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Quantum Theory

of the Atom

Light Waves, Photons, and the Bohr Theory

To understand the formation of chemical bonds,

you need to know something about the electronic

structure of atoms. Because light gives us

information about this structure, we begin by

discussing the nature of light. Then we look at the

Bohr theory of the simplest atom, hydrogen.

1. The Wave Nature of Light

3. The Bohr Theory of the Hydrogen Atom

Copyright Houghton Mifflin Company. All rights reserved.

7|2

The Bohr theory firmly establishes the concept of

energy levels but fails to account for the details of

atomic structure. Here we discuss some basic

notions of quantum mechanics, which is the theory

currently applied to extremely small particles, such as

electrons in atoms.

4. Quantum Mechanics

5. Quantum Numbers and Atomic Orbitals

Copyright Houghton Mifflin Company. All rights reserved.

7|3

oscillation in matter or in a physical field.

Light is an electromagnetic wave, consisting of

oscillations in electric and magnetic fields traveling

through space.

7|4

and frequency.

Wavelength, symbolized by the Greek letter

lambda, , is the distance between any two

identical points on adjacent waves.

7|5

is the number of wavelengths that pass a fixed

point in one unit of time (usually a second). The

unit is 1/S or s-1, which is also called the Hertz (Hz).

7|6

speed, which for light is c, the speed of light, 3.00

x 108 m/s.

c =

The relationship between wavelength and

frequency due to the constant velocity of light is

illustrated on the next slide.

7|7

When the

wavelength is

reduced by a

factor of two,

the frequency

increases by

a factor of

two.

7|8

with a frequency of 6.4 1014/s?

= 6.4 1014/s

c = 3.00 108 m/s

c = so

= c/

m

3.00 x 10

c

s

14 1

6.4 x 10

s

8

= 4.7 10-7 m

Copyright Houghton Mifflin Company. All rights reserved.

7|9

electromagnetic radiation is called the

electromagnetic spectrum.

7 | 10

diffractedthat is, they spread out when they

encounter an obstacle about the size of the

wavelength.

In 1801, Thomas Young, a British physicist,

showed that light could be diffracted. By the early

1900s, the wave theory of light was well

established.

7 | 11

Plancks Quantization of Energy (1900)

According to Max Planck, the atoms of a solid

oscillate with a definite frequency, .

He proposed that an atom could have only certain

energies of vibration, E, those allowed by the

formula

E = h

where h (Plancks constant) is assigned a value of

6.63 x 10-34 J. s and n must be an integer.

.Copyright Houghton Mifflin Company.All rights reserved.

712

Line spectra of atoms

Black body radiation

Heat capacity of solids

Photoelectric effect

713

Li+

Ca2+

Cu2+

Sr2+

Copyright Houghton Mifflin Company. All rights reserved.

Ba2+

7 | 14

Emission

(line)

spectra of

some

elements.

715

Blackbody radiation

716

717

Plancks Quantization of Energy.

The only energies a vibrating atom can have are

h, 2h, 3h, and so forth.

The numbers symbolized by n are quantum

numbers.

The vibrational energies of the atoms are said to

be quantized.

Solved the ultraviolet catastrophe in blackbody

radiation

.Copyright Houghton Mifflin Company.All rights reserved.

718

The photoelectric

effect.

719

Photoelectric Effect

The photoelectric effect is the ejection of electrons

from the surface of a metal when light shines on it.

Electrons are ejected only if the light exceeds a

certain threshold frequency.

Violet light, for example, will cause potassium to

eject electrons, but no amount of red light (which

has a lower frequency) has any effect.

720

By the early part of twentieth century, the wave theory of

light seemed to be well entrenched.

In 1905, Albert Einstein proposed that light had both

wave and particle properties to explain the

observations in the photoelectric effect.

Einstein based this idea on the work of a German

physicist, Max Planck.

721

Photoelectric Effect

The energy of the photons proposed by Einstein

would be proportional to the observed frequency,

and the proportionality constant would be Plancks

constant.

E = h

In 1905, Einstein used this concept to explain the

photoelectric effect.

.Copyright Houghton Mifflin Company.All rights reserved.

722

The photoelectric

effect.

723

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.

724

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.

725

Photoelectric effect

For a given metal, a

certain amount of

energy is needed to

eject the electron

This is called the work

function

Since E=h, the

photons must have a

frequency higher than

the work function in

order to eject electrons

.Copyright Houghton Mifflin Company.All rights reserved.

726

consist of a positive nucleus around which

electrons move (Rutherfords model).

This explanation left a theoretical dilemma:

According to the physics of the time, an electrically

charged particle circling a center would continually

lose energy as electromagnetic radiation. But this

is not the caseatoms are stable.

7 | 27

the observation of line spectra of atoms.

A continuous spectrum contains all wavelengths

of light.

A line spectrum shows only certain colors or

specific wavelengths of light. When atoms are

heated, they emit light. This process produces a

line spectrum that is specific to that atom. The

emission spectra of six elements are shown on the

next slide.

Copyright Houghton Mifflin Company. All rights reserved.

7 | 28

7 | 29

postulates to account for

1. The stability of the hydrogen atom

2. The line spectrum of the atom

7 | 30

Energy-Level Postulate

An electron can have only certain energy values,

called energy levels. Energy levels are quantized.

For an electron in a hydrogen atom, the energy is

given by the following equation:

RH

n

RH = 2.179 x 10-18 J

n = principal quantum number

Copyright Houghton Mifflin Company. All rights reserved.

7 | 31

An electron can change energy levels by

absorbing energy to move to a higher energy

level or by emitting energy to move to a lower

energy level.

7 | 32

given by

E E f E i

E R H

n2

f

1

2

ni

7 | 33

related to E:

E photon E electron h

h Planck' s constant

h R H

n2

f

1

2

ni

7 | 34

transition is from lower n to higher n (nf > ni). In this

case, E will be positive.

Light is emitted from an atom when the electron

transition is from higher n to lower n (nf < ni). In this

case, E will be negative.

An electron is ejected when nf = .

7 | 35

Energy-level diagram

for the hydrogen atom.

7 | 36

an electron in the

hydrogen atom.

7 | 37

when the electron in a hydrogen atom

undergoes a transition from n = 6 to n = 3?

1

E R H

2

2

n

n

i

f

hc

hc

E

so

ni = 6

nf = 3

RH = 2.179 10-18 J

1

1

-19

=

-1.816

x

10

J

2

2

6

3

E 2.179 x 10 18 J

m

6.626 x 10 J s 2.998 x 10

1.094 10-6 m

19

- 1.816 x 10 J

34

7 | 38

Planck

Vibrating atoms have only certain energies:

E = h or 2h or 3h

Einstein

Energy is quantized in particles called photons:

E = h

Bohr

Electrons in atoms can have only certain values of

energy. ForR hydrogen:

E

H

2

n

RH 2.179 x 10 18 J, n principal quantum number

Copyright Houghton Mifflin Company. All rights reserved.

7 | 39

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.

740

Quantum Mechanics

The first clue in the development of quantum

theory came with the discovery of the

de Broglie 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.

.Copyright Houghton Mifflin Company.All rights reserved.

741

de Broglie Relation

For a photon that has both wave and particle

characteristics:

E = h = hc/ (recall c= )

E = mc2

mc2 = hc/ or = h/mc

Since mc is the momentum of a photon, can we

replace this with the momentum of a particle?

= h/mv

This suggests that particles have wave-like

characteristics!

.Copyright Houghton Mifflin Company.All rights reserved.

742

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.

2

34 kgm

10

s

6.63

(0.145 kg )(27 m / s )

1.7 10

34

cannot be detected.

.Copyright Houghton Mifflin Company.All rights reserved.

743

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.

Molecules are of the dimension of a few pm, so the

wave character of electrons is very important in

molecules

744

Quantum Mechanics

If matter has wave properties, why are they not

commonly observed?

In 1927, Davisson and

Germer was

demonstrated that a

beam of electrons,

just like X rays, could

be diffracted by a

crystal.

745

Davisson-Germer experiment

746

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.

.Copyright Houghton Mifflin Company.All rights reserved.

747

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)(mvx )

4

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

uncertainties are small, but for electrons, high

uncertainties disallow defining an exact orbit.

.Copyright Houghton Mifflin Company.All rights reserved.

748

Heisenbergs Uncertainty

Principle

(x)(mvx ) h

749

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.

Erwin Schrodinger defined 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 .

750

1 u u

2

u ( x, t ) cos(2 t ) ( x)

2

2

v t

x

2

2 2

4

( x) 0

2

2

x

v

2

2

4

since v=

(

x

)

0

2

2

x

( x) A cos(2 x / )

2

751

Schrodinger equation

mv 2

E

V ( x), rearrange to give mv={2m[E-V ( x)]}1/ 2

2

h

h

de Broglie relation

mv {2m[E-V ( x)]}1/ 2

2 4 2

2 2m[E-V ( x)]

classical wave eqn.

2 ( x) 2

( x) 0

2

2

x

x

(h / 2 )

(h / 2 ) 2 2

Schrodinger eqn. V ( x) ( x) E ( x)

2

2m x

752

Postulates of Quantum

Mechanics

The state of a quantum mechanical system is completely

specified by its wavefunction, (x,t)

For every classical observable there is a linear, Hermitian

operator in quantum mechanics

In any measurement associated with an operator, the only

values observed are eigenvalues of the operator,

A (x,t) = a (x,t)

The average values of an observable is given by its

expectation value,

*

A Ad

equation,

h ( x, t )

H ( x, t )

753

The wavefunction

The square of the wavefunction 2 is the

probability density for finding the particle at that

location

The wavefunction must be

Single valued

Continuous

Continuous first derivative

Quadratically integrable

d must be finite

*

754

It can be easily proven that the variational energy is always

greater than or equal to

the exact energy of the lowest

*

energy state

H d

Evar

d

*

Eexact

as to minimize the energy, we obtain a better wavefunction

and energy

With enough flexibility in the wavefunction, we can get very

close to the exact energy

.Copyright Houghton Mifflin Company.All rights reserved.

755

Schrodinger equation

H E ,

(h / 2 ) 2 2

H

V ( x)

2

2m x

outside the box V ( x) ,

( x) 0

inside the box V ( x) 0,

( x)

1/ 2

n x

sin(

)

l

n2h2

E

, n 1, 2,...

2

8ml

756

1-Dimensional Harmonic

Oscillator

Schrodinger equation

(h / 2 ) 2 2 1 2

H E , H

kx

2

2m x

2

E h (n 1/ 2), n 0,1, 2,...

v

k

km

,

2

m

(

h

/

2

1

2

0 ( x)

1/ 4

exp( x 2 / 2),

1/ 4

2 ( x)

4

1/ 4

1 ( x)

1/ 2

(2 1/ 2 x) exp( x 2 / 2)

(2 x 2 1) exp( x 2 / 2)

757

Hydrogen-like Atom

Nucleus with charge Ze at origin,

Electron with charge -e at (x,y,z) or (r, , )

Schrodinger equation for hydrogen-like atom

H E ,

2

2

2

Ze 2

x 2 y 2 z 2 4 r

0

2

(h / 2 ) 2 2 2

1

Ze

2

H

2

2

2m r

r r

2mr

4 0 r

(h / 2 ) 2

H

2m

2

2

2

2

L (h / 2 )

cot

2

2

2

sin

.Copyright Houghton Mifflin Company.All rights reserved.

758

759

760

the lowest level of the

hydrogen atom is

shown to the left.

Note that its value is

greatest nearest the

nucleus, but rapidly

decreases thereafter.

Note also that it never

goes to zero, only to a

very small value.

Copyright Houghton Mifflin Company. All rights reserved.

7 | 61

Figure A illustrates the probability density for an

electron in hydrogen. The concentric circles

represent successive shells.

Figure B shows the probability of finding the

electron at various distances from the nucleus.

The highest probability (most likely) distance is at

50 pm.

7 | 62

7 | 63

described by four quantum numbers:

1.

2.

3.

4.

Angular momentum quantum number (l)

Magnetic quantum number (ml)

Spin quantum number (ms)

particular electron. The fourth quantum number

refers to the magnetic property of electrons.

Copyright Houghton Mifflin Company. All rights reserved.

7 | 64

an atomic orbital (described by three quantum

numbersn, l, ml). It describes a region of space

with a definite shape where there is a high

probability of finding the electron.

We will study the quantum numbers first, and then

look at atomic orbitals.

7 | 65

This quantum number is the one on which the

energy of an electron in an atom primarily

depends. The smaller the value of n, the lower the

energy and the smaller the orbital.

The principal quantum number can have any

positive value: 1, 2, 3, . . .

Orbitals with the same value for n are said to be in

the same shell.

Copyright Houghton Mifflin Company. All rights reserved.

7 | 66

letters:

Letter

n

K

1

L

2

M

3

N

4

...

7 | 67

This quantum number distinguishes orbitals of a

given n (shell) having different shapes.

It can have values from 0, 1, 2, 3, . . . to a

maximum of (n 1).

For a given n, there will be n different values of l,

or n types of subshells.

Orbitals with the same values for n and l are said

to be in the same shell and subshell.

Copyright Houghton Mifflin Company. All rights reserved.

7 | 68

letters:

l

Letter

n

0

s

1

1

p

2

2

d

3

3

f

4

...

minimum value of n for each type of subshell is

shown above.

Copyright Houghton Mifflin Company. All rights reserved.

7 | 69

This quantum number distinguishes orbitals of a

given n and lthat is, of a given energy and shape

but having different orientations.

The magnetic quantum number depends on the

value of l and can have any integer value from l

to 0 to +l. Each different value represents a

different orbital. For a given subshell, there will be

(2l + 1) values and therefore (2l + 1) orbitals.

7 | 70

7 | 71

The figure

shows

relative

energies for

the hydrogen

atom shells

and

subshells;

each orbital

is indicated

by a dashedline.

Copyright Houghton Mifflin Company. All rights reserved.

7 | 72

This quantum number refers to the two possible

orientations of the spin axis of an electron.

It may have a value of either +1/2 or -1/2.

7 | 73

sets of quantum numbers?

n = 4, l = 4, ml = 0, ms =

n = 3, l = 2, ml = 1, ms = -

n = 2, l = 0, ml = 0, ms = /

n = 5, l = 3, ml = -3, ms =

value of l is 3.

(b) Permitted.

(c) Not permitted; ms can only be + or .

(b) Permitted.

Copyright Houghton Mifflin Company. All rights reserved.

7 | 74

An s orbital is spherical.

A p orbital has two lobes along a straight line

through the nucleus, with one lobe on either side.

A d orbital has a more complicated shape.

Free orbital viewer available at

http://www.orbitals.com/orb/index.html

Copyright Houghton Mifflin Company. All rights reserved.

7 | 75

of a 1s orbital and a

2s orbital highlights the

difference in the two

orbitals sizes.

7 | 76

of the 1s and 2s orbitals

give a better sense of

them in three

dimensions.

7 | 77

7 | 78

7 | 79

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