Atkins / Paula

《 Physical Chemistry, 11th

Edition 》

Chapter 8.
Atomic structure and
spectra

1
 Content
8A Hydrogenic atoms
8A.1 The structure of hydrogenic atoms
8A.2 Atomic orbitals and their energies
8B Many-electron atoms
8B.1 The orbital approximation
8B.2 The building-up principle
8B.3 Self-consistent field orbitals
8C Atomic spectra
8C.1 The spectra of hydrogenic atoms
8C.2 The spectra of complex atoms
Singlet and triplet states
Spin-orbit coupling
Term symbols
Hund’s rules
Selection rules
I 8.1 Web resource : What is an application of this material ?

2
 引言

• 本章探討如何利用之前介紹的量子力學原則，來探索在原
子核附近電子結構，描述原子內部的電子的結構排列組態
” electronic structure” 。了解類氫原子的量子力學規則
與反應，是用於描述其他原子與分子構造的基礎概念。因
而具有很多廣泛的化學應用。

• 類氫原子系統 (Hydrogen-like atoms or hydrogenic atom

s): 類氫原子是最為簡化的單一個電子的原子。就像氫原
子，類氫原子也是極少數可以量子力學可完全求得解的問
題。
此部分將詳細探討以軌域的概念導入類氫原子的電子結
構。
• Impact 13: 應用上，可以原子光譜檢視外太空的恆星 , 可
以鑑定星際氣體及環繞恆星外層組成，進一步確認其物理
狀態與性質。並從原子光譜實驗得到的研究結果可驗證。 3
 引言
• 原子的電子構造 :
• 在描繪原子時，波函數中包含所有電子的性質與資訊。
• 並非所有系統的波函數都有分析解 (analytic solution) ，只有在
氫原子及單電子的類氫原子系統的波函數可以得到正確的解 (e
xact solution) 。
• 其他的多電子原子系統，必須採用估計方法求得近似的解 (app
roximate solution) 。 或以電腦趨近法計算 (iterative approximati
on) ，求得非常接近的數值解 (numerical solution) 。
• 在量子假說中新加入了”包利不共容原理” (Pauli exclusion pri
nciple) 。
• 電子只在特定的能階間可以發生轉換，伴隨光譜吸收或電磁波
釋放。此種限制的規則稱為選擇律 (Selection rule) 。

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 引言

• 設定一個電子的 Schrödinger 方程式，進一步得到其波函數

再細分為角度 (Y) 和徑向 (R) 部分。即是類氫原子 (hydrogen
ic atoms) 的『原子軌域』。
• 其次，類氫原子這些軌域用來描述多電子原子結構。 再與
Pauli 不相容原理相結合，可得到原子性質的週期性。
• 同樣的原則也適用於比氫更複雜的多電子原子的光譜。
• 在本章的結尾，將用項符號 ( term symbols) 來描述多電子原
子角動量耦合，並探討原子光譜其中的超精細結構的起源。

5
 Key ideas

 原子的電子結構排列 electronic structure of atoms, the arrange

ment of electrons around a nucleus.
 類氫原子 hydrogenic atom, a one-electron atom or ion of gener
al atomic number Z.
 多電子原子 many-electron atom (polylectronic atom), an atom
or ion with more than one electron.
 
THE STRUCTURE AND SPECTRA OF HYDROGENIC ATOM
S
 Balmer series, the lines arising from the transitions
n  2 in the spectrum of atomic hydrogen.

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 Key ideas

 Lyman series, the lines arising from the transitions n  1 in th

e spectrum of atomic hydrogen.
 Paschen series, the lines arising from the transitions n  3 in t
he spectrum of atomic hydrogen.
 Rydberg constant, the constant RH in the expression
ν̃ = RH(1/n12 – 1/n22).
 Bohr radius, the constant a0 = 4πε0h 2/mee 2.
 term symbols, a spectroscopic energy level. Tn = RH/n2
 Ritz combination principle: the wavenumber of any spectral
line is the difference between two terms:
ν̃ = T1 – T2.
 Radial wavefunction, Rn,l (r ) = Nn,lρ l Ln,l (ρ)e–ρ/2, ρ = 2Zr/na0.

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 Key ideas

8A.1 The structure of hydrogenic atoms

 separation of variables, the separation of the wavefunction int
o radial and angular factors: ψ(r,θ,φ) = R(r )Y (θ,φ).
 radial solution, with u = rR.
8A.2 Atomic orbitals and their energies
 The specification of orbitals,
 The energy levels, En = –Z2μe4/32π2ε02h2n 2 with n = 1, 2,....
 Ionization energies,
 Shells and subshells
 S Orbitals
 Radial distribution functions
 p Orbitals
 d-Orbitals
8
 TOPIC 8A hydrogenic atoms

8A.1 The structure of hydrogenic atoms

 reduced mass, 1/μ = 1/me + 1/mN.
 Bohr radius, the constant a0 = 4πε0h 2/mee 2.
 radial wavefunction, Rn,l (r ) = Nn,lρ l Ln,l (ρ)e–ρ/2, ρ = 2Zr/na0.

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 8.1 The structure of hydrogenic atoms
• 1910 年拉塞福 (Rutherford, b. 1871) 由 α 粒子撞擊實驗的結
果提出了現代的原子模型。在此模型中，原子絕大部分的質
量是集中在非常小 (< 10−13 m) 帶正電的原子核中，原子核外
圍的廣大空間裏則有帶負電的電子圍繞，維持原子的電中
性。 1912 年波爾 (Neils Bohr) 來到拉塞福實驗室並開始發展
他的原子理論。在波爾的氫原子理論中，電子遵守古典物理
定律並以圓周運動圍繞原子核，但與古典力學不同的是，波
爾假設在電子的運動中角動量是量子化的 .

 h 
L  mvr  n n
 2 

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 波爾的原子理論 (Bohr’s Atomic theory)
:
 1. 量子化的電子角動量，有最小 L  mvr  n 
單位 ℏ :
2. 向心力 = 離心力 Zq2 mv 2 e
依 且 εo (vacuum permittivity) F 2  q
r r 4 0
為
真空介電常數 εo = 8.854×10–12
C2/ J-m
mv 2 r 2 n 2  2 n 2
3. Bohr’s theory 可推導出軌域半 r 2
 2  ao
Zq Zq m Z
徑也是量子化的
4. Z 為原子核的質子數 . ao 稱為 2 2
ao  2
 2
 4 0 
波爾半徑，其值為 52.9177 mq me
pm 。

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 Bohr radius

• 波爾半徑 (Bohr radius, ao ) 是氫原子軌道中，能量最

低軌道的半徑。
2 4 0 2
ao  2

me q me e 2
• 定義為在氫原子的基態 (1s-orbital) 中，電子最可能被
找到的半徑等於 ao ，且伴隨的原子核具有無限質
量。 在討論原子和分子的結構時，最常選用的距離
單位就是波爾半徑。
• .

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 The structure of hydrogenic atoms
• 由此波爾推導出氫原子的總能量 E = 動能 + 位能
mv 2 Zq 2 1 Zq2 Zq 2
E  T V    
2 r 2 r r
1 Zq2 1 Z 2q2 1 Z 2 q 4m  2
  2
 2 2 ao 
2 r 2 n ao 2 n mq2
• 氫原子的電子個別能階不連續 , 大小與 n2 成反比
 Z 2 q 2 1  Z 2 q 4m 1
En  2

2ao n 2 2 n 2
• 若假設氫原子的能量可藉由釋放出一個光子時從高能
階降到低能階，則波爾理論可以完全解釋氫原子光譜
譜線的位置以及雷德堡 (Rydberg) 公式 : hν = E2 – E1
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• 軌道中量子數為 n 的電子具有能量是 :
 q4m Z 2 e4m Z2 e4m Z2
En   2 
2  4 0  n 32 2 0  2 n 2
2 2 2 2 2
2 n

• With ao   2
4  2
 0
mq2 me2

• or 4 ,
 so 4 e2 Z 2 2 Z 2
q  2 2 En   
m a0 8 0a0 n 2
2ma02 n 2

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 Rydberg constant RH

• Rydberg formula ，又稱芮得柏 - 里茲公式

• The Rydberg constant, R is

me e 4 me e 4
R 2 3 E1  hcR    Z  1
8 0 h c 32  0 ℏ2
2 2 2

• RH is defined by the same expression except for the repla

cement of μH by the mass of an electron, me
H
RH  R
me
• Now, the ground state of hydrogen is the state with n = 1
hc H e 4 H e4
E1  hcR H   2 3   2 2
8 0 h c 8 0 h
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 Rydberg 芮得柏公式

• Energy for an electron in an atom orbital with quantum n

umber n has
H e 4
Z 2
 Z 
2
En     hcRH  2 
32  0 ℏ n
2 2 2
2
2
n 
• Rydberg equation for hydrogen (Z=1):

~ En2  En1  1 1
   RH  2  2  ,
hc  n1 n2 
• To convert the wavenumber (cm–1) into the energy in J, h
c = 1.98644 × 1023 J cm

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Energy of widely separated
stationary electron and nucleus

Fig.8.5 The energy levels of a

hydrogen atom. The values are
relative to an infinitely separated,
stationary electron and a proton. (n:
principal quantum number)

H e Z4 2
 Z 
2
En     hcRH  2 
32  0  n
2 2 2 2
n 
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 氫原子光譜

• 氫原子內之電子，在不同能階躍遷時，所發射或吸收不同波
長、能量之光子，而得到的光譜，稱為氫原子光譜。
• 氫原子光譜為不連續的線光譜，自無線電波、微波、紅外光、
可見光、到紫外光區段都有可能有其譜線。根據電子躍遷的後
所處的能階，可將光譜分為不同的線系。理論上有無窮個線
系，前 6 個常用線系以發現者的名字命名。六個線系 (series) 有
• Lyman 來曼系列
• Balmer 巴耳末系列
• Paschen 帕申系列
• Brackett 布拉格系列
• Pfund 蒲芬德系列
• Humphreys 韓福瑞系列

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Figure 8.A1 The spectrum of atomic hydrogen. Both
the observed spectrum and its resolution into
overlapping series are shown. Note that the Balmer
series lies in the visible region.
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Rydberg Constant, RH
~  1 1 
Rydberg Equation:   RH  2  2  ,
 n1 n2 
Rydberg Constant: RH = 109,677 cm-1

• Lyman Series: ~ 1 1
  RH  2  2 ;n  2, 3, 4,...
1 n 

• Balmer Series: ~  1 1
  RH  2  2 ;n  3, 4, 5,...
2 n 

• Paschen Series: ~ 1 1
  RH  2  2 ;n  4, 5, 6,...
3 n 
selection rules: for hydrogenic atoms Δℓ = ±1 Δmℓ = 0, ±1
20
 The Lyman series is converging to 91 nm, Other series are obtained
in the same manner.

21
Self-test 8.1 Calculate the shortest wavelength line in the Paschen
series.
[821 nm]
~  R   ; n  

1 1
ANS: H 2 2
3 n 
ν̃ = RH / 9 = (109,677 cm–1 /9) = 12186.3 cm–1 = 821 nm

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 Ritz combination principle
• 1889
  年瑞典物理學家 Rydberg 提出的表示氫原子譜線的經
驗公式。
• 指出每個譜線的波數可寫成兩個項 (Term) 的差異，每個
項的形式為
Tn = RH / n2
• Ritz 組合原理 (Ritz combination principle) 表示任何譜線的
波數是兩個項之間的差異。我們可說兩個項 T1 和 T2 的”
結合”將產生譜線的波數 :
ν̃ = T1 – T2
因此，如果每個光譜項代表能量 hcTn, ，當原子在兩項之間
的轉換時，能量差是
ΔE = hc T1 – hc T2

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• 由原子光譜觀察顯示發射的輻射頻率 , 依玻爾頻率條件 ,
可由運算式子得到
v = c T1 – c T2.
• 此運算式重新排列成 Ritz 公式時 , 改用波數 (wavenumber)
表示。 Ritz 組合原則對所有類型的原子和分子都適用 ,
但只有對於氫原子做的項有簡單的形式 , 即 : T = ( 常數 )
/ n2
• 原子吸收輻射和發射輻射的光譜觀察顯示 , 電磁輻射僅在
某些波數下被原子吸收和發射，因此原子只允許某些能量
的狀態。在此也再確定這種能量量子化的起源，並找到可
允許的能量值並可對應到 RH 的值 ,
RH = 109,677 cm–1 。

24
 Example 8.1

• Measuring an ionization energy spectroscopically

The emission spectrum of atomic hydrogen shows lines at 82259,
97492, 102824, 105292, 106632, and 107440 cm-1, which corresp
ond to transitions to the same lower state. Determine (a) the ioniz
ation energy of the lower state, (b) the value of the Rydberg const
ant.

25
26
Answer The wavenumbers are plotted against 1/n2 in Fig. 8.6. Th
e (least-squares) intercept lies at 109679 cm, so the ionization
energy is 2.1788 aJ (1312.1 kJ/mol). The slope is, in this insta
nce, numerically the same, so RH= 109 679 cm-1. A similar extr
apolation procedure can be used for many-electron atoms.

27
Fig. 8.6 The plot of the data in Example
8.1 used to determine the ionization
energy of an atom (in this case, of H)

28
• Self test 8.3
• The emission spectrum of atomic deuterium shows lines at
15 ,238, 20,571, 23,039, and 24,380 cm–1, which correspond to
transitions to the same lower state. Determine (a) the ionizatio
n energy of the lower state, (b) the ionization energy of the gro
und state, (c) the mass of the deuteron (by expressing the Rydb
erg constant in terms of the reduced mass of the electron and t
he deuteron, and solving for the mass of the deuteron).

• [(a) 328.1 kJ mol–1, (b) 1312.4 kJ mol–1, (c) 2.8 x 10–27 kg,
• a result very sensitive to RD]

29
• The two other quantum numbers, l, and ml , come from the a
ngular solutions ( 球型共振 ), and specify the angular mome
ntum of the electron around the nucleus:
– An electron in an orbital with quantum number l has an a
ngular momentum of magnitude
{l(l + 1)}½ ℏ, with l =0, 1, 2, ... , n –1.
– An electron in an orbital with quantum number ml has a z
–component of angular momentum ml ℏ, with ml = 0, ±1,
±2, ... , ± l.
• Note how the value of the principal quantum number, n, cont
rols the maximum value of l and l controls the range of value
s of ml.

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 精細結構常數 , α (- 維基百科 )

• 波耳原子模型很好地解釋了氫原子光譜線的分布規律。
• 根據狄拉克的量子理論， n 量子數及 j 量子數相同但 l
量子數不同的氫原子能態應該是簡併態，也就是不會有能
量差值。 然而進一步研究發現，氫原子光譜線具有精細
結構，原先的一條譜線實際上是由幾條靠得很近的譜線組
成的，波耳原子模型不能解釋光譜的精細結構。
• 德國物理學家索末菲 (Arnold Sommerfeld) 在波耳原子模
型的基礎上做了一些改進，建立了索末菲模型。在這個模
型中，索末菲認為電子繞原子核運動的軌道不一定是正圓
形，而是橢圓形。電子的軌道能階不僅與波耳模型中的主
量子數 n 有關，還與角量子數有關。不同角動量量子數
的軌道之間的能階差正比於某個無因次常數的平方。這個
無因次常數是索末菲在解釋光譜的精細結構時引入的，因
此被稱為精細結構常數 α 。
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 蘭姆位移

• 物理學中，以威利斯 · 蘭姆 (Willis Lamb) 為名的蘭姆位移

(Lamb shift) 是指氫原子兩個能階 (2 S1/2 與 2 P1/2 間的微小
能量差。
• 1947 年，漢斯 · 貝特（ Hans Bethe ）首次對氫原子譜線中
的蘭姆位移做出解釋，並且對導引出量子電動力學的進程
建下基礎。蘭姆位移目前對於精細結構常數 α 的測量提供
了比百萬分之一還佳的精確度，使得量子電動力學預測的
正確性得到證實。

32
 精細結構常數

• 在量子電動力學 (Quantum Electrodynamics ，簡稱 QED)

中，電子之間通過相互交換光子而發生交互作用。相互交換
光子的複雜程度對最終結果的貢獻隨光子的吸收或發射次數
呈指數式下降，這個指數的底就是精細結構常數。
• 也就是說，任何電磁現象都可以用精細結構常數的冪級數來
表達。量子電動力學認為，精細結構常數是電磁交互作用中
電荷之間耦合強度的度量，表徵了電磁交互作用的強度。

33
  
• 引入精細結構常數後，波耳模型中電子的運動速度和能階
可以表示成更為簡潔的形式：
and

• 其中 E0 是電子的靜止質能 me c2 。
• 因此，原子光譜中，能階的粗結構主要是由庫侖交互作用
引起的，能量為 α2E0 數量級。

 q4m Z 2 e4m Z2 e4m Z2

En   2 
2  4 0  n 32 2 0  2 n 2
2 2 2 2 2
2 n

34
 玻爾模型的 Z 極限

 
• 根據玻爾模型，在原子序大於 137 時出現問題，因為在
(n =1) 電子殼層中 1s 電子的速度 v 為

• 其中 Z 為原子序， c 為光速， α 為精細結構常數。在這個

模型下， Z 大於 137 的原子中 1s 電子的速度會超過光
速。因此在 Z > 137 時必須使用相對論性模型。

35
 徑向函數

 
• 在量子力學裏，運動於球對稱位勢中的粒子的量子行為 (P
article in a spherically symmetric potential) 。這量子行
為，可以用薛丁格方程式表達為
V(r)ψ = E ψ
• 其中，ℏ是普朗克常數， μ 是粒子的質量， ψ 是粒子的波
函數， V 是位勢， r 是徑向距離， E 是能量。
• 由於球對稱位勢 V(r) 只與徑向距離 r 有關，與天頂角
θ 、方位角 𝜙無關，為了便利分析，可以採用球坐標 (r,θ,
φ) 來表達這問題的薛丁格方程式。然後，使用分離變數
法，可以將薛丁格方程式分為兩部分 : 徑向部分與角部
分。

http://zh.wikipedia.org/wiki/ 球對稱位勢

36
• A
  number of physical systems can be regarded intuitively as c
ombinations of motion of different kinds, such as motion throu
gh space and an internal motion. These intuitive notions can be
justified mathematically and typically result in the separate, bu
t sometimes linked, equations for each type of motion.
• (a) Particle on a sphere
• This section shows how to separate the Schrodinger equation f
or a particle able to move on the surface of a sphere into separ
ate equations for the azimuth ϕ and the colatitude θ.
• The Schrodinger equation for the motion of a particle of mass
m on the surface of a sphere is
=Eψ

37
•  The laplacian for particle on a sphere is :

• and the legendrian is:

• Because r is constant, the part of the laplacian that involves dif

ferentiation with respect to r can be discarded, and the equatio
n then becomes
=Eψ
• In terms of the moment of inertia, I = mr2, this expression bec
omes = –ε ψ with

38
39
• Division through by ΘΦ and multiplication by sin2θ gives

40
41
 (b) Hydrogenic atoms

• Step 1 Separate the internal motion from the external motion

42
43
44
45
46
 Internal relative coordinates

•  Now we write the overall wavefunction as the product

Ψtotal = Ψc.m.Ψ, where the first factor is a function of only the centre
of mass coordinates and the second is a function of only the relativ
e coordinates. The overall Schrödinger equation,
HΨtotal = EtotalΨtotal
then separates by the c.o.m and relative coordinate systems

• With Etotal = Ec.m.+ E. From now on we only consider the internal rel
ative coordinates:

47
48
 (b) Hydrogenic atoms

• Step 2 Write the Schrödinger equation associated with internal

motion:

• a solution of the form ψ =RY,

• Multiply through by r2/RY and obtain

49
50
• Step 3 Write an expression for the radial contribution

51
52
 薛丁格方程式

• 採用球坐標 ，將拉普拉斯算子2 展開：

• 滿足薛丁格方程式的本徵函數 ψ 的形式為：
Ψ(r,θ,φ) = R(r) Θ(θ) Φ(φ)

• 其中， R(r) ， Θ(θ) ， Φ(φ) ，都是函數。 Θ(θ) 與

Φ(φ) 時常會合併為一個函數，稱為球諧函數
Yl,m(θ,φ) = Θ(θ) Φ(φ)

• 這樣，本徵函數 Ψ 的形式變為： Ψ (r, θ, φ) = R(r) Yl,m (θ,

φ)

53
• For
  centrosmmetric potential (independent of angle), separate t
he wavefunction into radial R and angular Y components as:
Ψ(r,θ,𝜙) = R(r) Y(θ,𝜙)
• The Schrödinger equation can be separated into two equations,
one for R(r) and the other for Y(θ,𝜙), the equation does separa
te, and the equations we have to solve are:

• where

Veff 
Ze 2

 
l l 1  2

4 0 r 2 r 2
54
d2 2 d 1  d 2 R dR dR 
2
R R   r 2   
dr r dr r  dr dr dr 
1  d  dR  dR 
  r 
r  dr  dr  dr 
1 d  dR  
  r   R
r dr  dr  
1 d d 
   rR  
r dr  dr 
1 d2
 2
 rR 
r dr

55
 Separation of R and Y

• From the laplacian in three dimensions, it follows that the Schr

ödinger equation is
2  2 2  1 2 
  2   2   RY  V RY  E RY
2   r r r r 
• Because R depends only on r, and Y depends only on the angul
ar coordinates, this equation becomes
 2  d 2 R 2Y dR R 2 
  Y 2   2  Y   V RY  E RY
2   dr r dr r 
• If we multiply through by 1/RY, we obtain
 2  d 2 R 2 dR  2 1 2
  2     Y   V  E
2 R  dr r dr  2  r Y
2

2  d 2   2 
   rR    V    Y   rR   E  rR 
2

2   dr 2
  2 r Y
2

56
徑向部分解答 ( 維基百科 https://zh.wikipedia.org/wiki
/ 球對稱位勢 )

• 將角部分解答代入薛丁格方程式，則可得到一個一維的二
階微分方程式：

設定函數 u(r) = rR(r) 。代入方程式。經過一番的運算，可

以得到 :

• 徑向方程式變為

• 其中，有效位勢
• 這正是函數為 u (r) = rR(r) ，有效位勢為 Veff 的薛丁格
方程式。徑向距離 r 的定義域是從 0 到 ∞。新加入有
效位勢的項目，稱為離心位勢 (Centrifugal potential ) 。
57
 Centrifugal potential

• An electron in an orbital with quantum number l has an angul

ar momentum of magnitude (l(l+1))½ ħ , with l = 0, 1, 2,…, n–
1.
• The term in Y is the only one that depends on the angular varia
bles, so it must be a constant. When we write this constant as ħ
l (l+1)/2μ , the equation follows immediately as:

Veff 
Ze 2

 
l l1  2

4 0 r 2 r 2
• First term is called Coulomb potential (proportional to 1/r ). S
econd term is called Centrifugal potential (proportioal to
l (l +1)/r 2), which only exists when l > 0.

58
 Fig.8A.3 The effective
potential energy of an electron
in the hydrogen atom. When
the electron has zero orbital
angular momentum, the
effective potential energy is
the Coulombic potential
energy. When the electron has
nonzero orbital angular
momentum, the centrifugal
effect gives rise to a positive
Ze 2
l 
l  1  contribution which is very
2
Veff   large close to the nucleus. We
4 0 r 2 r 2
can expect the l = 0 and l  0
wavefunctions to be very
different near the nucleus.

59
 effective potential energy

• 檢查 Veff(r) 的形式 , 可以預測徑向波函數形狀的某些特徵。

方程式中的第一項是原子核中電子的庫侖勢能 ( 與 1 / r 成正
比 ) 。第二項源自古典物理學中所謂的離心力 ( 與 1/ r2 成正
比的排斥項 ) ，是由核周圍的電子角動量產生的。
• 當 l = 0 時 (S orbitals) ，電子沒有角動量，有效勢能純粹是
庫侖引力，在所有半徑都是吸引力。
• 當 l ≠ 0, 時，離心項的貢獻是 ( 排斥的 ) 正有效勢能。當電
子接近原子核 (r ≈ 0) 時，這個與 1/ r2 成正比的排斥項占主
導，壓過 與 1/r 成正比的庫侖吸引力，淨效應是有效的排
斥。
• 當電子靠近原子核時，來自核的兩個有效勢能 (l = 0 和 l ≠
0) ，在量上非常不同。然而，在遠距離時它們卻相似，因為
離心貢獻 ( 1/ r2 ) 比庫侖貢獻 (1 / r) 更快地趨向零 。因此，
我們可以預期 l = 0 和 l ≠ 0 的解在核附近非常不同但遠離
時即相似。 60
Justification 8.1( 補充 ) The shape of the radial wavefun
ction

 2
d2
u
  eq. 8.9 
•From V,effwith E u = rR (r)
u u(r)
2 dr 2

• When r is very small (close to the nucleus), u ≈ 0, so the right-

hand side of eqn is zero; we can also ignore all but the largest t
erms (those depending on l / r2) in eqn and write

• The solution of this equation (for r ≈ 0) is

• Because R = u/r, and R cannot be infinite at r = 0, we must set

B = 0, and hence obtain R ≈ Ar1 .

61
Justification 8.1 ( 補充 ) The shape of the radial wa
vefunction

•If its
  far from the nucleus, when r is very large, we can ignore all t
erms in 1/r and equation becomes

where ≈ means “asymptotically equal to”. Because

this equation has the form

The acceptable (finite) solution of this equation (for r large) is
R(r) = exp(–2μ|E| / ℏ2)r
and the wavefunction decays exponentially towards zero as r incre
ases.

62
 ( 補充 ) Associated Laguerre polynomial

 2r 
L2nll11   , n  l  1
 na0 

L0  x   1
L1  x    x    1
L2  x  
 x2
   2 x 
   2    1
2 2

L3  x  
  x 3

   3 x 2

   2    3 x    1   2    3

3! 2 2 6

63
 ( 補充 ) Associated Laguerre polynomials

• For the differential equation with an arbitrary real α :

xy"     1  x  y'  ny  0
• The polynomial solutions are called associated Laguerre poly
nomials. The simple Laguerre polynomials are recovered from
the generalized polynomials by setting α = 0:
xy"  1  x  y'  ny  0
• 這個多項式序列可以用 The Rodrigues' formula 遞推得到

Ln  x  
 
n! dx n
 e x 
ex d n x n

• Laguerre polynomials. 多項式在內積空間中 , 是正交多項

式
• 氫原子的薛丁格方程式徑向部分的解，就是 Laguerre pol
ynomials 的多項式。
64
 ( 補充 ) 角部分解答
• 球諧函數 Yl,m(𝜃,φ) = Θ(θ) Φ(𝜙) 的參數 𝜃為天頂角 、 𝜙為方位
角，滿足角部分方程式

• 其中，非負整數 l 是角動量的角量子數。 m 是角動量對於 z- 軸

的（量子化的）投影（滿足 – l ≤ m ≤ l ）。不同的 l 與 m 得到不
同的球諧函數解 Yl,m(𝜃,𝜙) ：

• 其中， Pl,m(cos θ) 是 Associated Laguerre polynomials( 伴隨勒讓德多

項式 ) ， i 是虛數單位，用方程式定義為

• 而 Pl(x) 是 l 階 Laguerre polynomial( 勒讓德多項式 ) ，可用 Rodrigu

es' formula ( 羅德里格公式 ) 表示
65
 2 2 Ze 2 2 2
     E H  
2 4or 2

In a spherical polar coordinates the Laplacian operator has the form

2  2
2  1  1     1  2

  2  2   sin   2 
2
r r r r  sin      sin   
The three ordinary differential equations are obtained by separating the
variables in radial parts operator and angular parts operator as
 2
For Φ part   ml
2

 2

 1   ml2 
For Θ part:   sin     l( l  1 )
 sin    sin  
2

 2   2 2   2  Ze2 l( l  1 ) 
For R part:   2    2   R  ER
2   r r r   4 0 r r 2

Ze2 l( l  1 ) 2
It follows that Veff  
4 0 r 2 r 2
66
 R(r) depend on the values of both n and l
Since the Radial wave equation depends on l and the radial
wavefunctions R(r) depend on the values of both n and l ( but not on
ml ) these functions all have the form
R(r) = r l × (polymial in r ) × (decaying exponential in r )
By simplifing forms:
2 Zr 4 o  2
 ao  2
ao : Bohr radius
n ao me e

Rn,l ( r )  N n,l  l L2nl11    e   / 2 n

Ln,l(ρ): Associate Laguerre polynomial

Expressions for some radial wavefunctions are given in Table 8.1
and illustrated in Fig. 8.4.
68
 Rn,l(ρ): the radial wavefunction
• The polynomial links the r ≈ 0 solutions on its left (corresponding to
R ∝ ρ l ) to the exponentially decaying function on its right. The poly
nomials have quite simple forms, such as 1, ρ, and 2 – ρ (they can be
picked out in Table 8.1). Specifically, we can interpret the components
of this expression as follows:
1. The exponential factor ensures that the wavefunction approaches zero
far from the nucleus.
2 The factor ρ l ensures that (provided l > 0) the wavefunction vanishes
at the nucleus.
3 The associated Laguerre polynomial is a function that oscillates from
positive to negative values and accounts for the presence of radial nod
es.

69
 Rn,l(ρ): the radial wavefunction

• Two features of the radial wavefunction are important:

1. close to the nucleus the radial wavefunction is proportional to
r l, and the higher the orbital angular momentum, the less like
ly the electron is to be found there(Fig. 8A.3).
2. Far from the nucleus all wavefunctions approach zero expone
ntially.

70
 Rn,l(ρ): the radial wavefunction

l

R n,l (  )  N n,l   Ln,l    e   / 2n
n 

2Zr 4 o  2
 ao  ao : Bohr radius
ao 2
me e
• Two types of nodes for atomic orbital: angular and radial
node
– Angular nodes are nodal planes in the spherical harmonics,
the total number of angular nodes is l.
– Radial nodes are surfaces where radial function R(r)
changes sign, the total number of radial nodes is (n– l–1).
So that the total number of nodes is (n–1).
71
The factor ρl ensures that (provided l > 0) the wave
function vanishes at the nucleus.
Fig.8A3 當靠近原子核， l = 1 的
軌域與 r 成正比， l = 2 的軌道與
r 2 成正比，而 l = 3 的軌道與 r 3
成正比。當 l 增加時電子逐漸從
原子核附近排除。只有 l = 0 的軌
域在原子核附近具有有限的非零值。

Close to the nucleus, orbitals with

l = 1 are proportional to r, orbitals
with l = 2 are proportional to r 2,
and orbitals with l = 3 are
proportional to r 3. Electrons are
progressively excluded from the
neighbourhood of the nucleus as l
increases. An orbital with l = 0
has a finite, nonzero value at the
nucleus.

72
 P(r) = r 2R 2(r )/a03

• Plot of r 2R 2(r )/a03 versus r /a0 for the first few H atomic orbitals. The curves
for n=2 and n=3 have been displaced vertically as indicated. The position of
the principal maxima for each orbital is indicated by an arrow.

73
 R 1,0 (r) R 3,0 (r) R 3,1(r)

R 2,0 (r) R 2,1(r) R 3,2 (r)

Fig.8A.4 The radial wavefunctions of the first few states of hydrogenic atoms of
atomic number Z. Note that the s orbitals (l=0) have a nonzero and finite value at the
nucleus. The horizontal scales are different in each case: orbitals with high principal
quantum numbers are relatively distant from the nucleus.(nodal plane # = (n– l –1)
74
Fig. 8.4

75
Fig. 8.4

76
77
 Illustration 8.1

• Calculating a probability density

78
 Self-test 8.2

• Evaluate
  the probability density at the nucleus of the electron for
an electron with n = 2, l = 0, ml = 0.
[(Z/a₀)3/8π ]

The probability density at r = 0 is

79
 8.2 Atomic orbitals and their energies
• An atomic orbital is a one-electron wavefunction for an electro
n in an atom.
• Each hydrogenic atomic orbital is defined by three quantum n
umbers, designated n, l, and ml.
• When an electron is described by one of these wavefunctions,
we say that it 'occupies' that orbital. We could go on to say that
the electron is in the state |n, l, ml >
• For instance, an electron described by the wavefunction Ψ1,0,0 a
nd in the state |1,0,0> is said to occupy the orbital with n = 1, l
= 0, and ml = 0.

80
 Key ideas

8A.2 Atomic orbitals and their energies

 atomic orbital, a one-electron wavefunction for an electron in an
atom.
 principal quantum number, the quantum number n that determines
the energy of an electron in a hydrogenic atom; n = 1, 2, 3... .
 bound state, a state in which the energy of the atom is lower than that
of the infinitely separated, stationary electron and nucleus.
 unbound state, a state in which the energy of the atom is equal to or
higher than that of the infinitely separated, stationary electron and
nucleus.
 Rydberg constant (theoretical value),
RH = (μH/me)R, R = mee4/8ε02h3c.

81
 Key ideas

9.2 Atomic orbitals and their energies (cont..)

 ionization energy, the minimum energy required to
remove an electron from the ground state of an atom; for a
hydrogen atom, I = hcRH.
 shell, all the atomic orbitals of a given value of n.
 subshell, all the atomic orbitals with the same value of n but
different values of l .
 s-, p-, and d-orbitals, atomic orbitals with l = 0, 1, and 2,
respectively.
 boundary surface, the surface that captures a high
proportion of the electron probability.

82
 Key ideas
9.2 Atomic orbitals and their energies (cont..)
 boundary surface, the surface that captures a high proportion of
the electron probability.
 radial distribution function, a probability density that when it
is multiplied by dr, gives the probability of finding the electron
anywhere in a shell of thickness dr at the radius r; P(r) = r2R(r)2.
For s-orbitals, P(r) = 4πr2ψ2.
 nodal plane, a plane dividing regions of opposite sign of the
wavefunction.

83
• 原子軌域是原子中單電子的波函數。 每個類氫原子軌域
由三個量子數所定義的，稱為 n ， l 和 ml 。 當電子由
這種波函數 Ψ 描述時，我們說電子“佔據”軌域。 也可
以說電子是處於 |n, l, ml > 狀態
例如，由波函數 Ψ1,0,0 描述的電子被稱為佔據軌域 |1,0,0>
狀態，其中 n = 1 ， l = 0 ，並且 ml = 0 。

84
 a) The specification of orbitals
• 原子軌域是基於原子的 Schrödinger equation 通過求解獲得
的氫原子的單電子波函數。
原子軌道的特徵是三個量子數 (QN):
– 主量子數 (The principle quantum number, n.)
– 角量子數 (The angular quantum number, l. )
– 磁量子數 (The magnetic quantum number, ml .)
• These QN are restricted to the following values:
– n = 1, 2,…
– l = 1, 2,…, n–1 選擇律 (election rules)
– ml = l, l–1, l–2,…, –l

85
• For a given n and l there are 2l+1 orbitals.
• The principle quantum number determines the energy of the el
ectron:
• An electron in an orbital with quantum number n has an energ
y given by eqn

H e 4
Z 2
 Z 
2
En     hcRH  2 
32  0  n
2 2 2 2
n 

86
  
• 另外兩個量子數 l 和 ml 來自角度部分波函數的解，並連
結了原子核周圍電子的角動量：
角量子數為 l 的軌道中的電子具有角動量 , 且幅度為
，其中 l = 0, 1, 2, ..., n – 1 。
• 量子數 ml 的軌域中的電子具有角動量 ml ℏ 的角動量 z-
分量，其中 ml = 0, ±1, ±2, ……, ±l 。
• 主量子數 n 的值控制 l 的最大值，而 l 控制 ml 值的
範圍

87
Chap. 8 Techniques and applications 88
 b) The energy levels

• 能量以及相鄰能階的分離與 Z2 成正比，因此 He （ Z =
2 ）中的能階水平是 H(Z = 1) 的四倍（並且 He 基態能量
亦是 H 能量的四倍）。方程式給的所有能量都是負的。指
的是原子的束縛態，其中原子的能量是低於無限分離的靜
止電子和原子核的能量（相當於零的能量 ) 。也是 Schrod
inger 方程式的解，但為正的能量。
• 這些解對應於電子通過高能碰撞或光子的未結合狀態 (unb
ounded states) ，即當電子從原子中射出時電子產生的狀
態。未束縛電子的能量不被量子化並形成原子的連續狀
態。

89
  
• 方程式預測的能量水平如圖 8A.5 所示。 能量以及相鄰水平的分
離與 Z2 成正比，因此水平相隔四倍，並且基態 Rydberg 常數對於
氫 (Z = 1) 的深度是四倍。

其中 μ 是氫的減縮質量。 Rydberg constant 本身 R 由相同的表

達式定義，除了用電子質量取代 μ ，對應無限核質量的

• 將基本常數的值插入 RH 的表達式中幾乎與實驗值一致。 唯一的

差異來自忽略相對論修正 ( 簡單來說，即質量隨速度而增加 ) ，
而非相對論的 Schrodinger 方程式 (non-relativistic Schrodinger eq
uation ) 忽略了這一點。

90
 c) Ionization energy ， EI 電離能

• 電離能（ Ionization energy ），或稱游離能、電離焓，常

簡記為 EI ，指的是將一個電子自一個孤立的原子、離子
或分子移至無限遠處所需的能量。
• 更廣義的用法，第一電離能定義為氣態原子失去一個電子
成為一價氣態正離子所需的最低能量，記作 I1 ；氣態一
價正離子失去一個電子成為氣態二價正離子所需的能量稱
為第二電離能，記作 I2 。依此類推。
• 第一電離能
• 第一電離能的數值和原子的有效核電荷密切相關，也和原
子大小、原子電負度，原子軌道中電子間的推斥作用等因
素有關。

91
• The ground state of hydrogen is the state with n=1

E1  hcR H  n  1
• The atom is ionized when the electron has been
excited to the level corresponding to n = ∞, the
ionization energy I is

I  hcRH
• The value I is 2.179 aJ , (a , for atto, is the
prefix that denotes 10-18) which corresponds to
13.60 eV.

92
 (c) Ionization energies

• Example 10.1 Measuring an ionization energy Spectroscopically

• The emission spectrum of atomic hydrogen shows lines at 82 259,
97 492, 102824, 105292, 106632, and 107440 cm", which corresp
ond to transitions to the same lower state. Determine (a) the ioniza
tion energy of the lower state, (b) the value of the Rydberg consta
nt.

93
 Example 8A.1
• Method
  The spectroscopic determination of ionization energie
s depends on the determination of the series limit, the wavenu
mber at which the series terminates and becomes a continuum.
If the upper state lies at an energy then,
• E = -hcRH / n2
• when the atom makes a transition to Elower, a photon of wavenu
mber.
• is emitted. However, because 1=-Elower it follows that
• A plot of the wavenumbers against 1/n2 should give a straight l
ine of slope -RH and intercept I / hc. Use a computer to make a
least-squares fit of the data to get a result that reflects the preci
sion of the data.

94
• Answer The wavenumbers are plotted against 1/n2 in Fig. 10.6. The
(least-squares) intercept lies at 109679 crn", so the ionization energy
is 2.1788 a] (1312.1 k] mol").
• Comment 10.2
• The particle in a finite well, discussed in Section 9.3, is a primitive b
ut useful model that gives insight into the bound
• and unbound states of the electron in a hydrogenic atom. Figure 9.15
shows that the energies of a particle (for example,
• an electron in a hydrogenic atom) are quantized when its total energ
y, E, is lower than its potential energy, V (the Coulomb interaction en
ergy between the electron and the nucleus). When E> V, the particle
can escape from the well (the atom is ionized) and its energies are no
longer quantized,

95
• Answer The wavenumbers are plotted against 1/n2 in Fig. 9A.7
The (least-squares) intercept lies at 109679 cm-1, so the ioniza
tion energy is 2.1788 aJ (1312.1 k] mol-1).

96
 (d) Shells and subshells

• 一個原子中，對應特定 n 值的所有軌域，形成單一的原子殼
層 (shell) 。
• 在類氫原子中，特定 n 值對應的所有軌域，屬於相同的原子
殼層，而且有相同的能量。一般以字母來標示連續的原子殼
層:

• n = 1 2 3 4 ...
K L M N…

97
 (c) Shells and subshells

• 因此，所有 n =2 的原子軌域形成 L 原子殼層，且依此類推。

• 具有相同 n 值，但不同 l 值的原子軌域，形成軌域層的’子
殼軌域層’ (subshell) 。子殼軌域層亦依字母命名 :
• l = 0 1 2 3 4 5 6 ….
s p d f g h i ….
• The letters then run alphabetically (j is not used). Figure 8.7 is a vers
ion of Fig. 8.5.

98
Fig.8A.8 The energy
levels of the hydrogen
atom showing the
subshells and (in square
brackets) the numbers of
orbitals in each subshell.
In hydrogenic atoms, all
orbitals of a given shell
have the same energy.

99
• Shell 主殼是在特定主量子數 n 值下的所有原子軌域。 all the at
omic orbitals of a given value of n.
• Subshell 子殼是具有相同 n 值但不同的 l 值下的所有原子軌
域。 all the atomic orbitals with the same value of n but different valu
es of l 。
• 當 n = 1 時，只有一個 子殼 : l = 0 ，且唯一允許的子殼， m1 =
0 僅包含一個軌域，是唯一允許的 m1 值。
• 當 n = 2 時，有四個軌域，並且一個在 S subshell 子殼中 (l =
0 ， m1 = 0) ，三個在 l = 1 的 P subshell 子殼中 , 且 m1 = + 1,
0, –1 。
• 當 n = 3 時有九個軌道 ( 一個是 l = 0 ，三個是 l = 1 ，五個是 l =
2) 。
• 在主量子數 n 的主殼中的總軌域數是 n2 ，因此在類氫原子中
每個能級是 n2 倍的簡併。 (each energy level is n2 -fold degenerat 100
Fig.8A.9 The organization of
orbitals into subshells
(characterized by l ) and
shells (characterized by n ).

101
 (d) Atomic orbitals

• 佔據基態的軌道是 n = 1 的軌道（當 n = 1 時， l = 0 且 m l =
0 ，這些量子數的唯一可能值）。因此，從表 8.1 中（對應
Z = 1 ）的原子軌域波函數可寫為：
1  r / ao
Ψ  e
a 
3 1/ 2
o

• 該波函數與角度無關，並且在固定 r 半徑的所有座標點處具
有相同的函數值，亦即 1S 軌道是球狀對稱的 (spherically sy
mmetrical) 。波函數的最大值在 r = 0 處為 l / (πao3)1/2 ，且
從核往外依指數衰減。由此可得出， 1S 電子出現的最大可
能點是核本身。

102
• 一般依基態波函數的形式下，原子能量是由勢能和
動能加總的貢獻。
• 在電子距離原子核越近時，有較低的平均勢能。然
而，這樣的波函數在近核處有極大值且有較高的平
均曲度，這形狀顯示它亦具有非常高的動能。
• 在原子核出現最大振幅高峰的波函數，應當得到最
低平均勢能以及較高的動能。（ Fig. 8.9).

103
Fig.8A.10 The balance of kinetic and
potential energies that accounts fo
r the structure of the ground state
of hydrogen(and similar atoms).
(a) The sharply curved but localiz
ed orbital has high mean kinetic e
nergy, but low mean potential ener
gy; (b) the mean kinetic energy is
low, but the potential energy is not
very favorable; (c) the compromis
e of moderate kinetic energy and
moderately favorable potential en
ergy.

104
• 然而，當波函數傳播到核中央以外顯著的距離時，
電子的平均勢能也相應地提高。且因波函數僅有非
常低的平均曲度，電子動能也相對較低。
• 實際的基態波函數是妥協在這二個極端之間： 波函
數從中央向外傳播， ( 因此勢能的期望值既不是像
在近核處非常低，但亦不是分散到非常高的勢能 )
，且有合理地平均曲度。 ( 因此動能的期望值不
是像在近核處一樣非常地高，但亦不是分散到非常
地低 ) 。

105
• 隨 n 增加， nS 軌域能量因而加大 , 由於電子與
核的平均距離也增加 , 也較不被原子核束縛 . 因
而電子變得較少負位能。
• 由 virial theorem : 2<Ek> = b <V> if
• 對簡諧運動 V = ½ kx2, 故 b = 2, 可得 <Ek> = <V
>
• 而勢能束縛的圓周運動， V = –A/r, 故 b = –1,
代入方程式 , 可得 <Ek> = – <V>/2.
• 因此 , 縱然隨 n 增加 , 電子平均動能降低 . 但總
能等於 <V>/2, 故隨 n 的增加，電子因較少負
的位能，總能也是增加的。
106
 boundary surface

• 一種描述電子概率密度的方法是用陰影密度表示 |
Ψ |2 。更簡單的程序是僅顯示邊界表面 (boundary
surface) ，該表面包圍捕獲的電子概率比例很高
（通常約 90 ％）。這邊界表面對於 1s 軌道，是
以核為中心的球體（圖 8A.11 ）。

107
Fig.8A.11 Representations of the 1s and 2s hydrogenic atomic orbitals in
terms of their electron densities (as represented by the density of sh
ading).
108
Fig.8A.11 The boundary surface of an s orbital, wit
hin which there is a 90 per cent probability of
finding the electron.

109
 (e) Radial distribution functions

• We can imagine a probe with a volume dr and sensiti

ve to electrons, and which we can move around near t
he nucleus of a hydrogen atom. Because the probabili
ty density in the ground state of the atom is |Ψ |2 ∝ e-2
Zrlao
, the reading from the detector decreases exponenti
ally as the probe is moved out along any radius but is
constant if the probe is moved on a circle of constant
radius (Fig. 8A.13).

110
Fig.8A.13 A constant-volume e
lectron sensitive detector (th
e small cube) gives its greate
st reading at the nucleus, and
a smaller reading elsewhere.
The same reading is obtained
anywhere on a circle of give
n radius: the s orbital is sphe
rically symmetrical.

111
• Now consider the probability of finding the electron anywhere
between the two walls of a spherical shell of thickness dr at a r
adius r. The sensitive volume of the probe is now the volume o
f the shell (Fig. 8A.14), which is 4πr 2dr (the product of its sur
face area, is 4πr 2dr , and its thickness, dr ).

112
Fig.8A.14 The radial distribution f
unction P gives the probability t
hat the electron will be found an
ywhere in a shell of radius r. Fo
r a 1s electron in hydrogen, P is
a maximum when r is equal to t
he Bohr radius ao. The value of
P is equivalent to the reading th
at a detector shaped like a spheri
cal shell would give as its radius
was varied.

113
 (e) Radial distribution functions

• Radial distribution function, P(r) , is a probability density th

at when it is multiplied by dr, gives the probability of finding t
he electron anywhere in a shell of thickness dr at the radius r;
P(r) = r2R(r)2.
• Probability = P(r) dr = r2R(r)2 dr
• For s-orbitals, P(r) = 4πr2ψ2.

114
 (e) Radial distribution functions

• The probability that the electron will be found between the inn
er and outer surfaces of this shell is the probability density at t
he radius r multiplied by the volume of the probe, or
|Ψ |2 × 4πr 2dr . The value of |Ψ |2 is the probability of finding a
n electron in any region.
• This expression has the form P(r)dr, where
P (r ) dr = |Ψ |2 × 4πr 2dr . (8.20)
• The more general expression, which also applies to orbitals tha
t are not spherically symmetrical, is
P (r ) = r 2 × R (r )2 . (8.21)
• where R(r) is the radial wavefunction for the orbital in questio
n.

115
 (e) Radial distribution functions

• 一般講原子或軌域的大小是與電子在 r 方向上的機率密
度分佈有關，由波函數與機率密度的關係可以得到在 r
方向上 ( 任何 θ, ϕ) 電子密度的機率分佈：

116
117
The radial distribution function P
• The probability that the electron will be found betwee
n r and (r+dr) is the radial distribution function P.
probability : P (r ) dr = r 2 R (r )2dr
• 通常 r 2 R (r )2 稱為 radial distribution function ， P(r)dr
代表電子出現在 r 到 r +dr 之間球殼中的機率。 我們
可以很容易的証明在 1s 軌域中， P(r) 的最大值出現在
r = ao 處。

118
8A.12 The variation of the mean radius of a hydrogenic atom with th
e principal and orbital angular momentum quantum numbers. Not
e that the mean radius lies in the order d  p  s for a given value
of n.

119
Example 8.2 Calculating the mean radius of an orbital

120
121
 example

• The
  ions with a single electron such as He+, Li2+, and Be3+ are
described by the 1s wave functions of H atom with Z/a0 where
Z is the nuclear charge. The wave function is

• Using this result, compare the mean radius of 1s electron at w

hich you would find the 1s electron in He+, Li2+, and Be3+.

122
Answer

123
• The general expression for the mean radius of an orbital with q
uantum numbers l and n is:
 1 l  l  1   a0 
rn ,l  n 1  1 
2
2   
 2 n   Z 
• The variation with n and l is shown in Fig. 8.12. Note that, for
a given principal quantum number, the mean radius decreases
as l increases, so the average distance of an electron from the n
ucleus is less when it is in a 2p orbital, for instance, than when
it is in a 2s orbital. <r> 隨 n 増大而加大但隨 l 增加而縮
小。

124
• Plot of r 2R 2(r )/a03 versus r /a0 for the first few H atomic orbitals. The curves
for n=2 and n=3 have been displaced vertically as indicated. The position of
the principal maxima for each orbital is indicated by an arrow.

125
All s-orbitals are spherically symmetric, but differ in the number of radial
nodes. For example, the 1s, 2s, and 3s orbitals have 0, I, and 2 radial nodes,
respectively. In general, an ns orbital has n-1 radial nodes.

126
 Mean distance from nucleus

• 由薛丁格方程式的解可以看出，電子不像波耳的氫原子模
型中有特定的軌道，而是依照機率密度有可能出現在各種
可能的位置。另一種估計氫原子大小的方法是計算電子與
原子核的平均距離：

127
 Radial distribution function, P (r )

4Z 3 2 2Z r / ao
For a 1s orbital, P r   3 r e
ao
Let's interpret this expression:
1 Because r 2 = 0 at the nucleus,
P (0) = 0 at the nucleus
2 As r → ∞, p (r ) → 0 on account of the exponential term.
3 The increase in r 2 and the decrease in the exponential factor me
ans that P passes through a maximum at an intermediate radius

128
• The maximum of P (r), which can be found by differentiation,
marks the most probable radius at which the electron will be f
ound, and for a Is orbital in hydrogen occurs at r = ao the Bohr
radius. When we carry through the same calculation for the rad
ial distribution function of the 2s orbital in hydrogen, we find t
hat the most probable radius is 5.2 ao = 275 pm. This larger val
ue reflects the expansion of the atom as its energy increases.

129
 Example 8.3

• Calculating the most probable radius

130
131
P(x ) = r2 (R2,0)2

Solved dP(x) / dx = 0 = d(x2 (2– x)2 exp(–x)) / dx

ρ = 0, 2, 3 ± √5 , maximum at 3 + √5 or r = 3.24 ao/Z

132
R2,0 , P2s(ρ) and d(r2R2,02)/d ρ

133
134
Fig.8.14 A representation of th
e most probable radius of on
e-electron atoms and ions.

135
 Justification 8.3

The linear combination of degenerate wavefunctions

• We justify here the step of taking linear combinations of degen
erate orbitals when we want to indicate a particular point. The
freedom to do so rests on the fact that,
• whenever two or more wavefunctions correspond to the same
energy, any linear
• combination of them is an equally valid solution of the Schrod
inger equation.
• Suppose Ψ1 and Ψ2 are both solutions of the Schrodinger equat
ion with energy E; then we know that HΨ1 =E Ψ1 HΨ1 =
E Ψ2

136
• Now consider the linear combination
Ψ = c1 Ψ 1 + c2 Ψ 2

where c1 and c2 are arbitrary coefficients. Then it follows that

H Ψ = H(c1 Ψ1 + c2 Ψ2) = c1 H Ψ1 + c2 H Ψ2
= c 1 E Ψ1 + c 2 E Ψ 2 = E Ψ

Hence, the linear combination is also a solution corresponding

to the same energy E.

137
 P orbital

Fig.8A.15 The boundary surfaces of p orbitals. A nodal plane passes

through the nucleus and separates the two lobes of each orbital. Th
e dark and light areas denote regions of opposite sign of the wavef
unction.

138
139
140
Fig.8A.16 The boundary surfaces of d orbitals. Two nodal planes in ea
ch orbital intersect at the nucleus and separate the lobes of each orbi
tal. The dark and light areas denote regions of opposite sign of the
wavefunction. 141
142
 Justification 8.4

• The identification of selection rules

•  The rate of transition between two states is proportional to the s
quare of the transition dipole moment, μfi , between the initial a
nd final states, where

• and μ is the electric dipole moment operator. For a one-electron

atom μ is multiplication by –er with components:
μX = –ex, μy = –ey, and μz = –ez. If the transition dipole mome
nt is zero, the transition is forbidden; the transition is allowed if
the transition moment is non-zero. Physically, the transition dip
ole moment is a measure of the dipolar 'kick' that the electron g
ives to or receives from the electromagnetic field.

143
8.3 Spectroscopic transitions and selection r
ules

8.3 Spectroscopic transitions and selection rules

• transition, a change of state.
• allowed and forbidden transitions, transitions allowed and disall
owed by selection rules.
• selection rule, a statement about which transitions are allowed; fo
r atoms, Δl = ±1, Δml = 0, ±1.
• Grotrian diagram, a diagram summarizing the energies of the sta
tes and the transitions between them.

144
Illustration 8.2 Applying selection rules

145
146