CH 12

Chapter 12 Quantum Mechanics and Atomic Theory
White light passing through two prims

400 B.C., Democritus and Leucippus: The concept of Atom.
John Dalton proposed the first systematic atomic theory.
Atomic structure accounts for periodicity in term of the electron arrangement in atoms.
Electrons play a key role in chemical reactions.
Particles Motion Behavior:
1. Classical Physics: developed by Isaac Newton are used to descript the motions of
macroscopic world.
2. Quantum mechanics: account for the behavior of light, electrons and atoms-
microscopic world.
12.1 Electromagnetic Radiation ：
Light is more properly called electromagnetic radiation(電磁波 ).
Electromagnetic radiation ：
Electronic and Magnetic fields that simultaneously oscillate in planes are
mutually perpendicular to each other and to direction of propagation.
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Wave ：
C ＝ λν
wavelength(λ) ， frequency(ν) and speed

(C).
Hz: 1/s or s-1 ；
Hertz : Frequency unit
All types of electromagnetic
radiation travel at the speed of light.

Radiation provides an important means of energy transfer via collisions or absorption.
As we proceed in the study of chemistry, we will consider many of the classes of

electromagnetic radiation and the ways in which they affect matters.
For example, in a microwave oven, H2O + hv  heat  increase the temperature.

12.2 Nature of Matter:
The end of 19th century, no intermingling
of matter (mass) and light (no mass).
Max Plank ： Blackbody radiation ( 黑體輻射 )
ΔE ＝ n hν (n ＝ 1 ， 2 ， 3……)
h ： Plank’s constant ＝ 6.626 × 10-34 Js
Energy is in fact quantized
and only be transferred in
discrete units of size hν.

Albert Einstein:
The electromagnetic radiation can be viewed as a steam
of “particles” now called as “photons”.
Ephoton ＝ hν ＝ hc / λ
Photoelectric effect ：
KEelectron ＝ 1/2 mv2 ＝ hν － hν0
hν ： energy of incident photon;
hν0 ： energy required to remove electron
from metal’s surface.

When hν ＜ hν0, no electrons are emitted regardless of the light intensity.
If hν ＞ hν0, the number of electrons emitted increase with
the intensity of light.
The kinetic energy of the emitted electrons
increases linearly with the frequency of the light.
Theory of special relativity ：
Kinetic energy ≡ K ＝ m0c2 /√(1 － v2/c2) － m0c2 ＝ m c2 － m0 c2
For photon m0 ＝ 0 (no rest mass)
E ＝ m c2
A photon has mass only in a relativistic sense (v → c)

it has no rest mass (v ＝ 0).
Louis de Broglie ：
Dual nature of light ： Wave ＋ Particulate
λ ＝ h / mν = h / p
All matter exhibits both particulate and wave properties.
For large pieces of matter, the associated wavelength is too small to be detected.
For small “pieces” of matter, exhibit predominantly wave property.
Exp. 12.2 Compare the wavelength of an electron and ball
h ＝ 6.626 × 10-34 Js ＝ 6.626 × 10-34 Kg m2 / s
λe ＝ 7.3 × 10 -11
m ©；
Copyright by λball ＝ 1.9
Houghton × 10Company.
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m All rights reserved.
The Wave Character of Particles:
Clinton Davisson and Lester Germer:
Diffraction of electrons by a crystal.
 Annealing leads to polycrystalline
sample to ordered planes of atoms.
With other particles (neutron, or H2)
the diffraction was observed.
 Particles have wave-like properties.
When examined on an atomic scale, the classical concepts of particle and wave melt
together,  (Particle + Wave) dual prosperities.

TEM 結構圖 :
奈米材料的鑑定 :
高解析度之穿透式電子顯微鏡 (TEM)
High-Resolution Transmission Electron Microscpe
Au nanoparticles:
(100)
(111)
(110)
1nm
Ag nanoparticles:
Au nanoparticles:
Diffraction results when light or electron beam is scattered from a regular array of
point or lines. 2dsinθ ＝ n λ
The lattice size of a regular array thus can be obtained.

12.3 Atomic Spectrum of Hydrogen:
H2 ＋ Energy 2H* 2H ＋ Emitting light
The hydrogen emission spectrum consisted of only a few lines are called
a line spectrum ( 線光譜 ).
White light containing all the wavelength of visible light is regarded as
a continuous spectrum ( 連續光譜 ).
Line spectrum: The energy of the electron
in the hydrogen atom is quantized.
ΔE ＝ Eexcited state － Eground state
＝ hν = hc/
Figure 12.8:
Continuous spectrum

12.4 The Bohr Model:
The electron in a hydrogen atom move around the nucleus
only in certain allowed circular orbits.
F ＝ attraction of positively charged nucleus and negatively charged electron
＝ mv2 / r
But the accelerating electron should emit light and lose energy  unstable atom model.
Energy levels are available to the electron in the hydrogen-like atom containing only one
electron.
E ＝ – 2.17×10-18 J(z2/n2)
z: atomic number ； H ＝ 1 ； He+ (z=2) ； Li2+ (z=3)…..
n ＝ 1 ， 2 ， 3……..(The larger n ， the larger orbital radius)
－： The energy of the bound

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n = 1 ； The lowest possible energy state
 Ground State
The emission or absorption wavelength of
ΔE = hv  λ ＝ hc /ΔE
ΔE = energy of level nfinal – energy of level ninitial
= – 2.178×10-18 J(1/nfinal2 － 1/ninitail2)
Example 12.3 Calculate the energy required to excite
the hydrogen electron from n = 1 to n = 2
E1= – 2.178×10-18 J ； E2= – 5.445×10-19 J
ΔE = E2 － E1 ＝ 1.634×10–18 J
λ ＝ hc /ΔE ＝ 1.216×10–7m = 121 nm (Ultraviolet

CuCl2
12.5 Quantum Mechanical Description of the Atom:
W. Heisenbery ， L. de Broglie and E. Schrodinger
: Wave mechanics Quantum mechanics
Standing waves( 駐波 ) in music instruments ：
Allowed wavelength n /2 λ ＝ L
Hydrogen electron visualized as
standing wave around the nucleus.
Schrodinger’s equation ：
HΨ＝ EΨ ; Ψ ： wave function (x ， y ， z)
H: operator ; Hamiltonian Operator
E: Potenial(V) + Kinetic(K) energy

Schrodinger’s equation ：
HΨ＝EΨ ; Ψ ： wave function (x ， y ， z)
H: operator ; Hamiltonian Operator: H ＝ – h2/2m ▽2 + V
E: total nergy : Potenial(V) + Kinetic(K) energy
– h2/2m ▽2 : kinetic energy operator = p2/2m
V : potential energy operator
Curvature of the function

Many solutions (Ψ) are found. Each solution consists of a wave
function Ψ that is characterized by a particular value of E.
Ψ describing the motion of the electron is often called an orbital.
Orbital( 軌域 ) is not a Bohr orbit( 軌道 ).
The wave function gives us no information about the movement of

electrons.
Heisenberg uncertainty principle ( 測不準原理 ):
There is a fundamental limitation to just how precisely we can know

both the position and the momentum of a particle at a give time.
Δx ． Δp≧ ħ / 2  Δt ． ΔE≧ ħ / 2
Macroscopic objects ： Uncertainty principle is negligible.
Small objects ： Uncertainty

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Example 12.5 The hydrogen atom has a radius on the order of 0.05 nm. Assume that we
know the position of an electron to accuracy of 1 %, calculate the uncertainty in the velocity
of the electron using Heisenberg Uncertainty principle.
Then compare this value with the uncertainty in the velocity of a ball of mass 0.2 kg and
radius 0.05 m whose position is known to an accuracy of 1 % of its radius.
Δx ． Δp = ħ / 2 = h / 4
For hydrogen: Δx = (0.01) (0.05 nm) = 5 x 10-13 m
 Δv = 1 x 108 m/s
For a ball: Δx = (0.01) (0.05 m) = 5 x 10-4 m
 Δv = 5 x 10-31 m/s
Macroscopic objects ： Uncertainty principle is negligible.
Small objects ： Uncertainty principle is important.

Δt ． ΔE≧ ħ / 2 ( E  v 頻率 )
 As the number of wavefunctions in superposition increases, the wave packet becomes
sharper on account of the more complete interference between the positive and negative
regions of the individual waves.
The infinite number of wavefunctions are needed in
the linear combination to generated a delta-function,
delta-function = i ci i (i = )
Hence, if we know the location of the particle
precisely, then its momentum is completely
unpredictable. (Its wavefunction is a superposition
of an infinite number of momentum eigenfunction)

Pulse
Figure12.12:
12.6 The Particle inWave/nucleus
a Box:
– ħ2/2m d2Ψ/dx2 ＝ EΨ; Ψ ＝ A sin kx ； E ＝ h2k2/2mL2
Boundary condition( 邊界條件 ):
(1). Particle can not be outside the box. (2). Total probability of finding the particle ＝ 1.
(3). Wave function must be continuous.
定義位能為 0
1. A fast method to get the energies of the particle in a box:
Each wavefunction to be a de Broglie wave that must fit within the container.
 L=nx½ ; n = 1, 2, 3, ……………………..
and therefore  = 2L/n  p = h/ = nh/2L
So the permitted energies: En = p2/2m = n2h2/8mL2 ; with n = 1, 2, 3 ………..
2. The method to solve the wavefunction 
The wavefunction k(x) = A sin kx
k(L) = A sin kL must be zero sin kL should be zero or A = 0 (unreasonable)
 kL = n  , n = 1, 2 , 3…………….
The value n = 0 is ruled out, because k(x) = 0 everywhere (unacceptable).
Negative values of n merely change the sign of sin kL
because sin (– x) = – sin x
 n(x) = A sin (nx/L) ; n = 1, 2, 3, …………………..

(b) Normalization:
Finding the normalization constant C:

L L
 2 dx = A2 0 sin2 (nx/L)dx = A2 x L/2 = 1
0
 A = (2/L)1/2 for all n.
En = n2h2/8mL2 , n = 1, 2, 3 ………………
n(x) = (2/L)1/2 sin (nx/L) for 0  x  L
A quantum number is an integer that labels the
state of the system.
A quantum number can often used to calculate
the energy corresponding to the state.

Figure 12.14: Three energy levels
The physically origin of the zero-point energy:
(1). The uncertainty principle: x px > ћ/2:
The particle’s location is not completely indefinite, so its momentum cannot be
precisely zero.  non-zero kinetic energy
(2). If the wavefunction is to be zero at the walls, but smooth, continuous, and non-zero
every where, then it must be curve.  Curvature implies the possession of Ek.
The separation between adjacent energy levels n and (n + 1) is
En+1 – En = (n +1)2h2/8mL2 – n2h2/8mL2 = (2n + 1) h2/8mL2
This separation decreases as the length of the container increases, and is very
small when the container has macroscopic dimensions.
As L  , atoms and molecules free to move. (not quantized)

Illustration:
For a container of length L = 1.0 nm, h2/8meL2 = 6.0 x 10-20 J (60 zJ). Therefore the
zero-point energy of an electron in such a box is E1 = 60 zJ. The minimum excitation
energy with n = 1 is 3 E1 = 1.1 eV.
Quantum-size effect in Nanochemistry:

Atomic force microscopy (AFM),
Atomic force microscopy (AFM), Scanning Tunneling Microscopy (STM)
Electrons as waves:
STM technology  electron wave functions
IBM researching groups:

12.7 Wave Equation for the Hydrogen Atom:
Ψ(x, y, z)  Ψ(r, θ, φ) ＝ R(r) θ(θ) Φ(φ)
H ＝ – h2/2m ▽2 － (Ze)(e) / r (r2 = x2 + y2 + z2)
En ＝ – Z2 /n2 (me4 / 802h2) ＝ – 2.178×10–18 J (Z2/n2)
n ： the principle quantum number ( 主量子數 )
l ： the angular momentum quantum number (角量子數 )
ml ： the magnetic quantum number. (磁量子數 )
The radial wave equation also depends on l, and hence
the radial wavefunctions depend on the values of both n and l.
All have the form: R(r) = (polynomial in r) x (decaying exponential in r)
These functions are most simply written in term of the dimensionless quantity ,
 = Z r /a0 ; a0 = 40ћ2/mee2
a0: the Bohr radius has the value 52.9177 pm;

Energy state transfer
Rn,l(r) = Nn,l (/n)l Ln,l() exp(– /2n) ; Ln,l(): associated Laguerre polynomial.
Note that, because R is proportional to l, all radial wavefunction are zero at the
nucleus unless l = 0.
Rn,l(r) = Nn,l (/n)l Ln,l() exp(– /2n) ; Ln,l(): associated Laguerre polynomial.
 (6 – )
To calculate the probability density for a 1s-electron at the nucleus, we set n = 1, l = 0 and
evaluate 2 at r = 0.
1,0,0 (0, , ) = R1,0(0)Y0,0(, ) = 2 (Z/a0)3/2 (1/4)1/2
The probability density 1,0,0 (0, , )2 = Z3/a03

12.8 The Physical Meaning of a Wave Function:
Attempt to attach physical significance to mathematic descriptions.
Ψ(ri,θi, φi)|2 d ＝ the probability of finding an electron near that point (i).
Probability distribution: The square of the wave function. Ψ|2
Radial probability distribution: The total probability of finding the electron at a particular
distance from the nucleus. Ψ|2 x 4r2

a
0
The Energy Levels:
En = – Z2e4/322ћ202n2
For H atom (Z =1),
En = – hcRH/n2; hcRH = He4/322ћ202
For hydrogen atom:
The Rydberg constant, R, is defined by the same
expression except for the replacement of H by the
mass of an electron.
RH = H/meR ; R = me e4/8202h3c
Shells and Subshells:
All the orbitals of a given value of n are said to form a single shell of the atom.
For hydrogenic atom, all orbitals of a given n,  same shell with same energy.
n = 1 2 3 4 ………………………
K L M N………………………
The orbitals with the same value of n but different l are
said to form a subshell of a shell.
l= 0 1 2 3 4 5 6…………………….(n – 1)
s p d f g h i…………………….
There are n subshells of a shell with quantum number n.
 n = 1, the one subshell with l = 0;
n = 2, two subshells, the 2s subshell (l = 0); 2p subshell (l = 1).

All s orbitals are spherically symmetric, but differ in the number of radial nodes.
Exp. 2s orbital has a radial node, where (2 – /2) = 0;  = 4  r = 2a0/Z.
Similarly, the 3s orbital has two nodes:
6 – 2 + (1/3)2 = 0 ; r = 1.90 a0/Z and 7.10 a0/Z.

p orbitals:
A p electron (l = 1) has nonzero orbital momentum  centrifugal effect.
 a profound effect on the shape of the wavefunction closed
to nucleus, zero amplitude at r = 0.
The same centrifugal effect appears in all
orbitals with l > 0.
In fact, that close to the nucleus a wavefunction
is proportional to rl,
p wavefunction  r; d wavefunction r2.
The increasingly strong dependence on as l increases
 the outcome of increasing centrifugal effects
from the increasing orbital angular momentum.

The three 2p orbitals are distinguished by three different ml values.
ml  orbital angular momentum around an arbitrary z-axis.
For ml = 0,  zero angular momentum around z-axis.
The wavefunction of a 2p orbital with ml = 0 is
p0 = R2,1(r) Y1,0(, ) = ¼(2)1/2 (Z/a0)5/2 r cos exp(–Zr/2a0) = r cos f(r)
Because in spherical polar coordinate z = r cos,  = z f(r)
All p orbitals with ml = 0 have wavefunction of
this form regardless of the n value.
Boundary surface:
Nodal plane
The wavefunction of 2p orbitals with ml = 1 have the following form:
px = –1/21/2 (p+1 – p–1 ) = r sin cos f(r) = x f(r) 3p orbital
py = i/21/2 (p+1 + p–1 ) = r sin sin f(r) = y f(r)

d orbitals:
When n = 3, l can be 0, 1, or 2.  one 3s orbital, three 3p orbitals, and five 3d orbitals.
For five d orbitals, ml = +2, +1, 0, – 1 , – 2.
The real combinations have the following forms: dxy = xy f(r) ; dyz = yz f(r) ;
dzx = zx f(r) ; dx2-y2 = ½ (x2 – y2)f(r) ; dz = (1/23) (3z2 – r2) f(r)

f orbitals:
When n = 4, l can be 0, 1, 2 or 3.  one 4s orbital, three 4p orbitals, five 4d orbitals and
seven 4f orbitals.
For seven f orbitals, ml = +3, +2, +1, 0, – 1 , – 2 – 3.

12.10 Electron Spin and the Pauli Principle
1925 Samuel Goudsmit, George Uhlenbeck:
The electron spin quantum number ms:
ms = +½ and -½.
Wolfgang Pauli: the Pauli exclusion principle:
In a given atom no two electrons can have the same set

of four quantum number (n, l, ml, ms).
+½ and -½
An orbital (same n, l, ml) can hold only two electrons,
and they must have opposite spins (different ms) .
+½ and +½
Electron spin

12.11 Polyelectronic Atoms
1. The kinetic energy of the electrons
2. The potential energy of attraction between the nucleus and the electrons.
3. The potential energy of repulsion between the two electrons.
The Schrödinger equation cannot be solved exactly.
Electron correlation problem: we cannot account for the effect a given

electron has on the motions of the other electrons in an atom
The quantum mechanical model  approximation
Treat each electron as if it were moving in a field of charge that is the net result of the
nuclear attraction and the average repulsions of all the other electrons.
The effect of the electron repulsions can be thought or as reducing the nuclear
charge. Effective nuclear charge, Zeff
This simplified atom has one electron like hydrogen.
Zeff > 1, each of the electron in He is bound more tightly than the electron in the H.
The Schrödinger equation, which contains energy terms that simultaneously involve two
different electrons, it cannot be solved exactly because the electron motions are correlated
and cannot be separated into equations that involve only one electron.
A computer is used to find the numerical values of the wave functions at each point in space
that produce the lowest overall energy for the atom.
 It is time-consuming for any but the simplest of atoms.
The results are very difficult to interpret physically.

The self-consistent field (SCF) method: a given electron is assumed to be moving in a
potential energy field that is a result of both the nucleus and the average “electron density”
of all the other electrons in the atom.
The many electrons Schrödinger equation is separated into a set of one-electron equations
that can be solved by computer.
 The same angular properties, Different radial characteristics;
the quantum number obtained in the description of the hydrogen
atom do not apply exactly to the orbitals obtained from the SCF.
12.14 Further Development of the Polyelectronic Model
A schematic of the SCF method

Aufbau principle:
As protons are added one by one to the nucleus to build up the

elements, electrons are similarly added to these atomic orbitals.
Pauli exclusion principle:
Two electrons with opposite spins can occupy an orbital.
Hund’s rule:
The lowest-energy configuration for an atom is the one having the maximum number
of unpaired electrons allowed by the Pauli principle in a particular set of degenerate orbitals
Na: 1s22s22p63s1
 [Ne] 3s1 [Ne]: core electrons
Mg: 1s22s22p63s2
 [Ne] 3s2
Al: 1s22s22p63s23p1
 [Ne] 3s23p1
12.13 The Aufbau Principle and the Periodic Table
Hund’s rule

For the polyelectronic atoms:
Different radial characteristics from those of hydrogen orbitals
Ens < Enp < End < Enf
The same angular properties as the orbitals of hydrogen.
The core electron shields outer electrons from the nuclear charge.
Penetration effect: an electron in the 3s orbital has a small

but significant probability of being quite
close to the nucleus.
The electron in the 3s orbital penetrates the shielding core electron “cloud” and “feels”
more of the nuclear charge.  E3s < E3p < E3d
The penetration effect: 4s > 3d
 E4s < E3d
K: : 1s22s22p23s23p64s1  [Ar] 4s1
12.15 Periodic Trends in Atomic Properties
Ionization energy: X(g)  X+(g) + e-
Koopman’s theorem states: The ionization energy of an electron is equal to the

energy
of the orbital from which it came.
It assumes that the electron left behind in the resulting ion will not reorganize in
Valence electrons: the electrons in the outermost principal quantum level of an atom
 Core electrons (inner electrons)
The elements in the same group have the same valence electron configuration.
Exp. Li, Na, K, Ca, Rb, Cs, Fr
Elements with the same valence electron configuration often shown similar chemical behavior.
K: 1s22s22p23s23p64s1  [Ar] 4s1 ; Ca: [Ar] 4s2
Sc: [Ar] 4s23d1 ; Ti: [Ar] 4s23d2 ; V: [Ar] 4s23d3

Figure 12.29:
Periodic table

1. The (n+1)s orbitals fill before the nd orbitals.
2. After lanthanum, [Xe]6s25d1, lanthanide series are elements in which the 4f
orbitals are being filled.
3. After actinium, [Rn]7s26d1, actinide series are elements in which the 5f orbitals
are being filled.
4. The group label tells the total number of valence electron for that group. IA, IIA,
IIIA, IVA, VA, VIA, VIIA, VIIIA
5. The groups labeled A are often called the main-group, or representative elements.

S: 1s22s22p63s23p4  [Ne] 3s23p4
Cd: 1s22s22p63s23p64s23d104p65s24d10  [Kr] 5s24d10
Hf: 1s22s22p63s23p64s23d104p65s24d105p66s24f145d2  [Xe] 6s24f145d2
Ra: 1s22s22p63s23p64s23d104p65s24d105p66s24f145d106p67s2  [Rn] 7s2

12.15 Periodic Trends in Atomic Properties
Ionization energy: X(g)  X+(g) + e-
Koopman’s theorem states: The ionization energy of an electron is equal to the

energy
of the orbital from which it came.
It assumes that the electron left behind in the resulting ion will not reorganize in
Al(g)  Al+(g) + e- I1 = 580 kJ/mol
Al+(g)  Al2+(g) + e- I2 = 1815 kJ/mol ; I = 1235 kJ/mol
Al2+(g)  Al3+(g) + e- I3 = 2740 kJ/mol ; I = 925 kJ/mol
Al3+(g)  Al4+(g) + e- I4 = 11600 kJ/mol ; I = 8860 kJ/mol
The increase in positive charge binds the electrons more firmly and the ionization energy
increases.
The large jump : valence electron  core electron

The first ionization energy increase across a period and decreases down a group.
Electrons in the same principal quantum level do not shield each other as well as core
electrons shield outer electrons.

Electron affinity: X(g) + e-  X-(g)
The energy change associated with the addition of an electron to a gaseous atom.
EA become more positive down a group, since the

electron is added increasing distances form the
nucleus.
The smaller energy Copyright

release of©Fbyatom has Mifflin
Houghton been attributed to rights
Company. All the small size of the 2p orbitals.
reserved.
Atomic radius decreases across a period and increases down a group.
Covalent atomic radius
Br2: 2r = 228 pm, r = 114 pm
Be2+, Mg2+, Ca2+, Sr2+:
Be2+ < Mg2+ < Ca2+ < Sr2+

12.16 The Properties of a Group: The Alkali Metals

Melting point

The Group 1A elements are very reactive.  low ionization energy.
2 Na(s) + Cl2(g)  2 NaCl (s)
2 Na(s) + S(s)  Na2S(s)
6 Na(s) + N2(g)  3 Na3N (s)
4 Na(s) + O2(g)  2 Na2O(s)
Reducing ability: Cs > Rb > K > Na > Li

2 M(s) + H2O(l)  H2(g) + 2 M+(aq) + 2 OH-(aq)
Reducing ability in aqueous solution : Li > K > Na
Hydration energy  charge density of ions

It follows from the Boltzmann distribution and the low temperature of a
molecular cloud that the vast majority of a cloud’s molecules are in their
vibrational and electronic ground states.
However, rotational excited states are populated at 10–100 K and decay

by the emission of radiation.
 Rotational spectrum of the Orion nebula ( 獵戶座大星雲 )

Over 100 interstellar molecules have been identified by their rotational
spectra, often by comparing radio telescope data with spectra obtained in the
laboratory or calculated by computational methods.
 hydrides, oxides (including water), sulfides, halogenated compounds,

nitriles, hydrocarbons, aldehydes, alcohols, ketones, and amides.
The largest molecules detected
by rotational spectroscopy is the
nitrile HC11N.
Interstellar space can also be investigated with vibrational
spectroscopy by using a combination of telescopes and
infrared detectors.
The experiments are conducted primarily in space-borne

telescopes because the Earth’s atmosphere absorbs a great
deal of infrared radiation.

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CH 12

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Chapter 12 Quantum Mechanics and Atomic Theory

White light passing through two prims

John Dalton proposed the first systematic atomic theory.

Electrons play a key role in chemical reactions.

Particles Motion Behavior:

Light is more properly called electromagnetic radiation(電磁波 ).

Electronic and Magnetic fields that simultaneously oscillate in planes are

mutually perpendicular to each other and to direction of propagation.

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wavelength(λ) ， frequency(ν) and speed

Hz: 1/s or s-1 ；

Hertz : Frequency unit

All types of electromagnetic

radiation travel at the speed of light.

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As we proceed in the study of chemistry, we will consider many of the classes of

For example, in a microwave oven, H2O + hv  heat  increase the temperature.

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The end of 19th century, no intermingling

of matter (mass) and light (no mass).

Max Plank ： Blackbody radiation ( 黑體輻射 )

h ： Plank’s constant ＝ 6.626 × 10-34 Js

Energy is in fact quantized

and only be transferred in

discrete units of size hν.

The electromagnetic radiation can be viewed as a steam

of “particles” now called as “photons”.

KEelectron ＝ 1/2 mv2 ＝ hν － hν0

hν ： energy of incident photon;

hν0 ： energy required to remove electron

from metal’s surface.

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If hν ＞ hν0, the number of electrons emitted increase with

the intensity of light.

The kinetic energy of the emitted electrons

increases linearly with the frequency of the light.

Theory of special relativity ：

Kinetic energy ≡ K ＝ m0c2 /√(1 － v2/c2) － m0c2 ＝ m c2 － m0 c2

For photon m0 ＝ 0 (no rest mass)

A photon has mass only in a relativistic sense (v → c)

Dual nature of light ： Wave ＋ Particulate

All matter exhibits both particulate and wave properties.

For small “pieces” of matter, exhibit predominantly wave property.

Exp. 12.2 Compare the wavelength of an electron and ball

h ＝ 6.626 × 10-34 Js ＝ 6.626 × 10-34 Kg m2 / s

Clinton Davisson and Lester Germer:

Diffraction of electrons by a crystal.

 Annealing leads to polycrystalline

sample to ordered planes of atoms.

With other particles (neutron, or H2)

the diffraction was observed.

 Particles have wave-like properties.

together,  (Particle + Wave) dual prosperities.

point or lines. 2dsinθ ＝ n λ

The lattice size of a regular array thus can be obtained.

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H2 ＋ Energy 2H* 2H ＋ Emitting light

a line spectrum ( 線光譜 ).

White light containing all the wavelength of visible light is regarded as

a continuous spectrum ( 連續光譜 ).

Line spectrum: The energy of the electron

in the hydrogen atom is quantized.

ΔE ＝ Eexcited state － Eground state