General Chemistry quantum chemistry chapter ppt

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General Chemistry quantum chemistry chapter ppt

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of the Atom

7.1 The Wave Nature of Light

7.2 Quantum Effects and Photons

7.3 The Bohr Theory of the

Hydrogen Atom

A wave is a continuously repeating

change or oscillation in matter or in a

physical field. Light is also a wave.

It consists of oscillations

in electric and magnetic

fields that travel

through space.Visible

light, X rays, and radio

waves are all forms of

electromagnetic

radiation.

A wave can be characterized by its

wavelength and frequency.

The wavelength, (lambda), is the distance between any

two adjacent identical points of a wave. The frequency,

(nyu), of a wave is the number of wavelengths that pass

a fixed point in one second.

The product of the frequency, (waves/sec) and

the wavelength, (m/wave) would give the

speed of the wave in m/s.

In a vacuum, the speed of light, c, is 3.00 x 108 m/s.

Therefore,

c

So, given the frequency of

light, its wavelength can be

calculated, or vice versa.

What is the wavelength of yellow light with a

frequency of 5.09 x 1014 s-1?

(Note: s-1, commonly referred to as Hertz (Hz)

is defined as cycles or waves per second.)

If c = then rearranging, we

obtain = c/

( 3.00 108 m / s )

5.09 1014 s 1

5.89 10 m or 589 nm

spectrum.

wavelength of 408 nm?

If c = then rearranging, we obtain = c/

3.00 108 m / s

408 109 m

14 1

7.35 10 s

Atom

Maxwell Planck-Black Body Radiation

1900Nobel Prize in 1918

radiation was quantized.

What is Quantized?

Energy can have only certain values (quantities),

not in between, instead of a continuum of values.

This is like energy existing on stairs of a

staircase instead of at any energy on a ramp.

Figure 7.2:

Emission

(line)

spectra of

some

elements.

hc

E=

c=speed of light 3.00 x 108 m/s

=wavelength of light

(6.626x10-34Js)(3.00x108m/s)

E=

(700x10-9m)

E= 2.84 x10-19Joules

(1905--Nobel Prize in 1921)

Intensity of the light had no effect. Energy is absorbed only

at quantized energies!

(Animation of Photoelectron Effect)

Photoelectric Effect

Einsteins assumption that an electron is ejected

when struck by a single photon implies that it

behaves like a particle.

When the photon hits the metal, its energy, h is

taken up by the electron.

The photon ceases to exist as a particle; it is said

to be absorbed.

Photoelectric Effect

The wave and particle pictures of light should

be regarded as complementary views of the same

physical entity.

This is called the wave-particle duality of light.

The equation E = h displays this duality; E is the

energy of the particle photon, and is the

frequency of the associated wave.

What is the energy of a photon

corresponding to radio waves of

frequency 1.255 x 10 6 s-1?

Solve for E, using E = h, and four

significant figures for h.

(6.626 x 10-34 J.s) x (1.255 x 106 s-1) =

8.3156 x 10-28 = 8.316 x 10-28 J

Hydrogen Atom

1913Nobel Prize in 1922

the atom could not be explained using the

then-current theories.

In 1913, using the work of Einstein and Planck, he

applied a new theory to the simplest atom,

hydrogen.

Before looking at Bohrs theory, we must first

examine the line spectra of atoms.

Hydrogen Atom

Bohrs Postulates

Bohr set down postulates to account for (1) the stability of

the hydrogen atom and (2) the line spectrum of the atom.

only specific energy levels in an atom.

2. Transitions between energy levels An electron

in an atom can change energy levels by

undergoing a transition from one energy level to

another.

Hydrogen Atom

Bohrs Postulates

Bohr derived the following formula for the energy

levels of the electron in the hydrogen atom.

Rh

E 2

n

value of 2.18 x 10-18 J.

Hydrogen Atom

Bohrs Postulates

When an electron undergoes a transition from a higher energy

level to a lower one, the energy is emitted as a photon.

From Postulate 1,

Rh

Ei 2

ni

Rh

Ef 2

nf

Hydrogen Atom

Bohrs Postulates

If we make a substitution into the previous equation that

states the energy of the emitted photon, h, equals Ei - Ef,

h E f E i

( )( )

Rh

2

nf

Rearranging, we obtain

h R h

1

1

n f2

n i2

Rh

2

ni

Hydrogen Atom

Atomic Line Spectra

In 1885, J. J. Balmer showed that the wavelengths,

, in the visible spectrum of hydrogen could be

reproduced by a simple formula.

1.097 10

1 1

m ( 22

n1 )

2

four visible lines for hydrogen

correspond to values of n = 3,

n = 4, n = 5, and n = 6.

Hydrogen Atom

Bohrs Postulates

Bohrs theory explains not only the emission of light,

but also the absorbtion of light.

When an electron falls from n = 3 to n = 2 energy

level, a photon of red light (wavelength, 685 nm) is

emitted.

When red light of this same wavelength shines on

a hydrogen atom in the n = 2 level, the energy is

gained by the electron that undergoes a transition

to n = 3.

A Problem to Consider

Calculate the energy of a photon of light emitted from a hydrogen atom when an electron falls from level n = 3 to level n = 1.

1 1

E h R h ( 2 2 )

nf ni

Note that the sign of E is negative because energy is emitted when an electron falls from a higher to a lower level.

E ( 2.18 10

18

J )(11 31 )

E 1.94 10

18

Quantum Mechanics

Bohrs theory established the concept of atomic

energy levels but did not thoroughly explain the

wave-like behavior of the electron.

Current ideas about atomic structure depend on

the principles of quantum mechanics, a theory

that applies to subatomic particles such as

electrons.

Quantum Theory

of the Atom

7.4 Quantum Mechanics

7.5 Quantum Numbers and

Atomic Orbitals

Quantum Mechanics

The first clue in the development

of quantum theory came with the

discovery of the de Broglie 1923 Nobel Prize in 1929

relation.

In 1923, Louis de Broglie reasoned that if light

exhibits particle aspects, perhaps particles of

matter show characteristics of waves.

He postulated that a particle with mass m and a

velocity v has an associated wavelength.

The equation = h/mv is called the de Broglie

relation.

Quantum Mechanics

If matter has wave properties, why are

they not commonly observed?

The de Broglie relation shows that a baseball

(0.145 kg) moving at about 60 mph (27 m/s) has a

wavelength of about 1.7 x 10-34 m.

34 kgm 2

s

6.63 10

( 0.145 kg )( 27 m / s )

1.7 10

34

cannot be detected.

Quantum Mechanics

If matter has wave properties, why are

they not commonly observed?

Electrons have wavelengths on the order of a few

picometers (1 pm = 10-12 m).

Under the proper circumstances, the wave character

of electrons should be observable.

Quantum Mechanics

In 1927, it was demonstrated that a beam of

electrons, just like X rays, could be diffracted

by a crystal.

The German

physicist, Ernst

Ruska, used this

wave property to

construct the first

electron

microscope in

1933.

Electron Clouds

Image Movie

Quantum Mechanics

Quantum mechanics is the branch of

physics that mathematically describes the

wave properties of submicroscopic particles.

We can no longer think of an electron as having

a precise orbit in an atom.

To describe such an orbit would require knowing

its exact position and velocity.

In 1927, Werner Heisenberg showed (from

quantum mechanics) that it is impossible to

know both simultaneously.

Quantum Mechanics

Heisenbergs uncertainty principle is a

relation that states that the product of the

uncertainty in position (x) and the

uncertainty in momentum (mvx) of a particle

can be no larger than h/4.

h

( x )(mv x )

4

When m is large (for example, a baseball) the

uncertainties are small, but for electrons, high

uncertainties disallow defining an exact orbit.

Erwin Schrdinger

1926 -Nobel Prize in 1933

Found the probability of finding an

electron in an atom, like flies to a

candle.

Erwin Schrdinger

1926 -Nobel Prize in 1933

Found the probability of finding an

electron in an atom, like flies to a

candle.

Quantum Mechanics

Although we cannot precisely define an

electrons orbit, we can obtain the probability

of finding an electron at a given point around

the nucleus.

this probability in a

mathematical

expression called a

wave function, denoted

(psi). The probability

of finding a particle in a

region of space is

defined by .

Atomic Orbitals

According to quantum mechanics, each

electron is described by four quantum

numbers.

Principal quantum number (n)

Angular momentum quantum number (l)

Magnetic quantum number (ml)

Spin quantum number (ms)

The first three define the wave function for a particular

electron. The fourth quantum number refers to the

magnetic property of electrons.

What do you need to know to find out where you live?

State

Principle

Quantum # (n)

City

Angular

Quantum # (l)

Street

Magnetic

Quantum # (ml)

House

Spin Quantum #

(ms)

Atomic Orbitals

The principal quantum number(n)

represents the shell number in which

an electron resides.

The smaller n is, the smaller the orbital.

The smaller n is, the lower the energy of the

electron.

Atomic Orbitals

The angular momentum quantum number

(l) distinguishes sub shells within a given

shell that have different shapes.

Each main shell is subdivided into sub shells.

Within each shell of quantum number n, there are n

sub shells, each with a distinctive shape.

l can have any integer value from 0 to (n - 1)

The different subshells are denoted by letters.

Letter

s p d f g

l

0 1 2 3 4 .

Atomic Orbitals

The magnetic quantum number (ml) distinguishes orbitals

within a given sub-shell that have different shapes and

orientations in space. Each sub shell is subdivided into

orbitals, each capable of holding a pair of electrons. m l can

have any integer value from -l to +l. Each orbital within a given

sub shell has the same energy.

The spin quantum number (ms) refers to the two possible spin orientations of

the electrons residing within a given orbital. Each orbital can hold only two

electrons whose spins must oppose one another. The possible values of m s

are +1/2 and 1/2.

Pictures

s-shape

Animations

3py

2py

3d

p-shape

s-shape

p-shape

1s 2s

3s

2px 3px

d-shape

3pz

2pz

d-shape

d-shape

Electron Clouds

Image Movie

Figure 7.23:

Orbital

energies of

the

hydrogen

atom.

(Click here

for nonhydrogen

atoms)

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