7.

1 Electromagnetic Radiation
Waves
Waves have 3 primary characteristics:
1. Wavelength (λ, 波長): 兩個波峰之間的距離.
2. Frequency (ν, 頻率): 每秒波通過空間中的某一定點的數目.
3. Speed (c, 波速): 光的速度為 2.9979 x 108 m/s.

c = ln
ln
n = c/l
l = wavelength (m)
n = frequency (s–1 or Hz)
c = speed of light (m/s)
 Electromagnetic radiation
• Electromagnetic radiation是能量在空間行進的一種方式
• Radiant energy (輻射能)展現與波類似的行為，在真空
中以光的速度前進.

Fig. 7.2: Classification of electromagnetic radiation

 7.2 The Nature of Matter

Particles:
things that had mass and whose position in space
could be specified.
Waves:
described as massless and delocalized.
 Black Body Radiation
Max Planck (1858 ~ 1947):
• 黑體是一個理想化的模型，可以吸收所有照射於表面的電
磁波，在某溫度下達熱平衡後會釋放出特定的電磁波。
• 蒲朗克由黑體幅射的研究發現物質能量的轉移是不連續的，
可用能量量子化來解釋。
• Energy can be gained or lost in whole-number
multiples of hv.

https://www.nuclear-power.com/nuclear-engineering/heat-
transfer/radiation-heat-transfer/plancks-law-plancks-hypothesis/
 Planck’s equation:
Planck’s equation:

nhc
E = nhv =
l
• E = change in energy, in J • n = frequency, in s–1
• n = an integer (1, 2, 3 ….) • l = wavelength, in m
• h = Planck’s constant, 6.626 × 10–34 J s • c = speed of light (m/s)
 Example 7.2

The blue color in firework is often achieved by heating CuCl to about 1200
oC. Then the compound emits blue light having a wavelength of 450 nm.

What is the increment of the energy (the quantum) that is emitted at 4.50 x
102 nm by CuCl?

c 2.9979  108 m/s

n= l = = 6.66  1014 s-1
4.50  10-7 m

E = hn = (6.626  10-34 Js)(6.66  1014 s-1) = 4.41  10-19 J

 Light also has particle nature:
Photoelectric effect
Albert Einstein (1879 ~ 1955)
• The effect refers to the phenomenon in which electrons are
emitted from the surface of a metal when the light strikes it.
• 光電效應的實驗結果:
1.只有達到某一頻率 (no) 以上的光才能將電子由金屬表
面移除。 這個頻率 (no) 稱為 threshold frequency 。

2.低於這個threshold frequency (門檻頻率)的光， 不管

強度如何，都無法將電子由金屬表面移除。

3.光的頻率如果高於threshold frequency ，則被移除的

電子的數目隨著光的強度增加而增加。

4.光的頻率如果高於threshold frequency ，則被移除的

電子的動能隨著光的頻率呈線性增加。

• 光電效應之問題:
1. 為何只有超過某數值頻率的光才能把電子從物質釋放出來？
2. 被釋放的電子的能量為何與光線的強度無關?
 Photons
• 光電效應的結果可以利用普朗克的光粒子假設解釋。

• Einstein concluded that electromagnetic radiation is

quantized and can be viewed as a stream of “particles”
called photons.

Ephoton = h n = hc/l

h = Planck’s constant

n = frequency of the radiation

l = the wavelength of the radiation

• 光線的強度只決定光子的多寡，光線的能量只由其頻率
而定。光線越明亮，光子密度越高，但光的頻率不會變。

• 光的強度愈強，激發越多電子，但不會增加電子能量

• 移除電子所需要的最小能量: Eo = hno

• 頻率高於threshold frequency的光，多出的能量變成電
子的動能

• Kinetic energy of an electron:

KEelectron = 1/2mv2 = hn – hn o

m = 電子質量 n = 入射光頻率
V = 電子速度 no =門檻頻率
 能量(energy) & 物質(matter)
• In his special theory of relativity, Einstein derived the
famous equation:

E = mc2
(E = energy; m = mass; c = speed of light)
Ephoton = hv = hc/l = mphotonc2
mphoton = h/lc apparent mass of photon

• 重要意義: 能量（光子）具有質量

11
Particle also has wave nature:
de Broglie’s equation
Louis de Broglie (French, 1892 ~ 1987)

• de Broglie’s equation

l = h / mv
l = wavelength, in m
h = Planck’s constant, 6.626 × 10–34 J s (= kg m2 s–1)
m = mass, in kg
v = velocity, in ms–1

• l = h / mphotonc
 Example 7.3

Compare the wavelength for an electron (mass = 9.11  10 −31 kg)

traveling at a speed of 1.0  107 m/s with that for a ball (mass =
0. 10 kg) traveling at 35 m/s.

使用λ = h / mv,

λe = (6.626 x 10 -34 ) / (9.11 x 10 - 31)(1.0 x 107) = 7.27  10-11 m

λb = (6.626 x 10 - 34 ) / (0.10)(35) = 1.9  10-34 m

In a range of X-ray
 電子的波動性
C. J. Davisson & L. H. Germer at Bell Laboratories (1927)
由實驗證實電子束照射在Ni晶體上會產生繞射---電子的波動性
 verified de Broglie’s relationship
 The Dual Nature of Light

Fig. 7.5: Electromagnetic radiation exhibits wave

properties and particulate properties.
上述 20 世紀科學的突破性研究結果，其重大意義為:
Matter and energy are not distinct.
All matter exhibits both particulate and wave properties.

16
 7.3 The Atomic Spectrum of Hydrogen

FIG. 7.7:
(A) 連續光譜:

(B)氫原子光譜
[線光譜]:

17
Fig. 7.8: A change between two discrete energy levels
emits a photon of light.

電子由高能階掉到低能階，會釋放出特定波長的
電磁波（能量），它的波長可以利用 Planck’s equation
E = hc/l 計算而得。 18
 7.4 The Bohr Model
Niels Bohr (1885 ~ 1962):
• Bohr 於1913年提出 quantum model for the H atom
• 在氫原子中，電子是以一些特定的圓形軌道繞行原子核。
• n =  時，E = 0 ; n = 1 時為 ground state (基態)
(ground state: 原子能量最低的狀態)
• Bohr's model doesn’t correctly describes atoms other than
hydrogen.
 
−1 8 Z
2

• E = − 2 . 178  10  2  J
n 
E = energy of the levels in the H-atom
Z = nuclear charge (for H, Z = 1)
n = an integer (n, orbit radius )

1 1
• E = Efinal – Einitial = -2.178 x 10-18 ( – 2
)J
nf 2 ni

例如: For H atom, n = 6 → n = 1

E = E1 – E6 = -2.117 × 10–18 J (release E)
l = hc/E = 9.383 × 10–8 m
(計算l時， E使用正值，因為負值沒意義)
7.5 The Quantum Mechanical Model of the Atom
wave mechanics (波動力學) or quantum mechanics (量子力學)
Based on the wave properties of the atom

• 電子具有駐波的性質

Fig. 7.10: The standing waves (駐波)

caused by the vibration of a guitar
string fastened at both ends. Each dot
represents a node (節點, a point of
zero displacement).
• 量子力學，以駐波描述氫原子
• 電子以駐波的方式描述時，僅容許
存在於某些特定波長。

Fig. 7.11: The hydrogen electron visualized

as a standing wave around the nucleus.
 Electrons behave as both particles and
waves. So, we can use the
wavefunction to describe the
electronic orbitals.

• Wavefunction (ψ):
the mathematical description of the shape of
the wave as it vibrates.
 Schrödinger equation
Erwin Schrödinger (1887 ~ 1961)
Schrödinger equation:
^
H = E
 = wave function (波函數)
Ĥ = mathematical operator (數學運算子)
E = total energy of the atom (系統總能，位能+動能)
• 解方程式，可以得到許多的解，每一個解含有一個
波函數，及一個總能量E。
• 特定的波函數通常稱為軌域.
 Particle in a box
• A simple illustration of how energy quantization.
• The particle in a box model describes a particle free to
move in a small space surrounded by impenetrable
barriers.
Solved by Schrödinger equation:
^ = E n2h2
H =
8ma2 Ψ

^ -h2 2
H =
82m ( x2 )

n2h2 Ψ = A sin rx + B cos sx

E = 8ma2
n : an integer
Particle in a box

Ψ Ψ2
 Heisenberg uncertainty principle
Werner Heisenberg (1901 ~ 1976)

x·(mv)  h
4
x = 位置
mv = 動量
h = Planck’s constant, 6.626 × 10–34 J s (= kg m2 s–1)

• 對於粒子位置的測量越正確，對動量產生的誤差會越大
• 對 large particles (如 baseball) 而言，此可忽略
• 對 small particles (如 electron, mass = 9.11  10 −31 kg ) 而言，
此限制則相當重要。
 Probability Distribution

2:稱為probability distribution等於在空間中的某一
點發現電子的機率

[(x1, y1, z1)]2 N1

[(x2, y2, z2)]2 = N2
 Probability distribution of 1s orbital

(a) 1 s 軌域在三度空間中的機率
分佈，亦稱為電子密度圖(2)

(b) 1 s 軌域距離原子核某處的機
率分佈(2)

Figure 7.12 (a) The probability distribution for the hydrogen 1s orbital in three-
dimensional space. (b) The probability of finding the electron at points along a line
drawn from the nucleus outward in any direction for the hydrogen 1s orbital.
 Radial probability distribution of 1s orbital
• Radial probability distribution 是在每一個球殼的機率分佈

Figure 7.13 (a) Cross section of the hydrogen 1s orbital probability distribution divided into
successive thin spherical shells. (b) The radial probability distribution.

• Bohr radius for H = ao = 5.29 x 10-2 nm = 0.529 Å

• 一般化學家定義 H 1s orbital size 為 the radius of the
sphere that encloses 90% of total electron probability.
 7.6 Quantum numbers (QN)
1. 主量子數 n (principal quantum number, n = 1, 2, 3, .
. .) – 與軌域的大小及能量有關.
2. 角動量量子數 l (angular momentum quantum
number, l = 0 to n − 1) – 與軌域的形狀有關.
3. 磁量子數 ml (magnetic quantum number, ml = l to −l)
– 與軌域在空間中的方位有關.
4. 電子自旋量子數 ms (spin quantum number, ms =
+1/2, −1/2) – 與電子的自旋狀態有關.

31
角動量量子數(l)與對應符號
 7.7 Orbital Shapes and Energies
Wave function Radial probability distribution

Ψ Ψ2

S Orbitals
 氫原子S軌域的三種表示

• # of nodal surfaces: n – 1

Figure 7.14 Three representations of the

hydrogen 1s, 2s, and 3s orbitals. (a) the
square of the wave function. (b) ”Slices”
of the three-dimensional electron density.
(c) The surfaces that contain 90% of the
total electron probability.
2s orbital
 p orbitals
For p orbitals:
• two lobes separated by a node at the nucleus
• n  2,
• Three degenerate orbitals: px , py , pz

Fig. 7.15: Representation of the 2p orbitals. (a) The electron probability distributed
for a 2p orbital. (b) The boundary surface representations of all three 2p orbitals.
3p 軌域電子機率分佈的截面圖
 d orbitals
For d orbitals: n  3
dxz , dyz, dxy dx²-y² dz²

FIG. 7.17: .
 f orbitals
For f orbitals: n  4

Fig. 7.18: Representation of the 4f orbitals in

terms of their boundary surface.
 氫原子軌域

• 氫原子為單電子系統，其氫原子軌域的能量由 n 決定，
具相同 n 之所有軌域具有相同能量，稱為 “degenerate”。

Fig. 7.19: Orbital energy levels for the hydrogen atom.

氫原子的結論：
1. 量子力學的模型將電子視為駐波，結果導致一系列用來
描述電子的能量及空間分佈的波函數。

2. 量子力學的模型無法詳細的描述電子的運動，而波函數
的平方表示電子在那個軌域的機率分佈，結果使我們可
以用probability distribution 或electron density maps 來描
述軌域。

3. 軌域的大小是任意定義含有90%總電子機率的表面。

4. 氫原子有許多種類的軌域，基態時電子存在於1s軌域，
電子可以吸收能量，激發到較高能量的軌域。
 7.8 Electron Spin and Pauli Principle
• Electron spin quantum number (ms = +½ , –½ )
電子自旋量子數 – relates to the spin states of the
electrons

Wolfgang Pauli (1900 ~ 1958)

Pauli exclusion principle
(庖利不相容原理)
▪ 在一個原子中，沒有任何兩個電子可以擁有四個相同的量
子數 (n, l, ml, ms).
▪ 因此, 一個軌域僅能容納兩個自旋方向相反的電子.
43
 7.9 Polyelectronic Atoms
多電子原子
• 利用量子力學解多電子原子的問題，需要處理下列能量:
(a) 電子運動的動能
(b) 電子與原子核之間的吸引位能
(c) 電子與電子之間的排斥位能

• Electron correlation problem: 由於電子的路徑未知，無法

正確計算電子間的斥力。量子力學使用近似的方法，以平
均電場的方式來處理，得到 hydrogen-like orbitals，它的
基本形狀與氫原子軌域相同。但是，軌域大小及能量不同。

• 多電子原子軌域能量
 Ens < Enp < End < Enf (“penetration effect”穿透效應)
 Penetration Effect in 2s & 2p

Penetration Effect

Fig. 7.21: 2s 與2p 軌域電子機率分佈的比較.

 Penetration Effect in 3s, 3p & 3d
E3s < E3p < E3d

FIG. 7.22: (A) 3S 軌域的電子機率分佈.

(B) 3S,3P, 3D 軌域的電子機率分佈.
多電子原子軌域能階圖
 7.10 The History of the Period Table

現代形式的週期表分別由二位化學家發展出來:
J. L. Meyer (German, 1834 ~ 1895) &
D. I. Mendeleev (Russian, 1834 ~ 1907)

門得列夫 is given most of the

credit 因為他強調利用其週期表
可以預測未知元素的存在與性質

現今的週期表與 Medeleev’s 的
週期表的差異在於現今的週期
表是以 atomic number 而非
atomic mass 排序。
Fig. 7.25: Mendeleev's early periodic table, published in 1872.
Note the spaces left for missing elements with atomic masses
44, 68, 72, 100.

Sc

Ga Ge
Tc
Ge
7.11 The Aufbau Principle and the Period Table
Aufbau Principle
(AUFBAU 為德文，意謂 “BUILDING UP”)
• 建構元素時，逐一將質子加入原子核, 同時電子也以相同的
方式加入這些 hydrogen-like orbitals.
• 電子填充的次序是先填到 (n + l) 值較小的軌域，這些軌域
有較低的能量。

Pauli exclusion principle

• 任何兩個電子不可以擁有四個相同的量子數
(n, l, ml, ms).

Hund’s Rule
• 在一組degenerate 的原子軌域中，具有最多非成對電子的
組態，是能量最低的組態。
51
 1s 2s 2px 2py 2pz
H: 1s1

He: 1s2

Li: 1s22s1

Be: 1s22s2

B: 1s22s22p1

C: 1s22s22p2

N: 1s22s22p3

O: 1s22s22p4
A diagram that summarizes the order in which the orbitals fill
in polyelectronic atoms.
多電子原子軌域，電子的填充次序
Fig. 7.26: The electron configurations in the type of orbital
occupied last for the first 18 elements.
Half-Filled Electron Configurations

第四週期元素

55
Lanthanide and Actinide series
Fig. 7.29: The periodic table with atomic symbols, atomic numbers,
and partial electron configurations.
 Broad Periodic Table Classifications

▪ Representative Elements 典型元素 (main group 主族):

filling s and p orbitals (such as Na, Al, Ne, O)

▪ Transition Elements 過渡元素: filling d orbitals (such

as Fe, Co, Ni)

▪ Lanthanide and Actinide Series 鑭系與錒系 (inner

transition elements 內過渡元素): filling 4f and 5f
orbitals (such as Eu, Am, Es)
 Valence electrons (價電子)
• 價電子:原子最外層主量子數的電子。
• 內層電子稱為 core electrons.
• 價電子與原子的鍵結有關。
• 同一族的元素具有相同的價電子組態。
• 同一族的元素具有相似的化學性質

Atom Electron # of valence e–

configuration
N 1s22s22p3 5
Ca [Ar]4s2 2
Br [Ar]4s24p5 7
Ar: 1s22s22p63S23P6
7.12 Period Trends in Atomic Properties

• Ionization Energy (游離能)：由氣相的原子或離

子移除一個電子所需要的能量.

X(g) → X+(g) + e− H

• Periodic Trends
First ionization energy (第一游離能):
▪ increases from left to right across a period; 大
▪ decreases going down a group. 小
 FIG. 7.31: THE VALUES OF FIRST IONIZATION ENERGY FOR
THE ELEMENTS IN THE FIRST SIX PERIODS.
第一游離能: 週期表由左至右逐漸增加;
週期表由上而下逐 漸減少.

Be: 2S2
B: 2S2 2P1

N: 2S2 2P3
O: 2S2 2P4

61
 第三週期元素的游離能

以鋁 (Al, [Ne]3s23p1) 為例：1st IE < 2nd IE < 3rd IE << 4th IE …..
 Fig. 7.32: Trends in ionization energies
(kJ/mol) for the representative elements.

游離能隨週期表由上而下逐 漸減少.
Photoelectron Spectroscopy (PES)

Eelectron = hv - KE

Can be used to determine the relative

energies of electrons in individual atoms
and molecules.

High-energy photons are directed at the

sample, and the kinetic energies of the
ejected electrons are measured.
Photoelectron Spectroscopy (PES) for Atom

Representation of the removal of Figure 7.33 The idealized PES

various electrons from N2. spectrum of phosphorus.
Photoelectron Spectroscopy (PES) for Atom

Figure 7.34 The idealized PES spectra of boron and fluorine.

66
 Electron Affinity (電子親和力)
Electron Affinity (電子親和力)：氣相的原子、或離
子得到一個電子，所產生的能量變化.
X(g) + e− → X−(g) H

Fig. 7.35: The electron affinity values for atoms among the first 20
elements that form stable, isolated X– ions.
 鹵素的電子親和力

週期表往下，電子親和力應該會變得較正(less
energy release)，因為電子放在離原子核較遠的位
置，所得到的穩定能量較少。但是通常電子親和力變
化不大，而且有許多例外。
 Atomic Radius (原子半徑)
共價半徑：雙原子分子，原子核距離的一半。

金屬半徑：固態金屬晶體中，原子與原子間距的一半。

凡得瓦半徑 : 原子與原子接觸最短距離的一半。
Fig. 7.37: Atomic
radii (in picometers)
for selected atoms.

原子半徑:
週期表由左至右
逐漸減少;

週期表由上而下
逐漸增加.

70
 7.13 The Properties of a Group

1. 同一族的元素具有相同的價電子組態 (基本上，
這些電子決定了元素的化學性質).

2. 瞭解週期表的排列，可以記得任何典型元素的電
子組態.

3. 某些族有特殊的名稱 (alkali metals, halogens, etc).

4. 金屬及非金屬具有它們特殊的化學及物理性質.
72
FIG. 7.38:
鈍氣
鹼金屬
鹵素
鹼土金屬

過渡金屬

鑭系
錒系
73
 The Alkali Metals

Alkali 的週期性質
• Expected reducing ability
Cs > Rb > K > Na > Li

• Observed reducing ability in water :

2M(s) + 2H2O(l) → H2(g) + 2M+(aq) + 2OH-(aq) + energy
Li > K > Na

• Li＋, Na＋, K＋ 的水合能

Hydration: M+(H2O)n
Q1 Q2
Hydration energy = ~
r