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Beginnings of Quantum Mechanics

CHEM 1300, Fall 2008

Dr. C. Bartels
1 Department

of Chemistry University of Manitoba

Lecture 3 - Sept. 11, 2008

Outline

Suggested Reading Cleanup and Reminders Radioactive Decay Theory of the Atom in the Early 1900s What Rutherford Missed Results that Rutherfords Model Cannot Explain What Else Was Being Discovered Strange Interactions with Light Particles and Waves

Suggested Reading

Todays lecture: Textbook Sections 19.3, 7.2, 7.3 Preparation for Next lecture: Textbook Sections 7.4, 7.5

Cleanup and Reminders


Radioactive Decay

Finishing up last lecture ... we still need to discuss radioactive decay. In general, chemistry and chemical reactions are concerned with behaviour and interactions of electrons in the atom. No chemical process alone can inuence the nucleus of the atom. However, there are still processes that can change the nucleus of the atom. These nuclear processes are the only way to change an atom from one element to another. Any other process (chemical processes) can only change the organization of electrons around the nucleus and the way different atoms share electrons.

Cleanup and Reminders


Radioactive Decay

So, what are some of the processes that change a nucleus? Radioactive Decay When an unstable nucleus undergoes a change to a more stable nucleus, it will eject a particle with high energy (fast moving particle). Alpha Decay () When a nucleus emits an 4 He nucleus to 2 become more stable. Beta Decay () When a nucleus emits an electron (0 e). 1 Positron Emission When a nucleus emits a positron (0 e), the +1 anti-matter equivalent of the electron. This is sometimes referred to as +-emission. Electron Capture When the nucleus absorbs an electron from an atomic orbital to become more stable.

Cleanup and Reminders


Radioactive Decay

Nuclear equations: Just as with normal chemical equations that you encountered in highschool, nuclear equations must be balanced. Specically, the atomic numbers (Z ) and the mass numbers (A) on both sides of a nuclear equation must be equal.

Cleanup and Reminders


Radioactive Decay

Example of -decay: Americium-241, the radioactive substance in smoke detectors, undergoes -decay:
241 95 Am

237 Np +4 He 2 93

(1)

Notice that the atomic numbers of He (2) and Np (93) add up to the atomic number of Am (95). Similarly, the mass numbers add up as well: 4 + 237 = 241. A convenient rule to remember is that when an atom undergoes -decay, it moves two spaces to the left on the periodic table.
Periodic Table

Cleanup and Reminders


Radioactive Decay

Example of -decay: Strontium-90, an isotope sometimes used as a source for radiotherapy, undergoes beta-decay.
90 38 Sr

90 Y +0 e 39 1

(2)

Notice that the atomic numbers of the -particle (-1) and Y (39) add up to the atomic number of St (38). Similarly, the mass numbers add up as well: 0 + 90 = 90. Remember: when an atom undergoes -decay, it moves one space to the right on the periodic table.
Periodic Table

Cleanup and Reminders


Radioactive Decay

Effectively what has happenned is that one of the neutrons has been converted to an electron and a proton:
1 0n

1 p +0 e +1 1

(3)

Any of these decays also releases a great deal of energy. It is this energy that allows the nucleus to become more stable. In the case of -decay, the electron has such a small mass that it typically is ejected with a very high speed.

Cleanup and Reminders


Radioactive Decay

An example of positron emission: Potassium-40, an isotope sometimes analysed in radiometric dating, undergoes positron emission.
40 19 K

40 Ar +0 e 18 +1

(4)

Notice that the atomic numbers of the positron (+1) and Ar (18) add up to the atomic number of K (19). Similarly, the mass numbers add up as well: 0 + 40 = 40. Remember: when an atom undergoes positron emission, it moves one space to the left on the periodic table.
Periodic Table

Cleanup and Reminders


Radioactive Decay

Effectively what has happenned is that one of the protons has been converted to a positron and a neutron:
1 +1 p

1 n +0 e 0 +1

(5)

Cleanup and Reminders


Radioactive Decay

An example of electron capture: Potassium-40, from the last example can also go through this form of decay.
40 19 K

+0 e 40 Ar 1 18

(6)

Notice that the atomic numbers of the electron (-1) and K (19) add up to the atomic number of Ar (18). Similarly, the mass numbers add up as well: 0 + 40 = 40. Remember: when an atom undergoes electron capture, it moves one space to the left on the periodic table.
Periodic Table

Cleanup and Reminders


Radioactive Decay

Effectively what has happenned is that one of the protons has absorbed an electron and been converted to a neutron. 1 0 1 (7) +1 p +1 e 0 n

Cleanup and Reminders


Radioactive Decay

Most nuclear decays will also produce gamma-rays (-rays) -rays are very high energy photons (we will talk about photons shortly) that are emitted during radioactive decay of a nucleus. The underlying cause of radioactive decay is an unstable nucleus, one side effect of this instability is excess energy that the nucleus attempts to get rid of. Ejecting - or -particles at high speed is one way to decrease the internal energy of the nucleus. Emitting a high energy photon (-ray) is another way to remove even more energy from the nucleus. How much energy must be ejected as -rays depends on the specic isotope and specic decay mechanism.

Cleanup and Reminders


Theory of the Atom in the Early 1900s

Remember where we left off at the end of the last lecture: 1904, Thomson proposes his plum pudding model of the atom. The model was awed, but it pointed the way towards our current understanding of matter. 1911, Rutherford proposed a better theory, the nuclear model. This model did not yet propose any of the structure that we now know exists in the electron cloud surrounding the nucleus.

What Rutherford Missed


Results that Rutherfords Model Cannot Explain

Since the late 1800s we have known about atomic emission spectroscopy: The atoms of any element can be excited into a high energy state. The energy that the atoms absorb will eventually expel the excess energy in the form of electromagnetic radiation. Even Thomson and Rutherford knew about this.

What Rutherford Missed


Results that Rutherfords Model Cannot Explain

The emission spectrum of hydrogen, the simplest atom

91.13 nm 364.51 nm

820.14 nm

Figure: Atomic emission spectrum of hydrogen. An atom with one proton and one electron, the simplest atom has a complex atomic emission spectrum, of which this is only a small portion. Compare Fig. 7.11 in your textbook.

Since Rutherfords model did not provide a detailed understanding of what the electrons do, it could not predict this spectrum.
deBroglie

What Rutherford Missed


What Else Was Being Discovered

Since 1865, physicists have had a precise, mathematical description of the nature of light in the form of Maxwells Equations. Maxwells Equations described light as moving waves of electromagnetic elds. Experiments since this time conrmed that light behaved as waves. Diffraction, interference, and many similar experiments produced results that could only be explained by waves.

What Rutherford Missed


What Else Was Being Discovered

Constructive Interference
2 1.5 1 0.5 0 -0.5 -1 -1.5 -2 -6 -4 -2 0 2 4 6 2 1.5 1 0.5 0 -0.5 -1 -1.5 -2 -6

Destructive Interference

-4

-2

Figure: Waves can undergo constructive interference and reinforce each other or ...

Figure: Waves can undergo destructive interference and cancel each other.

It is properties like interference that lead to experiments that proove that light behaves as waves.

What Rutherford Missed


What Else Was Being Discovered

] One interesting result if interferance is the result of the double slit interference experiment:

Lightsource

Figure: The double slit experiment is one test to determine if something behaves as a wave or as particle. Compare with Fig. 7.7 in the textbook.

What Rutherford Missed


What Else Was Being Discovered

Since 1897, thanks to Thomson, we have known about the existance of electrons. Results from many early experiments could be used to demonstrate that electrons were particles. For example, electrons always have the same charge and always have the same mass. How could something so discrete be anything but a particle? However, in the early 1900s, all of this certainty started to change...

What Rutherford Missed


Strange Interactions with Light

Two forced scientists to realize that there was more happenning. 1. Discovery of the photoelectric effect. 2. Double-slit experiment providing the same result with electrons as it did with light.

What Rutherford Missed


Strange Interactions with Light

Lightsource e

metal (Gold) e

Figure: The photoelectric effect occurs when light strikes the surface of a metal. If the wavelength of the light is short enough, it will cause electrons to be ejected from the metal surface.

What Rutherford Missed


Strange Interactions with Light

Only light with wavelengths below a certain threshold would work. Above the threshold, nothing would happen, nomatter how intense the light Below the threshold, more intense light would generate more electrons. This combination of factors leads to the conclusion that
1. Light is composed of particles that we call photons. 2. The energy (E) that a photon has is related to the wavelength () by the equation E= hc (8)

where h is Plancks constant (6.6261035 Js) and c is the speed of light (2.99792458108 ms1 ).

What Rutherford Missed


Strange Interactions with Light

Albert Einstein stated that the energy of light was quantized according to the equation from the previous slide. What he was refering to was that light comes in small portions, photons, and that each photon carries a specic amount of energy. In fact, if the amount of energy that a photon excedes the threshold needed in the photo electric effect, the excess energy went into making the expelled electrons move faster KE = hc 1 me v 2 = = h 2 (9)

where me and v are the mass and speed of the electron respectively, is the threshold energy (sometimes called the work function) and is the frequency of light, ( = c/).

What Rutherford Missed


Strange Interactions with Light

This result forced people to recognize a strange aspect of reality. Particle-Wave Duality When dealing with objects on the small scale in which atom, electrons, photons and other similar objects exist, the circumstances of an experiment can cause the object to behave as either a particle or a wave.

What Rutherford Missed


Particles and Waves

This dual behaviour also applies to objects the scientists were certain to be particles, before the 1920s. Objects like the electron. As was mentioned earlier, the electron provided results in the double-slit experiment similar to the results seen with light. The image projected by the electrons produced an interference patern that could only be explained by waves.
double slit experiment

What Rutherford Missed


Particles and Waves

In fact, deBroglie was able to show that the wavelength of a particle, such as an electron, was related to the particles momentum. h h = = (10) mv p where m and v are the mass and speed of the particle respectively. We are now ready to explain the lines from the hydrogen spectrum.
hydrogen spectrum

What Rutherford Missed


Particles and Waves

With the discovery of this dual nature of matter on an atomic scale, science was now ready for the next big step in the development of the theory of the atom. People once again started to think about the atom. Could the wave-like nature of electrons be used to explain the atomic emission spectrum of hydrogen?

What Rutherford Missed


Particles and Waves

Bohr eventually come up with a theory by noting the two points that
1. Electrons move as waves. 2. Waves interfere with each other.

He theorized that for an electron to orbit around the nucleus in Rutherfords model, the orbit must be of the correct size to form an whole number of wavelengths. Only in this way could the electron avoid interfering with itself and cancelling its own wave.

What Rutherford Missed


Particles and Waves

Figure: The Bohr model of the atom with an electron passing through eight entire wavelengths as it orbits the nucleus.

Bohr had now provided the tools needed to understand the atomic emission spectrum of hydrogen through the equation 1 1 1 1 = 2 (11) 2 Rh n2 n1

What Rutherford Missed


Particles and Waves

For next lecture we will understand where the equation 1 1 = Rh 1 1 2 2 n2 n1 (12)

comes from, what it means, and how it predicts the hydrogen atomic emission spectrum. We will also see the last major piece of information that was needed for our modern understanding of the atom, the Heisenberg Uncertainty Principle. From here we will complete the theory of the atom and begin discussing the Schrdinger wave equation and orbitals.

IUPAC Periodic Table of the Elements


1 1 18 2

H
hydrogen
1.007 94(7)

He
2
Key:

13 atomic number 5

14 6

15 7

16 8

17 9

helium
4.002 602(2)

10

Li
lithium
6.941(2)

Be
beryllium
9.012 182(3)

Symbol
name
standard atomic weight

B
boron
10.811(7)

C
carbon
12.0107(8)

N
nitrogen
14.0067(2)

O
oxygen
15.9994(3)

F
fluorine
18.998 4032(5)

Ne
neon
20.1797(6)

11

12

13

14

15

16

17

18

Na
sodium
22.989 769 28(2)

Mg
magnesium
24.3050(6)

Al
3 21 4 22 5 23 6 24 7 25 8 26 9 27 10 28 11 29 12 30
aluminium
26.981 538 6(8)

Si
silicon
28.0855(3)

P
phosphorus
30.973 762(2)

S
sulfur
32.065(5)

Cl
chlorine
35.453(2)

Ar
argon
39.948(1)

19

20

31

32

33

34

35

36

K
potassium
39.0983(1)

Ca
calcium
40.078(4)

Sc
scandium
44.955 912(6)

Ti
titanium
47.867(1)

V
vanadium
50.9415(1)

Cr
chromium
51.9961(6)

Mn
manganese
54.938 045(5)

Fe
iron
55.845(2)

Co
cobalt
58.933 195(5)

Ni
nickel
58.6934(2)

Cu
copper
63.546(3)

Zn
zinc
65.409(4)

Ga
gallium
69.723(1)

Ge
germanium
72.64(1)

As
arsenic
74.921 60(2)

Se
selenium
78.96(3)

Br
bromine
79.904(1)

Kr
krypton
83.798(2)

37

38

39

40

41

42

43

44

45

46

47

48

49

50

51

52

53

54

Rb
rubidium
85.4678(3)

Sr
strontium
87.62(1)

Y
yttrium
88.905 85(2)

Zr
zirconium
91.224(2)

Nb
niobium
92.906 38(2)

Mo
molybdenum
95.94(2)

Tc
technetium
[97.9072]

Ru
ruthenium
101.07(2)

Rh
rhodium
102.905 50(2)

Pd
palladium
106.42(1)

Ag
silver
107.8682(2)

Cd
cadmium
112.411(8)

In
indium
114.818(3)

Sn
tin
118.710(7)

Sb
antimony
121.760(1)

Te
tellurium
127.60(3)

I
iodine
126.904 47(3)

Xe
xenon
131.293(6)

55

56

57-71
lanthanoids

72

73

74

75

76

77

78

79

80

81

82

83

84

85

86

Cs
caesium
132.905 451 9(2)

Ba
barium
137.327(7)

Hf
hafnium
178.49(2)

Ta
tantalum
180.947 88(2)

W
tungsten
183.84(1)

Re
rhenium
186.207(1)

Os
osmium
190.23(3)

Ir
iridium
192.217(3)

Pt
platinum
195.084(9)

Au
gold
196.966 569(4)

Hg
mercury
200.59(2)

Tl
thallium
204.3833(2)

Pb
lead
207.2(1)

Bi
bismuth
208.980 40(1)

Po
polonium
[208.9824]

At
astatine
[209.9871]

Rn
radon
[222.0176]

87

88

89-103
actinoids

104

105

106

107

108

109

110

111

Fr
francium
[223]

Ra
radium
[226]

Rf
rutherfordium
[261]

Db
dubnium
[262]

Sg
seaborgium
[266]

Bh
bohrium
[264]

Hs
hassium
[277]

Mt
meitnerium
[268]

Ds
darmstadtium
[271]

Rg
roentgenium
[272]

57

58

59

60

61

62

63

64

65

66

67

68

69

70

71

La
lanthanum
138.905 47(7)

Ce
cerium
140.116(1)

Pr
praseodymium
140.907 65(2)

Nd
neodymium
144.242(3)

Pm
promethium
[145]

Sm
samarium
150.36(2)

Eu
europium
151.964(1)

Gd
gadolinium
157.25(3)

Tb
terbium
158.925 35(2)

Dy
dysprosium
162.500(1)

Ho
holmium
164.930 32(2)

Er
erbium
167.259(3)

Tm
thulium
168.934 21(2)

Yb
ytterbium
173.04(3)

Lu
lutetium
174.967(1)

89

90

91

92

93

94

95

96

97

98

99

100

101

102

103

Ac
actinium
[227]

Th
thorium
232.038 06(2)

Pa
protactinium
231.035 88(2)

U
uranium
238.028 91(3)

Np
neptunium
[237]

Pu
plutonium
[244]

Am
americium
[243]

Cm
curium
[247]

Bk
berkelium
[247]

Cf
californium
[251]

Es
einsteinium
[252]

Fm
fermium
[257]

Md
mendelevium
[258]

No
nobelium
[259]

Lr
lawrencium
[262]

Notes - 'Aluminum' and 'cesium' are commonly used alternative spellings for 'aluminium' and 'caesium'. - IUPAC 2005 standard atomic weights (mean relative atomic masses) as approved at the 43rd IUPAC General Assembly in Beijing, China in August 2005 are listed with uncertainties in the last figure in parentheses [M. E. Wieser, Pure Appl. Chem., to be published]. These values correspond to current best knowledge of the elements in natural terrestrial sources. For elements that have no stable or long-lived nuclides, the mass number of the nuclide with the longest confirmed half-life is listed between square brackets. - Elements with atomic numbers 112 and above have been reported but not fully authenticated. Copyright 2005 IUPAC, the International Union of Pure and Applied Chemistry. For updates to this table, see http://www.iupac.org/reports/periodic_table/. This version is dated 3 October 2005.

-decay

-decay

positron emisson

electron capture

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