8C.

Atomic Spectra

8C.1 The spectra of hydrogenic atoms

8C.2 The spectra of many-electron atoms
Singlet and triplet terms
Spin-orbit coupling
Term symbols
Hund’s rules
Selection rules
I 8.1 Impact on astrophysics: Spectroscopy of sta
rs
1
• 你為什麼需要知道這些材料 ?
– 瞭解原子中電子的能量，對於理解許多化學特性和化學
結合至關重要。
• 關鍵的想法是什麼 ?
– 原子進行電子躍遷時，伴隨的輻射 ( 發射或吸收 ) 的頻
率和波數，提供有關其電子能量狀態的詳細資訊。
• 需要預備的知識是什麼 ?
– 本主題利用了氫原子的能階分佈 (Topic 8A) ，多電子
原子的配置 (Topic 8B) 的知識， 在有些地方也用到角動
量的特性 (Topic 7F) 。

2
• 原子光譜學背後的一般理念很簡單 : 當原子中的電子分佈經
歷一個狀態的轉換 , 並伴隨 |ΔE| 的能量變化時 , 光譜中的線
( 在發射或吸收中 ) 就會發生。光譜就是由電子從任何初始軌
域狀態到任何其他軌域狀態的躍遷 (transition) 產生的。
• 在光譜學中 , 在兩個 terms 之間發生轉換。廣義地說 , 一個 te
rm 只是原子能階的另一個名稱。這種轉換並伴隨 |ΔE| 的能
量變化，導致發射 , 或吸收光子，依下列條件決定其頻率 v =
|ΔE|/h 和波數 ṽ = |ΔE|/hc 。

3
 Transition 能階躍遷

• 當氫原子狀態遷移時，進行遷移的電子來自量子數 n1, 11, ml

1
的軌域換到另一個 ( 低能量 ) 量子數 n2, l2, ml2 的軌域，並伴

隨 |ΔE| 的能量變化，丟棄的多餘能量轉作為電磁輻射的光
子，依 v = |ΔE|/h 的條件決定其頻率。光譜就是由電子從任
何初始軌道到任何其他軌域的躍遷 (transition) 產生的。
• 並非所有可能的遷移都是允許的，由於為光子具有 s = 1 的
固有自旋角動量。電子必須對應角動量變化的守恆，補償光
子帶走的角動量。

4
• 選擇規則的起源可以通過考慮類氫原子的轉換來確定。
• 光子具有與 s = 1(Topic 8B) 對應的內在自旋角動量。
• 由於總角度動量在過渡中守恆 (total angular momentum is conse
rved in a transition), 電子躍遷時的角動量改變，必須足以補償
光子帶走的角動量。類似地 , 若因為電子的角動量變化 , 不足
以彌補光子帶走的角動量，或一個光子不能承載足夠的角動量
變化，則電子不能向另一個能階遷移過渡。
• 更正式地處理選擇規則需要對原子的初始和最終狀態的波函數
進行數學操作。

5
 Selection rule 選擇律

• 因此，電子從任何初始軌道到其他軌域的遷移是受限制
的。因此 , 一個 d 軌域中的電子 (l = 2) 不能遷移到 s 軌
道 (l = 0) ，因為釋出的一個光子無法帶走足夠的角動
量。
• 類似地，一個 s 軌域（ l = 0 ）的電子不能遷移到另一個 s
軌域，因為電子的角動量沒有變化，不能彌補一個光子帶
走的角動量。
• 選擇律是通過在發射或吸收光子時，躍遷的角動量是否守
恆而得到的（對於整個原子）。因此，當一些光譜躍遷是
允許的，表示它們可以發生，而其他光譜躍遷是禁止的，
表示它們不會發生。

6
8C.2 The spectra of complex atoms

Δl = ±1 Δ ml = 0, ±1

7
 Selection rule 選擇律

• 所有類氫原子光譜躍遷的選擇規則是

Δl = ±1 Δ ml = 0, ±1

• 主量子數 n 可以是任何改變量，只需與 Δl 的變化要求

相一致，因為它與角動量沒有直接關係。

• 對一般多電子原子的選擇律，是總結以下規則 :

Δn = ±1, ±2, …, Δl = ±1, Δml = 0, ±1.

8
 E8C.13a

• Which of the following transitions between terms are allowed

in the electronic emission spectrum of many-electron atom: (i)
2s  1s, (ii) 2p  1s, (iii) 3d  2p?
For a single-electron transition these mount to
Δn = any integer, Δl = ±1, Δml = 0, ±1.
Hence
(i) 2s  1s, Δl=0, not an allowed transition
(ii) (ii) 2p  1s, Δl= –1, allowed.
(iii) (iii) 3d  2p, Δl= –1, allowed.

9
 E8C.13b

• Which of the following transitions between terms are allowed

in the electronic emission spectrum of many-electron atom: (i)
5d  2s, (ii) 5p  3s, (iii) 6p  4f?
For a single-electron transition these mount to
Δn = any integer, Δl = ±1, Δml = 0, ±1.
Hence
(i) 5d  2s, Δl= –2, not an allowed transition, forbidden (mus
t be Δl = ±1)
(ii) 5p  3s, Δl= –1, allowed. (iii) 6p  4f, Δl= +2, forbidde
n. (must be Δl = ±1)

10
 The identification of selection rules

• 原子或分子要能夠與電磁場相互作用 , 吸收或發射頻率為 v 的光
子 , 則必須至少具有一個以該頻率振蕩的偶極子。在物理上 , 以
躍遷偶極矩 ( μfi , transition dipole moment) 表示電子從電磁場 (elec
tromagnetic field) 給予或接收能量轉移的量度。
• 在以下步驟中探討了這一想法的結果。

11
 Step l

• Step
  1 Write an expression for the transition dipole moment
• The transient dipole is expressed quantum mechanically as the tr
ansition dipole moment, μfi , between the initial and final states i
and f, where
• 躍遷偶極矩 ( μfi , transition dipole moment) 在兩種能階狀態
之間的躍遷速率與在初始狀態 i 和最終狀態 f 之間的波函
數積分成正比 :
• 其中 是電偶極矩運算符 (electric dipole moment operator) 。
對於單電子原子是乘以 – er , 其中 向量是以 r 的元件
表示 :
μx = – ex, μ. y = – ey, 和 μz = – ez.
• 如果躍遷偶極矩為零 , 則為禁止轉換 (forbidden) ; 如果躍遷
偶極矩為非零 , 則為允許轉換 (allowed) 。
12
 Step 2

• Step
  2 Formulate the integrand in terms of spherical harmonics
• To evaluate a transition dipole moment, consider each component
in turn. For example, for the z-component,

• In spherical polar coordinates z = r cos θ. Then, according to Tabl

e 7F.l,
• The wavefunctions for the initial and final states are atomic orbit
als of the form (Topic 8A).
• With these substitutions the integral becomes

13
 Step 2

•  
• This multiple integral is the product of three factors, an integral o
ver rand two integrals (in blue) over the angles, so the factors on t
he right can be grouped as follows:

14
 Step 3

•  
• Step 3 Evaluate the angular integral
• It follows from the spherical harmonics properties that the integral

• is zero unless and . Because in the present case l = 1 and m = 0, the ang
ular integral, and hence the z-component of the transition dipole momen
t, is zero unless Δ l = ±1 and Δml = 0, . which is a part of the set of selec
ion rules.

15
 transition dipole moment

• We
  consider each component in turn. The same procedure, but co
nsidering the x- and y-components, From the properties of the sp
herical harmonics that the Integral is zero unless
Δ l = ±1 and Δml = 0, which is a part of the set of selection rules.
results in the complete set of rules:

and
• The principal quantum number n can change by any amount cons
istent with the value of for the transition, because it does not relat
e directly to the angular momentum.

16
 Brief illustration 8C.1

•  
• 要識別 4d 電子可能向其進行輻射躍遷的軌道 , 首先確定
l 的值 , 然後應用此量子數的選擇規則。

• 因為 l = 2, 因此最終軌道必須具有 l = 1 或 3 。因此 ,
電子可以從 4d 軌道過渡到任何 np 軌道 ( 受 ) 和任何 nf 軌
道 ( 受同一規則約束 ) 。但是它不能過渡到任何其他軌道 ,
如 ns 或 nd 軌道。

17
• The selection rules and the atomic energy levels jointly account
for the structure of a Grotrian diagram (Fig. 8C.l), which summ
arizes the energies of the states and the transitions between the
m. In some versions, the thicknesses of the transition lines in th
e diagram denote their relative intensities in the spectrum.

18
Fig. 8C.l

19
 8C.2 The spectra of many-electron atom

• The spectra of atoms rapidly become very complicated as the n

umber of electrons increases, in part because their energy level
s, their terms, are not given solely by the energies of the orbital
s but depend on the interactions between the electrons.

20
• 考慮一個氦原子 (He) 的能階 , 它的兩個電子於基態的配置為 l
s2, 激發態配置是電子被提升為不同的軌道 , 例如 , 配置 ls12s1 .
兩個電子不需要配對 , 因為它們佔用不同的軌道。
• 根據 Hund 的最大多重性規則 (Hund‘s maximum multiplicity ru
le, 主題 8B), 自旋平行的原子狀態在能量上低於成配對的狀
態。
• 兩種狀態都是允許的 , 對應於不同的 Terms, 並且可以對應到原
子的光譜。

21
 Singlet term

•  
• Parallel and antiparallel (paired) spins differ in their total spin angul
ar momentum. In the paired case, the two spin momenta cancel, and
there is zero net spin (as depicted in Fig. 8C.2(a)).
• Its state is the one denoted in the discussion of the Pauli principle (T
opic 8B):

• The state of the He atom in which the two electrons are paired and t
heir spins are described by eqn 8C.3a gives rise to a singlet term.

22
Fig.8C.2 Singlet and triplet states

When two electrons have parallel spins,

they have a nonzero total spin angular
momentum. There are three ways of
achieving this resultant, which are shown
by these vector representations. Note that,
although we cannot know the orientation of
the spin vectors on the cones, the angle
between the vectors is the same in all three
cases, for all three arrangements have the
same total spin angular momentum (that is,
the resultant of the two vectors has the
same length in each case, but points in
different directions). Compare this diagram
with Fig. 8C.20, which shows the
antiparallel case. Note that, whereas two
paired spins are precisely antiparallel, two
‘parallel’ spins are not strictly parallel.

23
•  
• The angular momenta of two parallel spins add to give a nonzero total
spin. As illustrated in Fig. 8C.2(b), there are three ways of achieving n
on-zero total spin. The three spin states are the symmetric combinatio
ns introduced in Topic 8B:

• The alternative arrangement, in which the spins are parallel and are de
scribed by any of the three expressions in eqn 8C.3b, gives rise to a tri
plet term.

24
 Singlet and Triplet

• Triplet
A triplet state of an atom or molecule is a state in which the total spin quan
tum number is S=1, For two electrons, a triplet state corresponds to paralle
l electron spins and id denoted ↑↑. There are three states:
αα (MS=+1), αβ+βα (MS=0), and ββ (MS= –1).
• Singlet
A singlet state is a state of atom or molecule with zero net electronic spin
(S=0). For two electrons, a singlet state is one with antiparallel (paired) spi
ns, and is denoted ↑↓. The wavefunction for a singlet state of two spins is –
and corresponds to S=0, MS=0.
• Triplet states of atoms (and of many molecules) generally lie lower in ener
gy than singlet states because the electrons they describe avoid one another
and so have a lower Coulombic repulsion.
• Singlet and triplet states are interconverted by spin-orbit coupling.

Chap. 8 Techniques and applications 25

• 事實上 , 在 He 原子的 ls12s1 配置中的三重態 Term, 以平行
排列的自旋態在能量上低於反平行排列的自旋單重態 , 現在
可以說 , 在激發態 He 的 ls12s1 配置下 , 三重態的 Term 在
能量上低於單重態的 Term 。
• 這是屬於一個一般性結論 , 適用於其他原子 ( 和分子 ): 對於
由同一配置引起的狀態 , 三重態 Term 通常低於單重態。
• “For states arising from the same configuration, the triplet term generally lies lower th
an the singlet term.”

26
• Singlet and triplet terms 能量差的起源在於自旋相關性 (spin
correlation) 對電子之間 Coulombic 相互作用的影響 , 對基
態配置時 Hund‘s maximum multiplicity rule Hund( 最大多重
性規則 ,Topic 8B): 具有平行自旋的電子往往相互避免。由
於原子中電子之間的 Coulombic 相互作用很強 , 因此相同
配置的 singlet and triplet terms 的能量差異可能很大。例如 ,
He 配置 ls12s1 的 singlet and triplet terms 相差 6421 cm–1
( 對應於 0.80 eV) 。

27
 The first excited state of He: 1s1 2s1

• To incorporate the spin part into the spatial function Ψb

  1  2 
 1   
 [1s(1)2s(2 )  2s(1)1s(2) ] x
   1   2   1   2 
 2   
  1   2 
  antisymm . x  symm .   antisymm .

thus a state with degeneracy of 3 due to spin is called the triplet.

• To incorporate the spin part into the spatial function Ψa

 1 
 [1s(1)2s(2 )  2s(1)1s(2) ] x 1   2   1  2 
 2 
  symm . x  antisymm .   antisymm .

thus a state with degeneracy of 1 due to spin is called the singlet.

Chap. 8 Techniques and applications 28
• 原子氦譜比原子氫的光譜複雜 , 但有兩個簡化特徵。
• 其一是 , 唯一要考慮的激發配置是形式 ls1nl1; 也就是說 , 只
有一個電子是激發的。兩個電子的激發需要的能量大於原子
的電離能 , 因此形成 He+ 電離而不是雙激發原子。
• 其次 , 正如本 Topic 後面所示 , 單重態和三重態之間沒有輻
射性躍遷 , 因為兩個電子自旋的相對方向在過渡過程中不能
改變。因此 , 單重態 ( 包括基態 ) 和三重態之間的轉換 ( 而
不是兩個譜項 Terms 之間的轉換 ) 產生了頻譜。從光譜上
看 , 氦像兩個不同的物種。圖 8C.3 中的氦氣 Grotrian 圖顯
示了兩組的躍遷。

29
 Grotrian diagram

• Fig.8C.3 Part of the Grotrian diagram for a helium atom. Note tha
t there are no transitions between the singlet and triplet levels.
30
 8C.2b Spin–orbit coupling
8C2(b) Spin–orbit coupling
 spin–orbit coupling, the interaction of the spin magnetic moment
with the magnetic field arising from the orbital angular momentum .
 total angular momentum quantum number, j for one electron, J
for many.
 level, a term of a configuration corresponding to a given value of j or
J.
 spin–orbit coupling constant, A in
El,s,j = ½hcA{j(j + 1) – l(l + 1) – s(s + 1)}.
 fine structure, the structure in a spectrum due to spin–orbit coupling.

31
 Angular Momentum of Many-electron Atoms
• An atom has total orbital angular momentum L and total spin ang
ular momentum S. They are conserved quantity and commute wit
h the Hamiltonian operator. Thus L2, Lz , S2 and Sz commute with
Ĥ.
ˆL2   2 L L  1 ˆLz  M L
• The angular momentum vector of atom add vectorially but
the z-components as a scalars sum of electrons’ ℓzi.

L  i Lz   zi
i i
• The magnetic quantum number of orbital angular momentum
of an atom is M  L m  i
i
32
 電子的自旋

 
• 由於電子的自旋與其軌道運動是獨立分離的。電子自旋的
角動量沿任意軸的投影（ projection ）值為 ℏ ，且為角
動量函數的本徵值，這表示電子自旋行為是一個遵守費米
子統計的範例。
• 類似軌道角動量，自旋角動量具有磁矩，其大小可表示為

• 在固體中，許多電子的自旋以共同行動來影響材料的磁性
和電磁特性，例如在鐵磁性物體中表現永久性的磁矩。

35
 (b) Spin-orbit coupling

• 電子具有由自旋產生的磁矩 (magnetic moment) 。同樣 , 具有

軌道角動量 (orbital angular momentum ) 的電子 ( 即具有 l > 0
的軌道中的電子 ) 實際上是一個迴圈電流 , 並且具有由軌道
動量 (orbital momentum) 產生的磁矩。自旋磁矩與軌道角動
量產生的磁場的相互作用稱為自旋軌道耦合 (spin-orbit coupl
ing) 。耦合的強度及其對原子能量水平的影響取決於自旋和
軌道磁矩的相對方向 , 因此取決於兩個角矩的相對方向 (Figu
re 8C.4) 。

36
Fig.8C.4(a) Angular momentum
gives rise to a magnetic mome
nt (μ). For an electron, the ma
gnetic moment is antiparallel t
o the orbital angular momentu
m, but proportional to it. For s
pin angular momentum, there
is a factor 2, which increases t
he magnetic moment to twice
its expected value (see Sectio
n 8C.2).

37
 The Spin-Orbit Interaction

 
• 原子中有一個相互作用 , 是取決於軌域 L 和自旋 S 的相對方
向。電子由於其軌道角動量 L 而具有磁矩和磁場。它的自旋角動
量 S 也具有磁矩 mB 和磁場 B 。磁矩和磁場之間存在相互作
用。它是由於電子磁矩通過原子核和其他電子的電場的相對運動
所產生。
• 相互作用的能量表示為 E = – m·B 其與方向相依，且與自旋和
軌道角動量的兩個向量的內積成比例 (E ∝L·S.) ，因此取決於兩
個向量的方向。在自旋磁矩和由軌道運動產生的磁場之間的相互
作用稱為自旋軌道耦合 (spin-orbital coupling) 。其能量 (E = ˗ m•
B) 大小與 L·S 成正比。電子內在磁矩 S 的 z 分量只能包含
兩個值 : 一個正值和一個負值。原子中電子的總角動量是軌道和
自旋角動量的向量和，並用方程式 E8C. 5 表示。

38
 The Spin-Orbit Interaction

•  For a single electron (s = 1/2) we have only

j = l + 1/2 or j = l – 1/2. If l = 0 then of course we have only
j = 1/2
• The total magnetic moment of an electron is the sum of its orbital a
nd spin parts:

• Because this is not proportional to J it generally does not commute

with H. This causes considerable complication of the details in ato
mic spectra and in the Zeeman effect.

39
40
Figure 8.16

• Schematic diagram for the a

ddition of angular momentu
m vectors add vectorially bu
t the components in the z dir
ection add as scalars.
Source: D. A. McQuarrie, Qua
ntum Chemistry, Mill Valle
y, CA: University Science B
ooks, 1983

41
• For an atom containing two electrons, the maximum value of
L is obtained when both orbital angular momenta are lined up,
and the minimum value of L is obtained when two orbital angu
lar momenta are opposed.
L= l1 + l2,…,| l1− l2|

• If atoms contains more than two electrons, the relation can be

applied successively.

42
• Since the spin angular momentum of electron is
1
S z  mS  mS  
2
• The total spin angular momentum of the atom in the z direction i
s proportional to the spin quantum number MS for the z compone
nt of the whole atom.
S Z  szi M S  msi
i i

• Depending on the orientation in a magnetic field, the value of M

S can range from -S to +S.
• For atom containing two electrons, the possible values of S are
S= s1+s2,…,|s1–s2|.

43
 S= s1+s2, …, |s1–s2|

Fig.8C.10 For two electrons (each of which have s = 1/ 2), only two total spin
states are permitted (S = 0, 1). The state with S = 0 can have only one value
of MS (MS = 0 ) and is a singlet; the state with S = 1 can have any of three v
alues of MS (+1, 0, –1) and is a triplet. The vector representations of the si
nglet and triplet states are shown in Figs. 8C.2a and 8C.2b, respectively.
44
8C.2 (a) singlet and triplet states

45
Fig.8C.5 The coupling of the spin
and orbital angular momenta of
a d electron (l =2) gives two pos
sible values of j depending on t
he relative orientations of the sp
in and orbital angular momenta
of the electron.

46
 spin-orbit interaction

• 自旋軌道交互作用依賴於自旋和軌道角動量的相對方向的一
個表示方法 , 是說它取決於電子的總角動量，亦即是其自轉
和軌道角動量的向量和 (it depends on the total angular moment
um of the electron, the vector sum of its spin and orbital moment
a) 。
• 因此 , 當自旋和軌道角動量幾乎平行時 , 總角動量較高 ; 當兩
個角矩相反時 , 總角動量較低。。

47
• 電子的總角動量 (total angular momentum ) 由量子數 j 和
mj 描述 , 其中 j = l + ½ ( 當軌道和自旋角動量位於同一方
向時 ) 或 j = l – ½ ( 當它們相反時 ; 這兩種情況均如圖 Fi
g. 8C.5 所示 ) 。對於一個給定 l 值 , 可以為 Term 的級別產
生不同的 j 值。
對於 l = 0, 唯一允許的值是 j = ½ ( 總角動量與自旋角動
量相同 , 因為原子中沒有其他角動量來源 ) 。當 l = l 時 , j
可以是 3/2 ( 自旋和軌道角動量在一個相同的角力矩上 ) 或
1/2( 自旋和角動量在相反的角力矩上 ) 。

48
 Brief Illustration

• To identify the levels that may arise from the configurations (a) d1
and (b) s1, identify the value of l and then the possible values of j.

(a) For a d electron, l= 2 and there are two levels in the configuratio
n, one with j = 2 + ½ = 5/2 and the other with
j = 2 – ½ = 3/2.
(b) For an s electron l= 0, so only one level is possible, and j = ½.

With a little work, it is possible to incorporate the effect of spin-orbit

coupling on the energies of the levels.

49
• The spin-orbit interaction gives the "doublet" structure of the spectr
um of alkali elements. In Na, for example, there is a strong yellow s
pectral line (which give sodium light its dominant color) arising fro
m the transition of the valence electron from a state with n = 3, ℓ =
1 to the ground state with n = 3, ℓ = 0. The upper state is split into t
wo levels, while the lower state is unsplit (because L = 0). The resu
lting spectrum has two closely spaced lines. (This also occurs in hy
drogen, but the splitting is very small.)
• This is called the spin-orbit interaction. The general term for such
splitting is fine structure.
• Atoms has their electrons which interact to each other, cause their e
lectron energy state become very complicate.
• It is common for spectroscopists to apply term symbol as a abbrevi
ated description of the energy of an atom in a particular state.

50
• The
  dependence of the spin-orbit interaction on the value of j i
s expressed in terms of the spin-orbit coupling constant, Ã (wh
ich is typically expressed as a wavenumber, cm–1).
• A quantum mechanical calculation leads to the result that the e
nergies of the levels with quantum numbers s, l, and j are give
n by
E l, s, j = hcÃ{j(j + 1) – l(l + 1) – s(s + 1)}.

51
 自旋軌道耦合的起源

•  自旋 - 軌道耦合導致與原子譜項相關的能級分裂，
E l, s, j = hcÃ{j (j + 1) – l (l + 1) – s (s + 1)}.

• 如圖 E8C.6 和 E8C.7 所示。這種分裂，在原子光譜中顯示

為精細結構，影響光譜的出現。

52
 Spin-orbital coupling
• Spin-orbital coupling
• As atom with orbital angular momentum L and spin angular momentum S of
ten has a term in its Hamiltonian of the form AL·S called the spin-orbit cou
pling term. Since the total angular momentum J=L+S commutes with the Ha
miltonian, the states of this atom can be labeled with the eigenvalues of
J 2, JZ, L2 and S2. Notice that L·S = ( J 2 - L2 - S 2 )/2, so that the eigenvalue
of L·S is
1
 J  J  1  L  L  1  S  S  1 
2
• This can lead to observable energy level splitting. For example, the excited s
tate of an alkali atom with the outermost electron excited from the s to the ne
xt higher p orbital will have L=1 and S=½. This leads to two possible J value
s: 3/2 and ½. Calculate the energy level splitting due to spin-orbital couplin
g.

53
 Deriving an expression for the
energy of spin-orbit interaction
• Classically, the energy of a magnetic moment μ in a magnetic f
ield B is equal to their scalar product – μ·B. Follow these steps
to arrive at an expression for the spin-orbit interaction energy.
The procedures for manipulating vectors are
• Step 1 Write an expression for the energy of interaction.
• Step 2 Express the scalar product in terms of the magnitudes o
f the vectors.
• Step 3 Replace the classical magnitudes by their quantum mec
hanical versions.

54
• Step
  1 Write an expression for the energy of interaction
• If the magnetic field arises from the orbital angular momentu
m of the electron, it is proportional to l; if the magnetic mome
nt μ is that of the electron spin, then it is proportional to s. It fo
llows that the energy of interaction is proportional to the scalar
product s·l:
• Energy of interaction = scalar product of –μ·B s·l:

55
 Step 2

• Step
  2 Express the scalar product in terms of the magnitudes o
f the vectors
• Note that the total angular momentum is the vector sum of the
spin and orbital momenta: j = l + s. The magnitude of the vect
or j is calculated by evaluating

• So
• That is
• This equation is a classical result.

56
 Step 3
• Step
  3 Replace the classical magnitudes by their quantum mechanica
l versions
• To derive the quantum mechanical version of this expression, replac
e all the quantities on the right with their quantum mechanical value
s, which are of the form j(j + 1)ℏ², etc
• That is:
• Then, by inserting this expression into the formula for the energy of
interaction (E ex: s·l) and writing the constant of proportionality as ,
obtain an expression for the energy in terms of the quantum numbers
and the spin-orbit coupling constant, (a wavenumber):
E l, s, j = hcÃ{j (j + 1) – l (l + 1) – s (s + 1)}.

57
 Angular Momentum of Many-e Atoms

•• The
  energy of interaction is a dot product of the magnetic moment vectors
E = μsμl ∝ s·ℓ
• The total angular momentum j = ℓ + s, the magnitude of vector j is
j·j = (ℓ+s)·(ℓ+s) = ℓ·ℓ + s·s + 2 s·ℓ
then s·ℓ = ½ (J2 – ℓ2 – s2)
the expectation value of s·ℓ is
<j, ℓ, s| s·ℓ | j, ℓ, s> = ½ <j, ℓ, s| J2 – ℓ2 – s2| j, ℓ, s >
= ½ [j(j+1) – ℓ (ℓ+1) – s(s+1)] ℏ2
• The energy of levels with quantum numbers s, ℓ and j are:
• E l, s, j = hcÃ{j (j + 1) – l (l + 1) – s (s + 1)}.
where à is the spin-orbital coupling constant in cm–1

58
59
 Brief Illustration 8C.3

• The
  unpaired electron in the ground state of an alkali metal ato
m has l = 0, so j = ½. Because the orbital angular momentum i
s zero in this state, the spin-orbit coupling energy is zero (as is
confirmed by setting j = s and I = 0 in eqn 8C.4). When the ele
ctron is excited to an orbital with I= 1, it has orbital angular m
omentum and can give rise to a magnetic field that interacts wi
th its spin. In this configuration the electron can have j = ½ or j
= and the energies of these levels are

60
• Fig.8C.6 The levels of a 2p1
term arising from spin-orbit
coupling. Note that the low-j
level lies below the high-j le
vel in energy. The number o
f states in a level with quant
um number j is 2j + 1.

61
•  
• The corresponding energies are shown in Fig. 8C.6. Note that t
he barycentre (the 'centre of gravity') of the levels is unchange
d, because there are four states of energy the hcà and two of e
nergy –hcÃ

62
• 自旋軌道耦合的強度取決於核電荷。為了理解為什麼會這
樣 , 想像一下 , 騎在軌道電子上 , 看到一個帶電的原子核顯
然繞著你運行 ( 就像太陽升起和設置一樣 ) 。因此 , 您發
現自己處於電流環的中心。核電荷越大 , 電流越大 , 因此
檢測到的磁場越強。由於電子的自旋磁矩與軌道磁場相互
作用 , 因此核電荷越大 , 自旋軌道相互作用就越強。 “ th
e greater the nuclear charge, the stronger is the spin-orbit inter
action.”

63
• 事實證明 , 耦合隨原子數增加而急劇增加 ( 如 Z4), 因為電
流不僅較大 , 而且電子更接近原子核。而耦合在氫原子 H
中僅很弱 ( 導致能階變化不超過 0.4 cm–1), 而在 Pb 這樣的
重原子中 , 耦合非常強 ( 約為數千個 cm–1) 。

64
 THE SPECTRA OF COMPLEX ATOMS

Term symbols and selection rules

 term symbol, a symbolic specification of the state of an
atom, 2S+1{L}J.
 total orbital angular momentum quantum number, L.

65
 8.10 Term symbols and selection rules

Term symbols and selection rules (cont..)

 total spin quantum number, S.

 total angular momentum quantum number, J.
 Clebsch–Gordan series, L = l1 + l2, l1 + l2– 1,...|l1 – l2|.
 multiplicity, the number of levels of a term; for S  L, the value of
2S + 1.
 Russell–Saunders coupling, a coupling scheme based on the view
that if spin–orbit coupling is weak, then it is effective only when all
the orbital momenta are operating cooperatively.

66
 8.10 Term symbols and selection rules
0 Term symbols and selection rules (cont..)
 jj-coupling, a coupling scheme based on the view that the
individual spin and orbital momenta of the electrons are
coupled into individual j values and these momenta are
combined into a grand total, J.
 correlation diagram, a correspondence between the low
spin–orbit coupling (Russell–Saunders coupling) and high
spin–orbit coupling (jj-coupling) schemes.
 selection rules, ΔS = 0, ΔL = 0, ±1, Δl = ±1, ΔJ = 0, ±1, but
J = 0 |J = 0

67
• 在原子光譜學中，級別 (level) 是原子的一組狀態，共享相
同的量子數 J 的值。 Level is a term of a configuration corre
sponding to a given value of j or J.
• 每個 level 由 2J + 1 個狀態 (state) 組成，每個狀態 state
是由量子數 MJ 來區分。
• 自旋 - 軌道耦合是電子配置的自旋和軌道角動量之間的
磁相互作用，譜項 (term symbol) 的各種級別 level 間的
簡併性 (multiplicity) 因自旋 - 軌道耦合的作用而被移除
了 , 並出現自旋多重性。
• 原子光譜中的精細結構 (fine structure) 是由自旋 - 軌道耦
合產生的線分裂。磁偶矩的耦合是將級別 level 分成各種 s
tate 的原因。

68
 Term Symbols 2p13d1

1 Spin-orbit
r
12 interaction For less than half filled
subshells (within Term of
1P 1P
1 equal L and S), state with
high J as the lowest energy.
1D 1D
2

1F 1F
1 1
3 For more than half filled
2p 3d
subshells (within Term of
3P
2 equal L and S), state with
3P
3P
1 low J as the lowest
3P
3D
0 energy.
3
3D
3D 2
3D
1
3 F4
3F
3F 3
3F
2

69
 spectral lines of fine structure in Na

• 當電子激發態鹼金屬原子的 p 電子回到較低的軌道時 , 觀察到

兩條光譜線。一條線是由於從較高的 term 的 j = 3/2 級別開始
的轉換 , 另一條線是由於在同一個 term 的 j = 1/2 級別開始的
轉換。這兩條線是光譜精細結構的一個共同例子 , 這種結構是
由於自旋軌道耦合造成的。
• 精細結構可以從放電引起的鈉蒸氣發射光譜中 ( 例如 , 在一種街
道照明中 ) 看到。 589 nm 的黃線 ( 接近 17 000 cm–1) 實際上是
一條雙線 , 由一條線組成 , 為 589.76 nm (16956.2 cm–1), 另一條
線為 589.16 nm(16973.4 cm–1); 此雙精度值的元件是頻譜的「 D
線」 ( 圖 8C.7) 。因此 , 在納原子 , 受到自旋軌道耦合影響能量
約 17 cm–1| 。

70
71
• E8C.9a Calculate the shifts in the energies of the two terms of
a d1 configuration that can arise from spin-orbit coupling?
• For d electron, l = 2 and s = 1/2 leads to j = 5/2 and 3/2. So the
term symbols are 2D3/2 and 2D5/2 , the lowest energy level has th
e lowest value of {j(j + 1) – l(l + 1) – s(s + 1)}, which is
2
D3/2.

72
 E8C.9a

•  According to the simple treatment of spin-orbit coupling, the e

nergy is given by
• E l, s, j = hcÃ{j (j + 1) – l (l + 1) – s (s + 1)}
• where is the spin-orbit coupling, constant. So,
• El,s,j (2D3/2) = ½hc{j(j + 1) – l(l + 1) – s(s + 1)}

• El,s,j (2D5/2) = ½hc{j(j + 1) – l(l + 1) – s(s + 1)}

73
• E8C.9b
  Calculate the shifts in the energies of the two terms of a f1 c
onfiguration that can arise from spin-orbit coupling?
• For f electron, the atom has L = 3 and S = 1/2 leads to J = 7/2 or 5/2.
The term symbols are 2F7/2 and 2F5/2 . The lowest energy level has the
lowest value of {j(j + 1) – l(l + 1) – s(s + 1)}, which is 2F5/2.
• According to the simple treatment of spin-orbit coupling, the energy
is given by El,s,j = ½hc{j(j + 1) – l(l + 1) – s(s + 1)} where is the spi
n-orbit coupling, constant. So,
• El,s,j (2F5/2) = ½hc{j(j + 1) – l(l + 1) – s(s + 1)}

• El,s,j (2F7/2) = ½hc{j(j + 1) – l(l + 1) – s(s + 1)}

74
 Figure 8C.17

• Low-lying energy levels in alkali

atoms. For J = 3/2 the energy ter
m equals A/2; for J = ½ it equals
(3/2)A –A, giving a splitting of (3/2) A. I
n Na atom, the observed splitting
of the intense yellow fluorescent l
ine is 17.2 cm-1; thus, A = 11.47 c
m-1.

75
Example 8C.1 Analysing a spectrum for the spi
n-orbit coupling constant
• The
  origin of the D lines in the spectrum of atomic sodium is s
hown in Fig. 8C.17. Calculate the spin-or bit coupling constant
for the upper configuration of the Na atom.
• Collect your thoughts
• It follows from Fig. 8C.7 that the splitting of the lines is equal
to the energy separation of the j = 3/2 and 1/2 levels of the exc
ited configuration. You need to express this separation in terms
of by using eqn 8C.4.
  E l, s, j = hcÃ{j (j + 1) – l (l + 1) – s (s + 1)}.

76
•  The solution The two levels are split by

• The experimental value of Δv is J7.2cm·1; therefore

• Comment. The same calculation repeated for the atoms of other al

kali metals gives Li: 0.23 cm-1, K: 38.5 cm-1, Rb: 158 cm-1, Cs: 370
cm-1 • Note the increase of A with atomic number {but more slowl
y than zt for these many-electron atoms).

77
 Example 8.C1

• Analyzing a spectrum for the spin-orbital coupling constant

• In the spectrum of atomic sodium (Fig. 8C.30), calculate the spin-orbit coupling
constant for the upper configuration of the Na atom.
Method the splitting of the lines is equal to the energy separation of the j = 3/2 and
1/2 levels of the excited configuration.
Answer The energy term due to spin-orbital coupling (½)A J·S will be

A
 J  J  1  L  L  1  S  S  1   A  J  J  1  11 1  1  1  1  A  J  J  1  11
2 2 2  2  2  4

the two levels are split by

ΔE s 1 3  3  1  1   3
Δ~
ν  A    1    1   A  17.2 cm1
hc 2 2  2  2  2   2
therefore the spin-orbit coupling constant is obtained A=11.47 cm-1

78
• Self-test 8C.7
• The configuration ... 4p65d1 of rubidium has two levels at 25 7
00.56 cm-1 and 25 703.52 cm-1 above the ground state. What is
the spin-orbit coupling constant in this excited state?

79
 (c) Term symbols

• The discussion so far has used expressions such as 'the j = f

• level of a doublet term with l = 1'. A term symbol, which is a s

y mbol looking like 2P3/2 or 3D2, conveys this information, spec

ifically the total spin, total or bital angular momentum, and tot
al overall angular momentum, very succinctly.

80
 Term Symbol

• A term symbol gives three pieces of information:

1) The letter (P or D in the examples) indicates the total orb
ital angular momentum quantum number, L.
2) The left superscript in the term symbol (the 2 in 2P3/2) gi
ves the multiplicity of the term.
3) The right subscript on the term symbol (the 3/2 in 2P3/2) i
s the value of the total angular momentum quantum num
ber, J, and labels the level of the term.

81
 spin-orbit coupling( 自旋 - 軌域偶合 )

 In atomic spectroscopy, a level is a group of states of an

atom that share the same value of the quantum number J.
Each level consists of 2J+1 individual states that are disti
nguished by the quantum number MJ .
 Spin-orbital coupling is the magnetic interaction between
the spin and orbital angular momenta of an electron whic
h removes the degeneracy of the various levels of a term.
 The fine structure in an atomic spectrum is the line splitti
ng that arises from spin-orbit coupling. The magnetic co
upling is the cause of the splitting of a configuration into
levels.

82
• The
  meaning of these statements can be discussed in the light of the c
ontributions to the energies summarized in Fig. 8C.8.
• When several electrons are present, it is necessary to judge how their i
ndividual orbital angular momenta add together to augment or oppose
each other. The total orbital angular momentum quantum number, L, g
ives the magnitude of the angular momentum through
. It has 2L + 1 orientations distinguished by the quantum number ML
which can take the values 0, ±1, ... , ±L. Similar remarks apply to the t
otal spin quantum number, S, and the quantum number MS, and the tot
al angular momentum quantum number, J, and the quantum number M
J.

83
 譜項簡介和表示方法

• 為了得到 L 、 S 和 J ，需要將系統中個別電子的自旋角動
量 s 和軌道角動量ℓ [ 在原子光譜學的討論術語中，我們
區分斜體 S 表示總自旋量子數，而用羅馬字母 S 為來自
譜項的標籤。而這裡的小寫 ℓ 對應電子的角動量，大寫 L
對應系統的總角動量。 ]
• 有兩種方法可以得到系統的軌道總角動量 L 、自旋角動量
S 和總角動量 J ：
1) 對於較輕的元素 [ 原子序數在 40 以下 , 小於 Br] ，所有
電子的軌道角動量 l 耦合產生總軌道角動量 L ，所有
電子的自旋角動量 s 耦合產生總自旋角動量 S ，然後
L 和 S 耦合得到系統的總角動量 J = L + S ；
2) 對於重原子，每個電子的自旋角動量 s 和軌道角動量 l
先耦合得到電子的總角動量 j ，然後所有電子的 j 耦合
得到體系的 J 。
84
 Table 8.4

Symbols for Angular Momenta in Atoms

Type One electron Total in Atom

Spin Orbital Sum Spin Orbital Total

Vector si ℓi ji S=Ʃsi L=Ʃℓi J=L+S

z component szi ℓzi jzi Sz=Ʃszi Lz=Ʃℓzi Jz=Lz+Sz
Quantum No. si (½) ℓi ji S* L J
Magnetic q.n. msi mi MS ML MJ
(=±½) (=Ʃmsi) (=Ʃmi) (=ML+MS)

* S= s1+s2,…,| s1– s2|; L= ℓ1+ℓ2,…,|ℓ1– ℓ2|; J=L+S,…,|L – S|.

85
 Clebsch-Gordan series:

• The value of L (a non-negative integer) is obtained by couplin

g the individual orbital angular momenta by using the Clebsc
h-Gordan series:

Clebsch–Gordan series,
L = l1 + l2, l1 + l2– 1,...|l1 – l2|.
S = s1+ s2,…,| s1 – s2|;

86
• The modulus signs are attached to l1 – l2 to ensure that Lis non
negative.
• The maximum value, L = l1 + l2 , is obtained when the two orb
ital angular momenta are in the same direction; the lowest valu
e, | l1 – l2 |, is obtained when they are in opposite directions.
• The intermediate values represent possible intermediate relativ
e orientations of the two momenta (Fig. 8C.9).
• For two p electrons (for which l1 = l2 = 1), L = 2, 1, 0. The co
de for converting the value of L into a letter is the same as for t
he s, p, d, f, ... designation of orbitals, but uses uppercase Rom
an letters:

87
 Term Symbols( 項符號 )

• A term symbol is a label for the term arising from a configuratio

n and the corresponding levels .
• For atom it has the form: 2S+1
<L>J
– where 2S+1 is the multiplicity ( 自旋多重性 )
– J is the total angular momentum of level,
– <L> is a letter denoted the total orbital angular momentum of
the atom. The nomenclature (S, P, D, F) is derived from the c
haracteristics of the spectroscopic lines corresponding to (s, 
p, d, f) orbitals: sharp, principal, diffuse, and fundamental; the
rest being named in alphabetical order from G onwards, exce
pt that J is omitted. 
<L>: S P D F G H I etc
L 0 1 2 3 4 5 6 …
88
89
 Fig.8.C8

Fig.8.C8 A summary of the types of interacti

on that are responsible for the various kind
s of splitting of energy levels in atoms. For
light atoms, magnetic interactions are smal
l, but in heavy atoms they may dominate t
he electrostatic (charge-charge) interaction
s. In the coupled representation where tota
l angular momentum J (spin + orbital) is tr
eated, the associated microstates (or eigen
states) are |J, MJ, S, L> and MJ = J, J–1,
…, –J+1, –J

90
• Thus, a p2 configuration has L = 2, 1, 0 and gives rise to D, P,
• and S terms. The terms differ in energy on account of the different
spatial distribution of the electrons and the consequent differences
in repulsion between them.
• A note on good practice Throughout this discussion of atomic spec
troscopy, distinguish italic S, the total spin quantum number, from
Roman S, the term label.

91
• A closed shell has zero orbital angular momentum because all th
e individual orbital angular momenta sum to zero.
• Therefore, when working out term symbols, only the electrons of
the unfilled shell need to be considered. In the case of a single el
ectron outside a closed shell, the value of Lis the same as the val
ue of l; so the configuration [Ne]3s1 has only an S term.
• The convention of using lowercase letters to label orbitals and up
percase letters to label overall states applies throughout spectrosc
opy. not just to atoms.

92
 L= ℓ1+ℓ2,…,|ℓ1– ℓ2|

Fig.8C.9 The total angular orbital

momenta of a p electron and a
d electron correspond to L = 3,
2, and 1 and reflect the differe
nt relative orientations of the t
wo momenta.

Clebsch–Gordan series,
L = l1 + l2, l1 + l2– 1,...|l1 – l2|.
S = s1+ s2,…,| s1 – s2|;
93
 Example 8C.2

• Deriving the total orbital angular momentum of a configuration

• Find the terms that can arise from the configurations (a) d2
(b) p3

• Collect your thoughts

• Use the Clebsch-Gordan series and begin by finding the minimu
m value of L (so that you know where the series terminates). Wh
en there are more than two electrons to couple together, you need
to use two series in succession: first to couple two electrons, and
then to couple the third to each combined state, and so on.

94
• The solution (a) The minimum value is | l1 – l2 |, = l1 – l2 = 0.
• Therefore,
L = 2+2, 2+2-1, .. . , 0 = 4, 3, 2, 1, 0
corresponding to G, F, D, P, and S terms, respectively.
(b) Coupling two p electrons gives a minimum value of II - 11 = 0. T
herefore,
L' = 1+1, l + l -l, ..., 0 = 2, l, 0
• Now couple l3 = l with L' = 2, to give L = 3, 2, l; with I.: = l, to giv
e L = 2, 1, 0; and with L' = 0, to give L = l. The overall result is
L=3, 2, 2, l, l, 1, 0
• giving one F, two D, three P, and on

95
• Self-test BC.2 Repeat the question for the configurations (a)
• f1d1 and (b) d3

96
• When there are several electrons to be taken into account, their tot
al spin angular momentum quantum number, S (a non-negative int
eger or half-integer), must be assessed. Once again the Clebsch-G
ordan series is used, but now in the form
(8C.6)
• to decide on the value of S, noting that each electron has s = ½.
• For two electrons the possible values of S are 1 and 0 (Fig. 8C.l0).
If there are three electrons, the total spin angular momentum is obt
ained by coupling the third spin to each of the values of S for the f
irst two spins, which results in S= 3/2 and 1/2.

97
• The multiplicity of a term is the value of 2S + 1. When S = 0 (as f
or a closed shell, like ls2) the electrons are all paired and there is n
o net spin: this arrangement gives a singlet term, 1S.

98
99
• 單個電子具有 S= s = ½ , 因此配置 ( 如 as [Ne]3s1 ), 可以產生
doublet term, 2S 。同樣 , 配置 [Ne]3p1 是 doublet, 2P 。當有兩
個未配對 ( 平行自旋 ) 電子 S = 1, 因此 2S + 1 = 3, 給出一個三
重態項符 triplet term, 例如 3D 。
• singlets and triplets 的相對能量在先前的主題討論過 , 看到它們
的能量因自旋相對方向而不同。量子數 j 給出了單個電子的自
旋和軌道角動量的相對方向。對多個電子原子 , 總角動量量子
數 J( 非負整數或半整數 ) 執行相同的功能。

100
• 如果閉合殼外有單個電子 , J = j, j 值為 l+ ½ 或 | l– ½ |.
• 若為 [Ne]3s1 配置 , 具有的 j = ½ ( 因為 l = 0 和 s = 1/
2), 因此 2S 組態具有 single 單一的能級 , 表示 2S1/2 .
• 而 [Ne]3p1 配置為具有 l = 1; 因此 , j = 3/2 和 1/2; 因而 ,
2
P 項符有兩個能級別 , 2P3/2 和 2P1/2 。
• 由於自旋軌道相互作用 , 這些能級在不同的能量上。

101
• 如果閉殼外有多個電子 , 則必須考慮所有自旋和所有軌道
角動量耦合。當自旋 - 軌道耦合較弱 ( 對於原子數較低的
原子 ) 時 , 通過使用 Russell-Saunders coupling scheme( 羅
素 - 桑德斯耦合方法 ) 可以簡化這個複雜的問題。該方法
基於這樣一種觀點 , 即如果自旋軌道耦合較弱 , 則只有在
所有軌道角動量協同運行 (operating cooperatively) 時才有
效。也就是說 , 所有軌道角動量的電子耦合給出一個總角
動量 L, 和所有自旋都同樣耦合 , 以給出一個總的角動量
S 。只有在這個階段 , 兩種角動量通過自旋軌道相互作用
耦合 , 給出總和角動量 J 。 J 的允許值由 Clebsch-Gordan s
eries( 克萊布施 - 戈爾丹系列 ) 給出 :
J = L+S, L+S–1, …, |L–S|

102
• 例如 , 在配置 [Ne]2p13p1 的 3D term 中 , 允許的值為
3 、 2 、 1.
( 因為 3D 具有 L= 2 和 S= 1), 因此該項符具有三個能級
別 , 即 3D3, 3D2, and 3D1 。
• 當 L ≧S 時 , 多重性等於級別數。例如 ,
項符 2P term (L = 1) > (S = 1/2) 具有兩個級別 2P3/2 和 2P1
/2 . 而項符 3
D , (L = 2) > (S = 1) 則具有三個級別 levels 3
D
3, D2, 和 D1 。
3 3

• 但是 , 當 L < S 時情況並非如此 , 例如 ,
項符 term 2S (L = 0, < S = ½ ), 只有一個級別 level 2S1/2 。
• J = L+S, L+S–1, …, |L–S| = 1/2

103
 Example 8C.3

• Deriving term symbols

• Write the term symbols arising from the ground-state configuratio
ns of (a) Na and (b) F, and (c) the excited configuration ls22s22p13
p1 of C.
• Collect your thoughts
• Begin by writing the configurations, but ignore inner closed shell
s. Then couple the orbital momenta to find L and the spins to find
S. Next, couple L and S to find J. Finally, express the term as 2S+1
{L}J, where {L} is the appropriate letter. For F, for which the vale
nce configuration is 2p5, treat the single gap in the closed-shell 2p6
configuration as a single spin-½ particle.

104
 The solution

• (a) For Na, the configuration is [Ne] 3s1, and consider only the sing
le 3s electron. Because L= l = 0 and S = s = ½. the only possible val
ue is J = 1/2. Hence the term symbol is 2S1/2 .
• (b) For F, the configuration is [He] 2s22p5, which can be treated as
[Ne] 2p-1 (where the notation 2p-1 signifies the absence of a 2p elect
ron). Hence L= l = 1, and S = s = ½. Two values of J are possible: J
=3/2, 1/2. Hence, the term symbols for the two levels are 2P3/2 and 2
P1/2
• (c) ls22s22p13p1 of C.
This is a two-electron problem, and l1 = l2 = 1, s1 = s2= ½. It follows
that L= 2, 1, 0 and S = 1, 0. The terms are therefore 3D and 1D, 3P an
d 1P, and 3S and 1S.

105
• (c) For ls22s22p13p1 of C. possible term are 3D and 1D, 3P and 1
P, and 3S and 1S.
• For 3D, L= 2 and S = 1; hence J = 3, 2, 1 and the levels are 3D3,
3
D2, and 3D1.
• For 1D, L = 2 and S = 0, so the single level is 1D2. The triplet o
f levels 3P is 3P2, 3P1, and 3P0, and the singlet is 1P1.
• For the 3S term there is only one level, 3S1 (because J = 1 onl
y), and the singlet term is 1S0.

106
• Comment. Fewer terms arise from a configuration like ... 2p2 or ...
3p2 than f rom a configuration like ... 2p13p1 because the Pauli exc
lusion principle forbids parallel arrangements of spins when two
electrons occupy the same orbital. The analysis of the terms arisin
g in such cases requires more detail than given here.

• Self-test 8C.3 Identify the terms arising from the configurations

(a) 2s12p1, (b) 2p13d1.

107
 jj-coupling

• Russell-Saunders coupling fails when the spin-orbit coupling

is large (in heavy atoms, those with high Z). In that case, the
individual spin and orbital momenta of the electrons are cou
pled into individual j values; then these momenta are combi
ned into a grand total, J, given by a Clebsch-Gordan series.
• This scheme is called jj-coupling. For example, in a p2 confi
guration, the individual values of j are 3/2 and 1/2 for each el
ectron. If the spin and the orbital angular momentum of each
electron are coupled together strongly, it is best to consider e
ach electron as a particle with angular momentum J = 3/2 or
1/2. These individual total momenta then couple as follows:

108
For heavy atoms, in which jj-coupling is appropriate, it is best to discuss their
energies b y using these quantum numbers.
Although jj-coupling should be used for assessing the energies of heavy atoms,
the term symbols derived from Russell-Saunders coupling can still be used as
labels. To see why this procedure is valid, it is useful to examine how the energies
of the atomic states change as the spin-orbit coupling increases in strength. Such
a correlation diagram is shown in Fig. 8C.ll.
109
• For heavy atoms, in which jj-coupling is appropriate, it is best
• to discuss their energies by using these quantum numbers.
• Although jj-coupling should be used for assessing the energies
• of heavy atoms, the term symbols derived from Russell Saund
ers coupling can still be used as labels.

110
• It shows that there is a correspondence between the low spin o
rbit coupling (Russell-Saunders coupling) and high spin orbit c
oupling (jj-coupling) schemes, so the labels derived by using t
he Russell-Saunders scheme can be used to label the states of t
he jj-coupling scheme.

111
112
• To see why this procedure is valid, it is useful to examine how
the energies of the atomic states change as the spin-orbit coupl
ing increases in strength. Such a correlation diagram is shown
in Fig. 8C.11.
• It shows that there is a correspondence between the low spin o
rbit coupling (Russell-Saunders coupling) and high spin orbit c
oupling (jj-coupling) schemes, so the labels derived by using t
he Russell-Saunders scheme can be used to label the states of t
he jj-coupling scheme.

113
 Hund’s Rule

• 罕德定則 (Hund’s rule) 是 : 當數個電子分別進入相同能

階或近似的軌域時 , 最低能量狀態會是以平行的自旋方
向 (parallel spins) 填入軌域中 , 以獲得最大的自旋多重
性 (multiplicity).
• 若有兩個電子在不同的軌域 , 則可得三重態 (triplet state).
亦即兩個電子為同向自旋為較低能量 , 反之為較高能量 .
即為單重態 (singlet state), 亦即兩個電子為反向自旋 .

07/17/2020

114
 Hund’s rule ( 漢德規則 )

• 漢德規則是原子物理學中對 L-S 耦合電子組態的能階順序的

一個規則，於 1925 年由德國物理學家弗里德里希 · 漢德提
出。
1. 對於一個電子組態形成的一組原子態，多重數為 2 S + 1. .2
S+1 最大的能量最低。其中 S 為總自旋量子數，因此也可
以表達為總自旋量子數最大的能量最低。
2. 總自旋量子數 S 相同時，總角量子數 L 最大的能量最
低。

115
 Hund’s rule ( 漢德規則 )

• 1927 年漢德又提出了附加規則：

3. 在一個譜項的譜支項中，如果電子數低於或等於次殼層電子
數的一半 ( 不足或等於半填滿 ) ，其總量子數 J （ J = L + S
又稱內量子數）。 J 最小的光譜支項能量最低，稱為正常
次序；

4. 如果電子數超過滿殼層電子數的一半，其總角量子數 J 。
J 最大的光譜支項能量最低，稱為倒轉次序。
• 例如，氦原子 P 能階的三重態即為倒轉順序。

• 漢德規則只能夠用來確定能量最低的光譜項和光譜支項，不能將漢德規則
116
 漢德最大多重度規則

• 漢德最大多重度規則
• （ Hund's rule of maximum multiplicity ）是漢德規則中的第
一條，於 1925 年由弗里德里希 · 漢德提出。可以表述為：
一個確定的電子組態的所有能態中，自旋多重度最高的能態
能量最低。
• 漢德規則的真正原因是 : 高自旋態下電子與原子核的吸引作
用受到較少的屏蔽。
• 因其在原子化學、光譜學、量子化學中的重要性，又常被簡
稱為漢德規則，而忽略漢德的另外兩條規則。
• 一些中學教材裡面介紹的漢德規則：「當電子排布在同一能
級的不同軌道時，總是優先單獨占據一個軌道，而且自旋方
向相同。」實際上即是本規則。

117
118
119
• This rule can be explained classically by noting that two electr
ons have a high orbital angular momentum if they circulate in
the same direction, in which case they can stay apart. If they ci
rculate in opposite directions, they meet. Tims, a D term is exp
ected to lie lower in energy than an S term of the same multipli
city.
• 3. For atoms with less than half-filled shells, the level with the
lowest value of} lies lowest in energy; for more than half-fille
d shells, the highest value of J lies lowest.

120
• This rule arises from considerations of spin-orbit coupling. Th
us, for a state of low }, the orbital and spin angular momenta li
e in opposite directions, and so too do the corresponding magn
etic moments. In classical terms the magnetic moments are the
n antiparallel, with the N pole of one close to the S pole of the
other, which is a low-energy arrangement.

121
 Examples

• The 3P lowest energy term of Silicon (Si) consists of three levels, J =

2 , 1 , 0. With only two of six possible electrons in the shell, it is less
than half-full and thus 3P0, is the ground state.

• For sulfur (S) the lowest energy term is again 3P, with spin–orbit lev
els J = 2 , 1 , 0, but now there are four of six possible electrons in th
e shell so the ground state is 3P2.

• If the shell is half-filled then L = 0, and hence there is only one valu
e of J (equal to S ), which is the lowest energy state. For example, in
phosphorus (P)the lowest energy state has S = 3 / 2 , L = 0 for three
unpaired electrons in three 3p orbitals. Therefore, J = S = 3 / 2 and t
he ground state is 4S3/2

122
 Excited states
• Hund's rules work best for the determination of the ground stat
e of an atom or molecule.
• They are also fairly reliable (with occasional failures) for the d
etermination of the lowest state of a given excited electronic c
onfiguration. Thus, in the helium atom, Hund's first rule correc
tly predicts that the 1s2s triplet state (3S) is lower than the 1s2s
singlet (1S). Similarly for organic molecules, the same rule pre
dicts that the first triplet state (denoted by T1 in photochemistr
y) is lower than the first excited singlet state (S1), which is gen
erally correct.
• However Hund's rules should not be used to order states other
than the lowest for a given configuration. For example, the tita
nium atom ground state configuration is ...3d2 for which a naïv
e application of Hund's rules would suggest the ordering 3F < 3
P < 1G < 1D < 1S. In reality, however, 1D lies below 1G.
123
(e) Selection rules

124
125
126
127
128
 (c) Term Symbols 譜項

• From atomic spectra:

一個原子可依特定的能階系列存在 , 個別能階以所謂的譜項號
(Term symbols) 標示 , 能階之間的轉移產生的光譜可以提供個
別能階的量子數與能量的訊息 . 原子的放射光譜可用氣體放
電管或火焰爐激發 . 而吸收光譜則以光源通過原子氣體而得
(AA). 但並非所有可能的能階轉移都會發生 .
• 當某一原子由高能階 Ei 躍遷到低能階 Ej 上時，發射出與兩能
階之差相應的譜線，其波數等於 ͞ ν = (Ei/hc) ˗ ( Ej/hc) 。
• (Ei/hc) 和 ( Ej/hc) 就是分別對應能階 i 和 j 的譜項。譜項定義
為
Tn = ( En/hc) ，所以譜項可以對應能級，是由於具有部分填滿
的外殼層的電子組態。瞭解譜項對於電子光譜很重要，因為
光譜源自於電子在譜項之間的躍遷。
129
 譜項簡介和表示方法

• 當物體具有自旋性質時，存在有定量的自旋角動量 (spin a
ngular momentum 或內稟角動量 intrinsic angular momentu
m) 與軌道角動量 (orbital angular momentum) 間的交換作
用。稱為自旋軌道耦合（ spin-orbit coupling ）。
• 「自旋軌道耦合」 : 原子的每一個譜項 (term) 都與一個確
定的能態相對應，而原子的能態可以用量子數 L 、 S 和 J
來描述，所以譜項也可以用量子數 L 、 S 和 J 來描述。
• L 是原子的總軌道角動量；
• S 是原子的總自旋角動量；
• J 是原子的總角動量，

130
 Atomic Term Symbols

• 存在於多電子原子的穩定狀態，都是由原子整體特性決定的，而
不是那些原子的單個的電子決定的。
這些整體的屬性是什麼？
• 電子的軌道角動量， L 。 (The total orbital angular momentum of
the electrons,)
• 電子的自旋角動量， S 。 (The total spin angular momentum of the
electrons)
• 原子的總角動量， J 。 (The total angular momentum of the atom)

因此，原子的哈密頓量為本徵態 (eigenstates of the Hamiltonian)

，是由這些屬性標記。這些標籤被稱為原子能態的能譜項符號
(Atomic Term Symbols) ( 簡稱為譜項或項符 ) 。

131
• 用 L 、 S 和 J 表示譜項的方法是：
1. L 值為 0 ， 1 ， 2 ，…能態用大寫字母 S ， P ， D ， F……
表示，
2. 將（ 2S+1 ）的具體數值寫在 L 的左上角， 2S+1L 就是原子的
譜項。 2S+1 稱為譜項的多重性 (multiplicity) 。
3. 軌道和自旋相互作用使每個光譜項分裂為（ 2S+1 ）或（ 2L+
1 ）個譜支項， The number of possible microstates is (2S+1)×
(2L+1 ） . 不同的 J 也表示有 (2J+1) 個微組態 microstates
的統計權重貢獻，在譜項右下角寫出 J 的具體數值，便得到
相應的譜支項 :

2S+1
LJ
132
 Atomic state term symbols

• This is only the simplest way to find out the ground state term sy
mbol of any given atom. As the number of electrons increases, the
number of different ways of assigning them increases. it need mor
e complicate method to calculate when atoms have a lot of atomic
states,
Ex.: There are 15 micro states for carbon with two p electrons.
• n: number of sites
• e: number of electrons
• h: number of holes n! 6!
  15   2 S  1 2 L  1

e! h! 2!4!

133
 Clebsch-Gordan series

• 如果閉殼層外有複數電子，必須考慮在所有自旋和所有軌
道角動量的複雜的耦合。對於原子序數較低的原子，若當
自旋 - 軌道耦合相對較弱時，這個問題可以簡化，因而
可以選用 Russell-Saunders 耦合法。 RS 耦合法是基於假
設：如果自旋軌道耦合很弱，那麼只有當所有軌道角動量
合力運行時耦合才有效。因此可以想像所有的電子的軌道
角動量的向量和得到總軌道角動量 L ，並且類似地將所有
的自旋角動量的向量和以得到總自旋角動量 S 。直到這個
階段，才想像兩種角動量 L,S 通過偶極的耦合相互作用，
產生自旋 - 軌道耦合。總 J 的允許值是依照 Clebsch-G
ordan series
J = L + S, L + S – 1, …, | L – S |

134
 羅素 - 桑德斯 (Russell-Saunders) 耦合

• 在量子力學的譜項符號，是以多電子輕原子中角動量量子數
作簡要描述。一個特定電子組態各能階是依假設 LS 耦合 (L
S coupling) 來定義 total angular momentum J 。以描述預測
原子基態的能階。且由 NIST 依其特定的規則確定並編制成
表。
Russel-Saunders coupling (also known as LS coupling)
− Couple all individual orbital angular momenta ℓ to give a res
ultant total orbital angular momentum L. (L= Σℓi)
− Couple all individual spin angular momenta s to give a result
ant total spin angular momentum S. (S= Σsi)
− Finally couple L and S to give the total angular momentum J f
or the entire atom.
− Russel-Saunders coupling works well for the light elements u
p to bromine 135
 Electron configuration

• 電子組態是表示原子或分子的電子軌域的填充形式 , 一個
單一的電子組態可延伸出一系列的” TERMS”.
• Pauli exclusion principle : 不能存在兩個以上的電子佔用相
同的電子軌域 , 對相同軌域的兩個電子 , 其自旋態 (spin st
ates) 必須是成對的 (paired).
• 此定理延伸自更普遍化的 Pauli principle. 在分子組態中用
以決定分子的填充次序 .
• 微組態 (microstates): the different ways in which the electron
s can occupy the orbitals are called the microstate of configura
tion. Use the notation (mi±, mj±, mk±,…), the ± superscript in
dicates ms =+½ (+) and ms= –½ (–).

136
 單電子的微組態數
• The number of basis states in the uncoupled system with given S and
L is represented by |S, mS, L, mL>, here mS and mL are z-axis
components of total spin and total orbital angular momentum
respectively, as mS = S, S–1,…, –S+1, –S and mL = L, L–1,…,
–L+1, –L. Also where S, mS, L, mL are good quantum numbers whose
corresponding operators mutually commute. With given S and L, the
eigenstates in this representation span the function space with
dimension of (2L+1) (2S+1).

137
 Rules for term symbol

The following rules are helpful in determining the term symbol(s) arising fro
m an electron configuration.
• Rule 1: Filled subshells don't matter. Any filled subshells have a total orbital
angular momentum L = 0 and spin angular momentum S = 0.
• Rule 2: Each term symbol 2S+1L represents a state described by one or more “
L-S” eigenfunctions. An L-S eigenfunction is a function which is an eigenfu
nction of L2̂ ; L̂z; Ŝ 2, and Ŝ z simultaneously.
(This means, for example, that the L-S eigenfunction has definite values of
L; ML; S; MS). There is one L-S eigenfunction for each possible (ML;MS) pai
r, where
• ML = –L; –L+1; … ; L–1; L, and
• MS = –S; –S+1; … ; S–1; S.
There are (#ML)*( #MS) = (2L+1)(2S+1) L-S eigenfunctions for each term sy
mbol.
138
 Rules for term symbol

• Rule 3: For each Slater determinant with given values of ML and MS, there is
exactly one L-S eigenfunction with L ≥ ML and S ≥ MS and having the same ei
genvalues ML and MS of the operators L̂z and Ŝz, respectively.
• Corollary: If an L-S state or term symbol is possible for a particular configur
ation, then it must be possible to construct at least one Slater determinant wit
h ML = L and MS = S.
• Rule 4: The scalar L must be less than or equal to the sum of the magnitudes
of the orbital angular momenta of the individual electrons,
• L ≤ l1 + l 2 + l3 + … + l n (1)
• Similarly, S ≤ n/2, where n is the number of electrons outside closed shells.

139
 Assigning Term Symbols
Source: http://inorganic.chemistry.pu.edu.tw/first/New/L2/D.html

1. The ground state of hydrogen atom is 2S1/2

Draw the most stable electronic configuration (don't care about the i
nner full subshell electrons).
2. Calculate the ML and MS (ML= Σmℓ and MS= Σms) (just add all the m
ℓ
and ms value of electrons together)
3. Find out the L and S values, (L is the biggest number of ML and S is
the biggest number of MS)
4. Calculate the J value, (J = L+S, L+S-1, L+S-2, ..., |L–S|).
5. For L, you must use alphabet capitals not numbers, L=0 is S, L=1 is
P, L=2 is D, L=3 is F, L=4 is G, L=5 is H...
6. Put all the S, L, J values on, you got the term symbol
2S+1
LJ

140
 Example 8.12 2s1 and 2p1
• What are the atomic term symbols for lithium and boron in their lowes
t states?
• Since Li and B each have a single electron outside of closed shells, the
ir possible term symbols are readily identified. Since Lithium has a 2s
electron with ℓ=0, its magnetic quantum number m must also be zero.
m m S ML MS MJ
0 ±½ 0 ±½ ±½
Thus, L = 0, S = ½, and J = ½, and the term symbol is 2S1/2.
• Boron has a p electron with ℓ=1, so that.
m m S ML MS MJ
0 ±½ 0 ±½ ±½
±1 ±½ ±1 ±½ ±1/2; ±3/2
Thus, L = 1, S = ½, and J = 3/2, so there are two possible term symbol
s, 2P3/2 and 2P1/2.
141
 Example 8C.7 Deriving term symbols

• Write the term symbols arising from the ground-state configurat

ions of (a) Na and (b) F
Answer (a) For Na, the configuration is [Ne ]3s1, and we consider t
he single 3s electron. Because L = ℓ = 0 and S = s = 1/2 it is possib
le for J = j = s = 1/2 only. Hence the term symbol is 2S1/2
(b) For F, the configuration is [He]2s22p5, which we can treat as [N
e]2p1 (or the notation 2p-1 signifies the absence of a 2p electron). H
ence L = 1, and S = s = 1/2· Two values of J = j are allowed: J = 3/
2, 1/2 . Hence, the term symbols for the two levels are is 2P3/2, is 2P1
/2 .

142
 Examples ns1and ns2

1
H(1s1)
– mℓ=0, ML=0, L=0
ms=1/2 or ˗1/2, Ms=1/2 or ˗1/2, S = 1/2, multiplicity 2S+1=2
– J = L+S, ..., |L˗S| = 1/2
• So the term symbol of atomic state of H atom is 2S1/2
 
2
He(1s2)
– mℓ=0+0=0, ML= 0, L=0
– ms= (1/2) and (˗1/2) ; Ms= (1/2)+(˗1/2) = 0, S = 0 , multiplicity 2S+1 =
1
– J = L+S = 0
• So it's atomic state term symbol is 1S0

143
 Examples 2p1 and 2p5
5
B (1s22s22p1)
– mℓ=1, ML=0(s)+0(s)+1(p)=1, L=1
ms=1/2, MS=1/2, S=1/2, 2S+1=2
– Σ(2L+1)(2S+1) = 6; J = L+S,...,|L–S| = 1/2, 3/2
• So it's atomic state term symbol is 2P1/2, 2P3/2
• The lowest atomic state is the smallest value of J, so it is 2P1/2.

9
F (1s22s22p5)
– mℓ=1+1+0+0+(-1)=1, ML=1, L=1
ms=3(1/2)+2(-1/2)=1/2, MS=1/2, S=1/2; 2S+1=2
– Σ(2L+1)(2S+1)=6; J=L+S,...,|L-S|= 1/2, 3/2
• So it's atomic state term symbol is 2P1/2, 2P3/2
• For the fluorine atom, it has more than half filled electron configuration, the lowest
atomic state is the biggest J, so it is 2P3/2.
144
 2 electrons

• When 2 electrons are in two separate orbitals u and v, the poss

ible spin arrangements are:

• if S = 1, then MS must be 1, 0, and –1. a triplet states, (α α, αβ

+βα, and ββ).
• If S = 0, then MS must be 0, a singlet state (αβ–βα)

145
 Multiple-electron Atomic Term Symbols

1. S 值和 L 值的組合稱為譜項 (Term) ，並具有 (2S+1)×(2L+1)

個可能的微組態數 ;
2. 多電子原子 S ， L 和 J 的組合稱為級別 (Level) 。 特定級
別所對應的微組態數為 (2J+1) ，這是相應譜項中，與該級別
相關的可能的微組態數 ( 即級別的統計權重 );
3. L ， S ， J 和 MJ 的組合，才可確定單個微組態 (micrstat
e) 。
4. In the coupled representation where total angular momentum J (s
pin + orbital) is treated, the associated microstates (or eigenstate
s) are |J, MJ, S, L> as MJ= J, J–1,..., –J+1, –J , these states span t
he function space with dimension of

146
 Multiplicity ( 自旋多重性 )

• 例如，在 [Ne] 2p13pl 的電子配置推得 3D 譜項時， J 的

允許值為 3, 2, 1 ( 因為 L = 2 且 S = 1) ，因此該項具有三
個級別 (levels) ， 3D3 , 3D2 和 3D1 。
• When L ≥ S, the multiplicity is equal to the number of levels.
For example, a 2P term has the two levels 2P3/2 and 2P1/2, and 3D
has the three levels 3D3 , 3D2 和 3D1
• However, this is not the case when L < S: the term 2S, for exa
mple, has only the one level 3S1/2 .

147
 Example np2

• 舉例， 6C(1s22s22p2)
• To calculate all possible term symbols for a given electron configura
tion
of 6C(1s2 2s2 2p2) ?
• First, how many ways of atomic state are there in the term symbols
對特定的 p2 電子配置，首先找出電子排列的可能性有多少？
• 對 p2 電子配置具有 S = 1 ， L = 2 ，則存在
(2S+1)×(2L+1) = (2×1 +1)×(2×2 +1 ） = 15 個的微組態，可
對應於 p2 配置的譜項 ;
• 於全部微組態中屬於 J = 3 級別的微組態有 (2×3 + 1) = 7 個。
集合同一譜項中所有級別的微組態數（ 2J + 1 ）之總和將等於
15 。 在此例，級別 J 可以是 1, 2 或 3 ，所以 ∑ (J+1) = 3 +
5 + 7 = 15 。

148
6
C (1s2 2s2 2p2)

• Second: draw all the possibilities

-1 0

-2 0

149
 p2 configuration

• The following table summarizes all the possible arrangements of elec

trons in the 2p2 configuration in the 2p orbitals. The spin of the electro
ns in each arrangement is indicated by arrows that point either up or
down for spin up and spin down. Here, ML represents the algebraic s
um of the value of m, for each electron while MS is the algebraic sum
of the value of m, for each electron. 

150
 np2

• Third: count the number of microstates for each ML—MS possi

ble combination and set up a table for total numbers

151
 np2

• Fourth, extract smaller tables representing each possible term.

Each table will have the size (2L+1) by (2S+1), and will contai
n only "1"s as entries. The first table extracted corresponds to
ML ranging from −2 to +2 (so L = 2), with a single value for M
S (implying S = 0). This corresponds to a D term.
1

(a) S=0, L=2, J=2   Ms

1
D2   0

• Number of microstates +2 1
+1 1
are ∑(2J + 1) = 5 Ml 0 1
−1 1
−2 1

152
 np2
The remaining table is 3×3. Then we extract a second table,
removing the entries for ML and MS both ranging from −1 to +1 (and
so S = L = 1, a 3P term). The remaining table is a 1×1 table, with L =
S = 0, i.e., a 1S term.
(b) Number of microstates (c) S=0, L=0, J=0
are ∑(2J + 1) = 5 +3 + 1 = Number of microstates
9 are ∑(2J + 1) = 1
Ms

  +1 0 −1
+1 1 1 1
Ml 0 1 1 1 Ms

−1 1 1 1   0
Ml 0 1

153
Table 8C.3E

154
 j = ℓ+s, ℓ+s–1, …,|ℓ–s|.

Fig. S9.30 The coupling of the

spin and orbital angular
momenta of a d electron (ℓ = 2)
gives two possible values of j
depending on the relative
ℓ

orientations of the spin and

ℓ

orbital angular momenta of the

electron.

156
 Case of two equivalent electrons

• If only two equivalent electrons are involved, there is an "Eve

n Rule" which states that, for two equivalent electrons, the onl
y states that are allowed are those for which the sum (L + S) is
even.

157
 Example ns2

• What is the atomic term symbol for helium in its ground state?
ANS: Electron configuration for helium in its ground state: 1s2
• Magnetic quantum number mi of both electrons are zero, and
• since the electrons are paired in configuration 1s2, the quantum numbe
r msi for the z component of the spin is +½ for one electron and -½ for
the other, as shown in the following summary:
m1 m1S m2 m2S ML MS MJ
0 +½ 0 ˗½ 0 0 0
• Since ML=0 and there is only one possible state, the total orbital angul
ar momentum quantum number L for the helium atom must be equal t
o zero.
• Similarly, since MS = 0, the total spin angular momentum quantum nu
mber S for the helium atom must be equal to zero.
• Since MJ = ML + MS is equal to zero, the total angular momentum qua
ntum number J for the atom is zero, and the term symbol is 1S0.
158
 Example ns2

• What are the atomic term symbols for a two-electron atom wit
h the electrons in different s orbitals?
• Suppose an atom with ns2 valence electrons is excited to a stat
e with valence electrons ns1n’s1, where n’ is a higher principal
quantum number. Now the electron spins do not have to be pai
red and so there are four possible states, which in general will
have different energies:
m1 m1S m2 m2S ML MS MJ
0 +½ 0 +½ 0 1 1
0 +½ 0 -½ 0 0 0
0 -½ 0 +½ 0 0 0
0 -½ 0 -½ 0 -1 -1

159
 Example ns2
m1 m1S m2 m2S ML MS MJ
0 +½ 0 +½ 0 1 1
0 +½ 0 -½ 0 0 0
0 -½ 0 +½ 0 0 0
0 -½ 0 -½ 0 -1 -1
• In the first row the spins are parallel, so the z component of the spin quantum numb
er MS for atom is 1 and quantum number S for the spin angular momentum is one.
• Since the valence electrons are both s electrons, mℓ = 0 and L = 0.
• For all four possibilities, quantum number ML for orbital angular momentum is zer
o.
• Therefore the quantum number L for the total angular momentum is zero.
• Since the largest value of MS is unity, the total spin quantum number S for the atom
can have values of 1 and 0.
• If S=1 and L=0 then J=1 and the term symbol is 3S1. Note that for this case, MS=1,
0,-1, so that we have a triplet state. If S=0 and L=0, then J=0 and the term symbol is
1
S0, a singlet state. As indicated by Hund’s first rule, the triplet state is the most stabl
e. 160
 Excited state of Helium atom

2
He (1s12s1)
– mℓ=0, ML=0+0=0, L=0
msi=±1/2, Ms= 1 ,0,-1 or 0; S=1; 2S+1=3 or 1
– Σ(2L+1)(2S+1)=4; J=L+S,...,|L-S|= 1 ,0

ML 0 1 2 1

• So it's atomic state term symbol is 3S1, 1S0. -1 0 1

S=1,L=0, J=1 S=0,L=0, J=0 MS

ML 0 1
ML 0 1 1 1

0
-1 0 1 1
S0
S1
3
MS
M 161
 Example 8C.2
Example 8C.2 Deriving the total orbital angular momentum of a configuration

162
 (a) Exercise nd2
22
Ti(1s22s22p63s23p64s23d2)
 The total number of states from the d2 configuration must b
10!
e C(10,2) =
8! 2!
 45 ;
 Start with the highest MS value; since there are 2 electrons,
ms= (1/2), (–1/2); MS=1, 0, -1; S = 1, 0; 2S+1 = 3, 1
 For S =1, L =3, J=4, 3, 2. 3F4, 3F3, 3F2 (9+7+5=21 states)
 For S =1, L =1, J=2, 1, 0. 3P0 , 3P1 , 3P2 (1+3+5=9 states)
 For S =0, L =4, J=4. 1G4 (9 states)
 With detail procedure, all the atomic state term symbols of 2
2
Ti are : 3F2 , 3F3 ,3F4 , 3P0 , 3P1 , 3P2 , 1G4 , 1D2 , 1S0.

163
 d2 configuration

10 microstates for MS = +1 and 10 microstates for MS = −1. By

symmetry, an equivalent pattern must be observed for negative
value of mS = -1/2 , so as MS = −1.
164
 Table for d2

• Microstates of the d2 configuration

MS
ML -1 0 +1
+4 (2+,2-)
+3 (2-,1-) (2+,1-) (2-,1+) (2+,1+)
(2+,0-) (2-,0+)
+2 (2-,0-) (2+,0+)
(1 ,1 )
+ -

(2+,-1-), (2-,-1+),
+1 (2 ,-1 ), (1 ,0 )
- - - -
(2+,-1+), (1+,0+)
(1 ,0 ) (1 ,0 )
+ - - +

(2+,-2-) (2-,-2+)
0 (2-,-2-) (1-,-1-) (1+,-1-) (1-,-1+) (2+,-2+) (1+,-1+)
(0+,0-)
-1~-4 (the lower half is a reflection of upper half)

165
 d2 configuration

• The following steps will be illustrated for a d2 configuration.

STEP 1 (Number of Microstates)
N = n!/e! h! = n!/e!(n-e)! = 10!/(2!*8!) = 45
STEP 2 (Values of ML and MS)
For a d orbital, ml may range from +2 through –2 so there are
5 acceptable ml values. The maximum value of ML for 2 electr
ons is when ml = +2 and when m2 = +2 or ML = 4 (this can onl
y occur if MS = 0). ML will range +4, +3, …, -4.
The allowed values for MS are 1, 0, -1 since two electrons ma
y be spin aligned (up or down) or paired.

166
 (a) Exercise nd2

• These are the 25 microstates for MS = 0

• Therefore, 10 (MS = +1) + 10 (MS = −1) + 25 (MS = 0) = 45
microstates as required by Step 1

167
(a) Exercise nd2

168
 (a) Exercise nd2

STEP 3
The Pauli allowed microstates can be drawn as shown on the follo
wing pages. Remember that certain combinations of quantum num
bers are not allowed (e.g., ML = −4 and MS = +1 since this would r
equire two parallel spins in the same orbital).

169
 (a) Exercise nd2

STEP 4. Chart Microstates

On left column put range of ML values
On bottom row put range of MS values
Then enter the total number of microstates that have equivalen
t ML and MS values
The sum of the values in this chart must total 45, the total nu
mber of microstates.

170
 (a) Exercise nd2
Table 1
• STEP 4. Chart Microstates 4 1
On left column put range of ML
3 1 2 1
values On bottom row put range
of MS values. Then enter the tot 2 1 3 1

al number of microstates that ha 1 2 4 2

ve equivalent ML and MS value ML 0 2 5 2
s. The sum of the values in this
-1 2 4 2
chart must total 45, the total nu
mber of microstates. -2 1 3 1
-3 1 2 1
-4 1
-1 0 1
MS

171
 (a) Exercise nd2

STEP 5. Resolve Microstates

4 1
Go to the upper central corner (red) elem
ent. This element yield a microstate whic 3 1

h correspond to ML = 4 and MS = 0. This 2 1

must be a G state since L = 4 and it must 1 1

be an orbital singlet since MS = 0 or S = ML 0 1

0. Therefore, the first term is 1G (with 9 -1 1

microstates) with L = 4, S = 0 and J = 4. -2 1
-3 1
-4 1
-1 0 1
MS
G4
1

172
 (a) Exercise nd2
Table 2
• Elements Removed: G (9 micros
1
4 0
tates in 9 × 1 matrix).
3 1 1 1
• A 1G representation corresponds t
2 1 2 1
o a 9 × 1 matrix (ML × MS) since
1 2 3 2
L can range from +4 through –4
ML 0 2 4 2
(9 elements) and S can only equal
0 (1 element). (Notice that the ele -1 2 3 2

ments removed for 1G came from -2 1 2 1

the MS = 0 column, with one fro -3 1 1 1
m each ML row as required.) -4 0

• Removing 9 microstates from Ta -1 0 1

ble 1 yields Table 2. MS

173
 (a) Exercise nd2

• Now go to the upper right corner

4
(red) element. The ML and MS v
3 1 1 1
alue for this element yield the ne
2 1 1 1
xt microstate representation. ML
1 1 1 1
=3 therefore L = 3, <L> ≡ F.
ML 0 1 1 1
• Also MS =1 therefore S = 1, and
-1 1 1 1
2S +1= 3, a triplet, so the eleme
-2 1 1 1
nt is 3F. with L = 3, S = 1 and J =
-3 1 1 1
4, 3, 2.
• 3F is a 7 × 3 matrix = 21 microst -4

ates that are removed to give Ta -1 0 1

ble 3. MS
3
F4 , 3F3 , 3F2
174
 Table 3 for nd2
Table 3
• Elements Removed: 1G, 3F (9+21 = 30 4 0
microstates) 3 0 0 0
• Now go to the right corner (red) elemen
2 0 1 0
t. The ML and MS value for this element
1 1 2 1
yield the next microstate representation.
ML 0 1 3 1
ML=1, MS=1
-1 1 2 1
-2 0 1 0
-3 0 0 0
-4 0
-1 0 1
MS

175
 for nd2

• Since ML=1, therefore L = 1, <L> ≡ P. 4

• Also MS =1 therefore S = 1, and 2S +1= 3
3, a triplet, so the element is 3P. with L = 2
1, S = 1 and J = 2, 1, 0. 1 1 1 1
• 3P is a 3 × 3 matrix = 9 microstates that ML 0 1 1 1
are removed to give Table 4. -1 1 1 1
-2
-3
-4
-1 0 1
MS
3
P2 , 3P1 , 3P0

176
 Table 4 for nd2
Table 4
• Elements Removed: 1G, 3F, 3P (9+21+9 4 0
= 39 microstates) 3 0 0 0
• Now the upper central corner (red) elem
2 0 1 0
ent yield a microstate which correspond
1 0 1 0
to ML = 2 and MS = 0. This must be a D
ML 0 0 2 0
state since L = 2 and it must be an orbita
-1 0 1 0
l singlet since MS = 0 or S = 0
-2 0 1 0
-3 0 0 0
-4 0
-1 0 1
MS

177
 for nd2

• Therefore, this term is 1D (5 microstate 4

s) with L = 2, S = 0 and J = 2. which giv 3
es 1D (ML = 2, MS = 0).
2 1
• Remove this 5 × 1 matrix yielding Table
1 1
4.
ML 0 1
-1 1
-2 1
-3
-4
-1 0 1
MS
1
D2

178
 Table 5 for nd2
Table 5
• Elements Removed: 1G, 3F, 3P, and 1D 4 0
(9+21+9 +5 = 44 microstates) 3 0 0 0
• Now the only element left is a microstat
2 0 0 0
e which correspond to ML = 0 and MS =
1 0 0 0
0. This must be a S state and it must be
ML 0 0 1 0
an orbital singlet since MS = 0 or S = 0.
-1 0 0 0
• Therefore, the last term is 1S (1 microsta
-2 0 0 0
tes) with L = 0, S = 0 and J = 0.
-3 0 0 0
• the d configuration gives:
2
-4 0
• G, F, D, P, S (45 microstates)
1 3 1 3 1
-1 0 1
MS
1
S0

179
 Assigning J values for nd2

• J = L + S …|L–S|: number of microstates = 2J + 1 For

• 1G (L =4, S =0, and J = 4) → 1G4 9 microstates
• 3F (L =3, S =1, J =4, 3,2) → 3F4 3F3 3F2 (9+7+5) = 21 microstates
• P (L = 1, S =1, J =2,1,0) → 3P2 3P1 3P0 (5+3+1) = 9 microstates
3

• D (L =2, S =0 , and J = 2) → 1D2 5 microstates

1

• 1S (L = 0, S =0 , and J = 0) → 1S0 1 microstate

• Notice that the total number of microstates equal 45 at this point. W
e now have accounted for all 45 microstates:
1
G4, 3F4, 3F3, 3F2, 3P2, 3P1, 3P0, 1D2, 1S0,

180
 (a) Exercise nd2

4 1
#
3 1 2 1 Term microstate L S J
2 1 3 1 3
F 7x3=21 3 1 4,3,2
1 2 4 2 3
P 3x3=9. 1 1 2,1,0
ML 0 2 5 2
1
G 9x1=9 4 0 4
-1 2 4 2
1
D 5x1=5 2 0 2
-2 1 3 1
-3 1 2 1
1
S 1x1=1 0 0 0

-4 1 total = 45

-1 0 1
MS

181
 (a) Exercise nd2

• Thus, for nd2 the triplet terms are

3
F4 (9 microstates)
3
F3 (7 microstates) 21 microstates
3
F2 (5 microstates)
3
P2 (5 microstates)
3
P1 (3 microstates) 9 microstates
3
P0 (1 microstate)
We must now arrange these in a predicted orbital energy scheme.
， d2 未達半填滿 , 為正常次序 (J 最小的譜支項能量最低 ).
F2 < 3F3 < 3F4 < 3P0 < 3P1< 3P2 < 1G4 < 1D2 < 1S0
3

182
 (a) Exercise nd2

Predicted ground state is 3F2 for nd2 , in actual experiment result is 3F2

183
 Case of 'inequivalent electrons’

• Write the term symbols arising from the excited configuration Is2
2s22p13p1 of C.

• We are treating an excited configuration of carbon because, in th

e ground configuration, 2p2, the Pauli principle forbids some term
s, and deciding which survive (1D, 3P, 1S, in fact) is quite complic
ated. That is, there is a distinction between 'equivalent electrons',
which are electrons that occupy the same orbitals, and 'inequivale
nt electrons', which are electrons that occupy different orbitals.

184
 2p13p1

• The excited configuration of C under consideration is effectively 2p

1
3p1. This is a two-electron problem, and ℓ1 = ℓ2 = 1 , s1 = s2 = ½ foll
ows that L = 2, 1, 0 and S = 1, 0. The terms are therefore 3D and 1D,
3
P and 1P, and 3S and 1S.
• For 3D, L = 2 and S = l; hence J = 3, 2, 1 and the levels are 3D3, 3D2,
and 3D1.
• For 1D, L = 2 and S = 0, so the single level is 1D2.
• The triplet of levels of 3P is 3P2 , 3P1 ,and 3P0 , and the singlet is 3P1 .
• For the 3S term there is only one level, 3S1 (because J = 1 only), and
the singlet term is 1S0 .

185
 Self-test 8C.11 2s12p1

Self-test 8C.11
• Write down the terms arising from the configurations (a) 2s12p
1
(b) 2p13d1,

[(a) 2s12p1 : Will be 3P2 , 3P1 , 3P0 , 1P1 ]

186
 ns1d1
Table 8C.4E

187
 2p13d1

(b) 2p13d1 : terms will be

3
F4 , 3F3 , 3F2 , 1F3, 3D3 , 3D2 , 3D1 , 1D2, 3P2 , 3P1 , 3P0 , 1P1

188
 Term Symbols 2p13d1

1 Spin-orbit
r
12 interaction For less than half filled
subshells (within Term of
1P 1P
1 equal L and S), state with
high J as the lowest energy.
1D 1D
2

1F 1F
1 1
3 For more than half filled
2p 3d
subshells (within Term of
3P
2 equal L and S), state with
3P
3P
1 low J as the lowest
3P
3D
0 energy.
3
3D
3D 2
3D
1
3 F4
3F
3F 3
3F
2

189
 (b) Exercise np3

• (b) What are the atomic state term symbols of 7N (1s2 2s2 2p3) ?
• First calculate how many possibilities of electron arrangement wil
l be ? n! 6!
• It has 20 micro states: e ! h !  3!3!  20

190
 (b) Exercise np3
• First, coupling of two electrons out of 3 gives a minimum value of
|1–1|= 0. Therefore, L' = (l1 + l2 ),…, | l1– l2 | = (1+1), (1+1–1), ... ,
|1–1| = 2, 1 ,0. Now L = (L’ + l3 ), …, | L’– l3 |
• If couple l3 with L' = 2, to give L = 3 (Not allowed), 2, 1;
• If couple l3 with L' = 1, to give L = 2, 1, 0; and
• If couple l3 with L' = 0, to give L = 1. The overall result is
L = (3,) 2, 1, 2, 1, 0, 1 giving (one F,) two D, three P, and one S ter
m
• S = 3/2, 1/2; multiplicity is 2S+1 = 4, 2

191
 np3

• Calculate J as:
1. if less than half of the subshell is occupied, take the minimu
m value J = | L − S | ;
2. if more than half-filled, take the maximum value J = L + S;
3. if the subshell is half-filled, then L will be 0, so J = S.
• Then for half-filled p3, L will be 0, J = S = 5/2, 3/2, 1/2. (number
of microstates are 2J+1)

192
 ML MS
np3

• Second draw all the possibilities:

7
N(1s22s22p3)
• P electrons have mℓ= –1, 0, 1;
ML= 2, 1, 0, –1, –2; L= 2, 1, 0
each p electron mS= 1/2, –1/2;
• Three p electrons can be
MS = 3/2, ½, –½ , –3/2;
S = 1/2, 3/2; and 2S+1 = 4, 2
• J = 5/2, 3/2, 1/2
• Σ(2L+1)(2S+1) = 20;
• So the atomic state term symbol
are 4S3/2 , 2D3/2 , 2D5/2 , 2P1/2 ,2P3/2
• The lowest atomic state is the sm
allest value of J, so it is 4S3/2.  

193
 Table for p3

• 20 Microstates of the p3 configuration

MS
ML -3/2 -1/2 +1/2 +3/2
+2 (1+,1-,0-) (1+,1-,0+)
(1-,0+,0-) (1+,0+,0-)
+1
(1-,1+,–1-) (1+,1+,–1-)
(1+,0-, –1-) (1+,0+, –1-)
+0 (1-,0-, –1-) (1-,0+, –1-) (1-,0+, –1+) (1+,0+, –1+)
(1-,0-, –1+) (1+,0-, –1+)
(0+,0-,-1-) (0+,0-,-1+)
–1
(1-,-1+,–1-) (1+,-1+,–1-)
-2 (0-, –1+,–1-) (0+, –1+,–1-)

194
 np3

• Third: set up a table for total numbers

ML

MS

195
 np3

• Fourth: break down the table to smaller unit cell

ML ML
ML

MS

MS

MS 4
S3/2

P3/2
2 2
P1/2
2
D5/2 D3/2
2

196
 np3

• 若一個特定結構的原子可能存在一個以上的狀態。在對應於
各種譜項狀態的原子能量可以計算出來，通常某些模式已經
可被遵循，讓基態配置的原子的最低能階有可能被識別出
來。
• 在總自旋量子數 S 相同時，總角量子數 L 最大的能量最
低。
• 組態 np3 達半填滿 , 為正常次序 , 相等 2S+1 及相等總角量
子數 L 的條件下 , J 最小的譜支項能量最低 . 因此
• Finally, the order of atomic state term symbols of 7N are :
• 4S3/2 < 2D3/2 < 2D5/2 < 2P1/2 < 2P3/2

197
 f1d1 and d3

• Self-test 8C.5 Repeat the question for the configurations (a) f1d1
and (b) d3

• ANS:
(a) f1d1 : H, G, F, D, P;
(b) d3 : I, 2H, 3G, 4F, 5D, 3P, S

• Throughout our discussion of atomic spectroscopy, distinguish it

alic S, the total spin quantum number, from
roman S, the term label.

198
 f1d1

• ANS:
(a) f1d1 : H, G, F, D, P;
• Coupling two electrons gives a minimum value of |3–2|= 1. Th
erefore, L = 3+2, 3+2–1, ... , 1 = 5, 4, 3, 2, 1
• The overall result is
L = 5, 4, 3, 2, 1 giving one H, one G, one F, one D and one P te
rm
• S=1; multiplicity is 2S+1= 3

199
 nd3

• ANS: (b) d3 : I, 2H, 3G, 4F, 5D, 3P, S

• Coupling two electrons gives a minimum value of |2–2|= 0. Th
erefore, L‘ = (l1 + l2 ),…, | l1– l2 | = (2+2), (2+2–1), ... , |2–2|
= 4, 3, 2, 1, 0
• Now couple l3 =2 with L‘ = 4, to give L = (6,) 5,4,3,2;
• Now couple l3 =2 with L' = 3, to give L = 5,4,3,2,1;
• Now couple l3 =2 with L' = 2, to give L = 4,3,2,1,0;
• Now couple l3 =2 with L' = 1, to give L = 3, 2, 1;
• Now couple l3 =2 with L' = 0, to give L = 2;
• L = (6,) 5, 4, 3, 2, 5, 4, 3, 2, 1, 4, 3, 2, 1, 0, 3, 2, 1, 2 giving (on
e I,) two H, three G, four F, five D, three P, and one S term
• Three mS give S=1/2, 3/2. Multiplicity can be 2S+1 = 2, 4
200
• L = (6,) 5, 4, 3, 2, 5, 4, 3, 2, 1, 5, 4, 3, 2, 1, 0, 3, 2, 1, 2
• S=1/2, 3/2.
• If less than half of the subshell is occupied, take the minimum
value J = | L − S | ; For : I, 2H, 3G, 4F, 5D, 3P, S
• Calculate J as: (number of microstates are 2J+1)
• (I: J = 15/2, 13/2, 11/2, 9/2. and 13/2, 11/2)
• H: J = 13/2, 11/2, 9/2, 7/2. and 11/2, 9/2
• G: J = 11/2, 9/2, 7/2, 5/2. and 9/2, 7/2
• F: J = 9/2, 7/2, 5/2, 3/2. and 7/2, 5/2
• D: J = 7/2, 5/2, 3/2, 1/2. and 5/2, 3/2
• P: J = 5/2, 3/2, ½ and 3/2, 1/2
• S: J = 3/2. and 1/2.

201
202
Case of three equivalent electrons, ℓ3 (wikipedi
a)
• For three equivalent electrons occupying one subshell with the
same orbital quantum number ℓ, there is also a general formul
a (denoted by X(L, S, ℓ) below) to count the number of any all
owed terms with total orbital quantum number L and total spin
quantum number S.

• where the floor function [x] denotes the greatest integer not e
xceeding x.
203
• Example: d3 (ℓ = 2, and S = 3/2, 1/2 )
• For S = 1/2 and L = 1, 0
X(L, S, ℓ) = L – [L/3] = 1, 0, [2P ,2S ]
• For S = 1/2 and L = 5, 4, 3, 2
X(L, S, ℓ) =ℓ – [L/3] = 2, 1, [ 2H , 2G , 2F , 2D ]
• For S = 3/2 and L =1, 0
X(L, S, ℓ) = [L/3] – [(L–ℓ)/2] + [(L–ℓ+1)/2] = 0, [ 4P , 4S ]
• For S = 3/2 and L = 3, 2
X(L, S, ℓ) = [L/3] – [(L–ℓ)/2]] = 1, 0,[4F , 4D ]
4
F3/2 , 4P3/2 , 2H3/2 , 2G3/2 , 2F3/2 , 2D5/2 (2), 2P1/2 ,

204
• 為什麼在自旋 - 軌道耦合常數 Ã 如此強烈依賴原子序數 Z ？
• 因為自旋軌道相互作用是電子自旋與電子軌道運動產生的磁
矩的交互作用。或者，從電子的角度來看，它是電子自旋和
原子核軌道運動之間的交互作用。並且，發現對於不同的原
子，能級的自旋 - 軌道分裂是不同的。在較重的原子即具有
較大核電荷的原子中，自旋 - 軌道交互作用 (s·l) 通常與自旋
- 自旋交互作用 (s·s) 或軌道 - 軌道交互作用 (l·l) 一樣大或更
大。
• 而且對於較重的原子，分裂趨勢是更大。在這種情況下，每
個軌道角動量 l 傾向於與源自相同電子的自旋角動量 s 組
合成相應的單一電子總角動量 j 。然後再以 j 耦合形成總
角動量 J ，使得氫原子中的分裂像 Z4 一樣。這就是為什麼對
於重原子的內電子來說耦合常數 Ã 形成的分裂要大得多。 ht
tps://physics.stackexchange.com/questions/273937/why-is-spin-or
bit-splitting-larger-in-heavier-atoms 205
 spin-orbital coupling( 自旋 - 軌域偶合 )

 There are two system for resolving the total angular momentum i
nto contributions from individual electrons:
 LS coupling (also called Russell-Saunders coupling): The total spin angul
ar momentum and total orbital angular momentum as the vector sum of ea
ch electron,

S = Ʃsi ; L = Ʃℓi ,
then the total angular momentum of atom J is the sum of spin and orbita
l J = L + S.
 j-j coupling: find a total angular moment for each electron first, ji = li + si
then the total angular momentum of atom is the vector sum of each electr
on’s

J = Ʃ ji .
 The j-j coupling model is for heavier atoms where the spin-orbit
coupling is comparable to or greater than the e-e repulsion
206
• 當推算重原子電子譜項時， Russell-Saunders 耦合法失
敗。（因電子的自旋 - 軌道耦合作用很大） 在此情況
下，單個電子 i 的自旋和軌道角動量先以向量耦合到單獨
的 ji 值中 ; 然後將這些 ji 元素組合成一個總數， J 。這
個方法叫做 jj-coupling 。

207
 jj-coupling

• 例如，在原子的電子配置為 p2 時，對每個電子的 j 值各
別是 3/2 和 1/2 。如果個別電子的自旋和軌道角動量強烈
耦合在一起，最好先將每個電子視為角動量為 j = 3/2 或
1/2 的粒子。然後這些個別總角動量耦合如下：

• j1 = 3/2 and j2 = 3/2 then J = 3, 2, 1, 0,

• j1 = 3/2 and j2 = 1/2 then J = 2, 1,

• j1 = 1/2 and j2 = 3/2 then J = 2, 1,

• j1 = 1/2 and j2 = 1/2 then J = 1, 0

208
• 對於重原子較合適的 jj 耦合，最好使用量子數來討論它們
的能量。雖然 jj 耦合應該用於評估重原子的能量，但是從
Russell-Saunders 耦合得到的譜項仍然可以用作標記。
• 原子態的能量隨著自旋 - 軌道耦合強度的增加而變化。
這種相關性展示於 8C.11 圖。

209
210
• 圖 8C.11 表明倆種耦合法 : 低自旋軌道耦合法（ Russell-S
aunders 耦合）和高自旋軌道耦合（ jj - 耦合）法存在對應
關係，因此通過使用 Russell-Saunders 法導出的標籤可用
於標記 jj- 耦合法的狀態。

211
 2) j-j coupling

− Couple individual orbital l and spin s angular momenta first to

the complete electron angular momentum j. (j= ℓ+ s)

− Couple all j to give the total angular momentum J. (J = Σ ji)

− j-j coupling is much more complicated to treat, but should be u

sed for elements heavier than bromine.

• → L and S define the spectroscopic term

212
 np2

– mℓ= -1,0,1; ML=2,1,0,-1,-2; L = 2,1

ms=1/2,-1/2; MS=1,0,-1, S = 0,1; 2S+1 = 1,3
– Σ(2L+1)(2S+1)=3×3+5×1+1×1 = 15; J=2, 1, 0
• 組態 np2 不足半填滿為正常次序 , J 最小的光譜支項能
量最低 . 因此 atomic state term symbol is 3P2, 3P1, 3P0
• The lowest atomic state is the smallest value of J, so it is 3P0
• Finally, all the atomic state term symbols of 6C are :
3
P0 < 3P1 < 3P2 < 1D2 < 1S0

213
• Fifth, applying Hund's rules, deduce which is the ground state
(or the lowest state for the configuration of interest.) Hund's ru
les should not be used to predict the order of states other than t
he lowest for a given configuration. (See examples at Hund's r
ules#Excited states.)

• If only two equivalent electrons are involved, there is an "Eve

n Rule" which states
“For two equivalent electrons the only states that are allowed
are those for which the sum (L + S) is even. “
http://en.wikipedia.org/wiki/Term_symbol

214
• The energy difference between levels can be less than or equal to th
e splitting of states. Therefore, the only configuration we are certai
n of is the ground state. The actual order is give at the far right.
• Miscellaneous Information:
1. It usually is not productive to associative a particular electron conf
iguration with a specific term symbol since there can be considera
ble overlap.
2. Orbitals with L = odd number have odd parity (ungerade). Orbitals
with L = even number have even parity (gerade).
3. Filled, 1/2 filled, or empty orbitals represent orbital singlets.
4. For lighter elements, L and S coupling (Russell – Saunders) is a go
od description.
• Spin–orbit coupling (j – j) can have an effect, for heavy elements.

215
 Selection rules

5. Selection rules for transitions

– Δl = ±1
– ΔS = 0
– Δj = ±1 or 0
– i.e. 3P2 → 3D3 allowed
1
S0 → 3P1 not allowed (spin forbidden)

216
 Molecular Term symbols
• For linear molecules a term has the form:
2S+1
<Λ>±g/u
– where 2S+1 is the multiplicity ( 自旋多重性 )
– g/u is the parity, g × g = g; g × u = u; u × u = g.
– <Λ> is a Greek letter representing the component of the or
bital angular momentum around the internuclear axis.
<Λ>: Σ Π Δ Φ etc
Λ 0 ±1 ±2 ±3 …
– ± is the reflection symmetry only for Σ term under reflectio
n plane that includes the intermolecu;lar axis.

217
A17.5 The coupling of spin and orbital angular momenta in a linear
molecule: only the components along the internuclear axis are
conserved. 218
• The total magnetic quantum number ML
• ML works like Mℓ, except that there is no formula for finding t
he combinations.

• The total spin magnetic quantum number MS

• MS works exactly like Ms. Electrons can either point with or ag
ainst the z‐axis, and being in a molecular orbital versus an ato
mic orbital doesn’t change this. MS can range from
ms1 + ms2 to |ms1 ‐ ms2|

219
 Two new components: parity and reflection

8C.20a The parity of an orbital is e

ven (g) if its wvefunction is unc
hanged under inversion through
the center of symmetry of the m
olecule, but odd (u) if the wavef
unction changes sign. Heteronuc
lear diatomic molecules do not h
ave a center of inversion so for t
hem the g/u classification is irrel
evant.

220
• 8C.20ba The parity of an or
bital is even (g) if its wvefu
nction is unchanged under in
version through the center o
f symmetry of the molecule,
but odd (u) if the wavefuncti
on changes sign.

221
 reflection

9.3 The + or – on a term symbol refers to the overall symmetry of a

configuration under reflection in a plane containing the two nuclei.

222