 Sem2-2013-14

37

Allowed Values of the Quantum

Numbers

• Will denote here as (n, l, m

l

)

• Some allowed values:

– (1,0,0), (5,4,-1), (2,1,0), (2,0,0),

(4,3,3)

• Some impossible values:

– (1,1,0), (5,4,-5), (2,1,-2), (2,0,1),

(0,3,3), (0,0,0)

• By convention lower-case

letters have been used to

designate the l QN.

l Letter

0 s

1 p

2 d

3 f

4 g

5 h

37 CM1502 Sem2-2013-14

38

Another Way…

• At around the same time Schrödinger developed the

matter wave equation, another scientist was

formulating quantum mechanics in an entirely different

way.

• Heisenberg used linear algebra, or matrix algebra, and

developed quantum matrix mechanics.

• A very important, finding from this approach is

Heisenberg Uncertainty Principle.

CM1502 Sem2-2013-14

39

Heisenberg Uncertainty Principle

• Heisenberg uncertainty principle states that it is

impossible to know simultaneously the position

and momentum of a particle.

∆ p . ∆ q ≥

h

4π

where

∆q = uncertainty in position

∆p = uncertainty in momentum

h = planks constant

m = mass of the particle

∆p = m.∆u

CM1502 Sem2-2013-14

40

The Heisenberg Uncertainty Principle

• Because energy is directly related to p, what the

uncertainty principle means for us is that because

the energy of an atom is known with considerable

accuracy, the location of the electron within the atom

is not known at all, accurately.

• This means that nice circular orbits of electrons

around nuclei can not be correct.

• Worse is that electron positions can only ever be

known in terms of probabilities rather than assigning

to them a special spot around the atom.

CM1502 Sem2-2013-14

41

The Probable Location of the electron

• While we cannot know the exact

position of the electron, we can know

where it probably is. i.e. where it

spends most of its time.

ψ

2

is called the probability density, a

measure of probability of finding the

electron in some tiny volume of the

atom.

• Electron probability density in the

ground state H-atom is shown in the

figure.

• The probability density decreases

with r but does not reach zero.

CM1502 Sem2-2013-14

42

Radial probability distribution

• The total probability of finding the electron at

some distance r from the nucleus is called

radial probability distribution.

CM1502 Sem2-2013-14

43

Probability Density vs Radial

Probability Density (RDF)

Dartboard analogy to a 1s orbital.

Imagine that a single dart (electron)

is thrown at a dartboard 1500 times.

The board contains 90% of all the

holes; it is analogous to the 1s

orbital. Where is a thrown dart most

likely to hit? The number of holes per

unit area is greatest in the “50”

region-that is, the “50” region has the

greatest probability density. The

most likely score is “30,” however.

Even though the density of holes is

not as great, the total area, and

hence the total number of hits, is

greater in the “30” ring than in the

“50” ring. The probability of scoring

“30” is greater than that of scoring

“50.”

43 CM1502 Sem2-2013-14

44

Analyzing the Dart Board

Zone N

holes

Area ρ

holes

Prob %

50 169 3.14 53.79 11

40 358 9.42 37.98 24

30 401 15.71 25.53 27

20 268 21.99 12.19 18

10 154 28.27 5.45 10

Probability per unit area is

highest in the 50 zone ≡ ψ

2

Most likely place to find

a dart, however, is in

the 30 zone ≡ RDF

Not as many holes per unit area as,

but a lot more places for the holes to go.

Even more places for the holes to go, but far

too few holes per unit area

44 CM1502 Sem2-2013-14

45

Shape of ‘s’ orbitals

An orbital with l=0

has

a spherical shape

with the nucleus at

its centre is called ‘s’

orbital. Because a

sphere has only one

orientation, an s

orbital has only one

m

l

value.

Node is the region

where the probability

of finding the

electron drops to

zero.

( )

0

/ 2 / 3

0 0 , 0 , 1

1

, ,

a r

e a r

− −

=

π

φ θ ψ

( )

0

2 /

0

2 / 3

0 0 , 0 , 2

2

2 4

1

, ,

a r

e

a

r

a r

− −

− =

π

φ θ ψ

Ψ

3,0,0

(r,θ,φ) =

CM1502 Sem2-2013-14

Shape of 2p orbital

An orbital with l=1 is called p orbital and

has two regions of high probability, one

on the either side of the nucleus.

there are three possible ml values

M

l

=-1,0,+1. Hence three possible

orientations in mutually perpendicular

directions.

46 CM1502 Sem2-2013-14

Shape of 3d orbital

47 CM1502 Sem2-2013-14

48

Shape of orbitals with higher l values

Orbitals with l=3 are f orbitals.

They have 7 orientations.

Given figure shows one of the seven

orientations.

• What does an h orbital look like?

• Check out these site:

• http://www.orbitals.com/orb/orbtable.htm

• http://winter.group.shef.ac.uk/orbitron/

J ust for interest…

CM1502 Sem2-2013-14

49

Radial Distribution

Functions/Bohr’s radius

Note the probability maxima

occurs at the same orbit

radius fixed by Bohr

CM1502 Sem2-2013-14

50

Radial Distribution Functions

CM1502 Sem2-2013-14

51

Summary

• Atomic orbitals are solutions to the Schrödinger equation

for hydrogenic atoms.

• Atomic orbitals are characterized by three quantum

numbers (QN).

– n the principal QN and ranges from 1 up to infinity. The larger

the n, the more extended the orbital.

– l the orbital angular momentum QN, and ranges from 0 up to n-1.

l gives the shape of the orbital.

• l = 0 is an s orbital, l = 1 is a p orbital, l = 2 is a d orbital, etc.

– m

l

the orbital angular momentum projection QN, and ranges from

–l up to l in steps of 1. m

l

gives the orientation of the orbital.

• ψ

2

is the probability density of finding the electron at

position (r,θ,φ) or (x,y,z).

• The radial distribution function gives the probability

density of finding the electron at a distance r from the

nucleus, regardless of direction.

• We finally arrive at the shapes of different atomic

orbitals.

CM1502 Sem2-2013-14

asdf

asdf

Are you sure?

This action might not be possible to undo. Are you sure you want to continue?

We've moved you to where you read on your other device.

Get the full title to continue

Get the full title to continue listening from where you left off, or restart the preview.

scribd