Atkins / Paula

《 Physical Chemistry, 11th

Edition 》

Chapter 7.
Quantum theory
7E Vibrational motion
 Content
7E Vibrational motion 振動運動
7E.1 The harmonic oscillator 簡諧運動
(a) The energy levels 能階
(b)The wavefunctions 波函數
7E.2 The property of oscillation 振動的性質
(a) Mean values 平均性質
(b)Tunnelling 穿隧性質
 Vibrational Motion 振動運動

 
• 簡諧運動，或稱簡諧振動、諧波、諧振、 SHM(Simple Harmon
ic Motion) ，即是最基本也是最簡單的一種機械振動。如果質
點經歷與其位移成正比的恢復力 , 它就會進行簡諧運動 (harm
onic motion): 當某物體進行簡諧運動時，物體所受的力跟位移
成正比，並且恢復力總是指向平衡位置。
• 依虎克定律 Hooke‘s law F = −kx . 其中 :.
x 為相對平衡點的位移 (displacement from equilibrium position)
F 為恢復力 (restoring force) ，單位為 Newtons (N = kg m s–2).
k 為力常數 (Hooke constant), " 彈簧 " 越硬 (stiff), k 的值就越
大。力常數 k 的單位 k = kg s–2
• 動能與勢能 (kinetic and potential energies) T and have units of N
ewton-meters, E = Fd) or Joules (J = kg m2 s–2).
  ( 𝑥) = 1 𝑘 𝑥2( 𝑡 )
𝑉
2
 Toolkit 18 The Classic Harmonic Oscillator

 
• 對於一維的簡諧振動，其動力學方程式是二階微分方程
式，可由牛頓第二運動定律得

• 回復力又可表示為 , F= –kx, 所以有

• 解上述方程式，得到的的解含有正弦函數 :

• 其中 , 為角頻率 (angular frequency), has units of (kg s–2/

kg)1/2 = s–1.
  
• 一個簡諧運動的質點 m, 其位移隨時間的變化是一個簡諧函
數,

其 ,
• If x = 0 at t = 0, a solution is
• 質點速度是位移對於時間 t 求導數 :

• 加速度是速度對於時間 t 求導數 :

• 最大位移 A; 最大速度 ( 在平衡位置 ); 而最大加速度

( 在最大位移處 )
• 依牛頓第二定律得 , 可得
 諧振子的勢能特性

 
• 而恢復力 F 與勢能 V 有關， 其關係
式為 F = – dV/dx,
• 此式可對應的勢能 V(x) 表示式為

• 這個算式是一個抛物線方程式 ( 見圖 ),
屬
“抛物線勢能” (parabolic potential ener
gy) ，此為諧振子的勢能特性。
 Classical turning points

 
• 可預見到，當粒子遠離平衡位置時，位能增加，同時動能
與速度也在減少。在某一點位移下，諧振子全部能量轉為
位能，即為在古典運動的轉捩點 (V = E 的位置，因此動
能 T 為零 ) 。此時粒子有最大的振幅 (xtp), 稱為轉捩點。
• 因為古典粒子在轉捩點 (turning point) 移動最緩慢，最有可
能在轉捩點附近被發現，而在零位移時最不可能被發現。
因在零位移的地方粒子移動最迅速。古典轉捩點 ( xtp) 出現
在位能 V = E 的位置 :
Trajectories of a harmonic oscillator mechanics

• 根據牛頓經典力學定律 (A+
B) 和量子力學 (C+H) 的 Schr
ödinger 方程 , 諧波振蕩器的
一些軌跡。在 A+B 中 , 粒
子 ( 表示為附著在彈簧上的
球 ) 來回擺動。在 C–H 中 ,
顯示 Schrödinger 方程式的
解 , 其中水平軸表示位置 , 垂
直軸是波函數的實部 ( 藍色 )
或虛部 ( 紅色 ) 。 C,D,E,F 是
能量的。 H 是一種相干涉狀
態 (coherent state), 一種 近似
於經典軌跡的量子狀態。 -
wikipedia
 Example

• Two masses connected by a spring exhibit harmonic motion

Show that equation also applies to mass m1 connected to mass m2 by
a spring as show below

d 2 x1
m1 2  k  x2  x1  o 
dt
d 2 x2
m2 2  k  x2  x1  o 
dt
d 2  x2  x1   1 1 
2
  k    x2  x1  o 
dt  m1 m2 
d 2x
let x   x2  x1  o   2  kx  0
dt
d2 x k k 1 k
  
 
 x   2
x ω 
dt 2
  2π 
10
 Diatomic Molecules and Reduced Masses

• Diatomic molecules are a bit more complicated because each o

f the two atoms moves, having masses m1 and m2.
• Consider atom 1 with mass m1 at position x1, and atom 2 with
mass m2 at position x2, separated by the equilibrium bond lengt
h l0. Then Newton's equations of motion become:
o

d 2 x1
m1 2  k  x2  x1  0   a  and x1 x2
dt
d 2 x2
m2 2   k  x2  x1  0   k  x1  x2  0   b
dt
• Now, let's rethink the definition of displacement for a diatomic
oscillator. Instead of the tedious but precise equation involving
x2 –x1 – l 0 , instead define a relative displacement coordinate
x = x2 – x 1 – l 0 .
• We can now divide equations (a) and (b) above by the masses
m1 and m2, and subtract the re-scaled equations (a) and (b), obt
aining
d 2x 2 d 2x 1 d 2
  2  x 2  x 1
dt 2
dt 2
dt
k k
  x 2  x 1  0    x 2  x 1  0 
m2 m1
 1 1 
 k    x 2  x 1  0 
 m1 m2 
• After staring at this equation for a while, and toying with some
algebra, it will make sense if we now write
1 1 m2  m1 1 m1m2
   or  
m1 m2 m1m2  m1  m2

• Quantity μ is called the reduced mass. Now the classical equat

ion of motion for a diatomic harmonic oscillator can be much
more simply written as
d 2x
 2  kx  0 x"   2 x
dt
• This differential equation has the same sinusoidal solutions as
before, but with the angular frequency ω redefined as  k 
•  Kinetic energy μ = Effective Mass

x F =μa = –kx
• Let
V(x)
• Kinetic energy

• Potential energy

• 總能量 E=T+V 是常數，可表示為 : x

 7E.2 The energy levels 允許的能階

 2
d 2
 1 2
•  粒子的 Schrödinger 方程式是 :
2
 kx   E
2 m dx 2
• 此式是微分方程理論中的一個標準方程 , 其解為數學家所
熟知 。在邊界條件產生了能級的量化 。
• 由于振盪子不能被無限的壓縮或擴展 , 因此唯一允許的解
是在 x = ±∞ 時 Ψ(x)= 0 。而允許的能階是
Example Problem 1

2
  2 ℏ
𝑘𝑥 =
2𝜇
16
  
• 其中角速度 () 隨著力常數的增加和質量的減小而增加。
因此 , 相鄰層之間的能階分離為

• 對所有 v 都是相同的值。因此 , 形成一個均勻的階梯狀

的 , 。能量分離對於宏觀物體 ( 大質量的物體 ) 來說是
微不足道的小 , 但對於質量類似于原子的物體來說卻非常
重要。
  
• 因為量子數 v 的最小允許值是 0, 所以從
• 中可以看出 , 諧波振盪子具有零點能量

• 零點能量的數學原因是 v 不能取負值 , 因為如果這樣做 ,

波函數就會是行為不良 (wavefunction would be ill-behaved)
。
• 物理原因與正方形井中的粒子相同 : 當粒子是被限制時 ,
測不準原理指出在它的位置不能完全確定的時候 , 因此它的
動量與它的動能也不能完全為零。
• 我們可以將這種零點狀態假想為粒子圍繞其平衡位置不斷
波動的狀態 , 而古典力學是允許粒子完全靜止的。
Illustration 8.3 Calculating a molecular vibrational abso
rption frequency
• Atoms vibrate relative to one another in molecules with the bo
nd acting like a spring. Consider an X-H chemical bond, wher
e a heavy X atom forms a stationary anchor for the very light
H atom. That is, only the H atom moves, vibrating as a simple
harmonic oscillator. Therefore, eqn 7E.25 describes the allowe
d vibrational energy levels of a X-H bond. The force constant
of a typical X-H chemical bond is around 500 N m-1.
• For example k = 516.3 N m-1 for the 1H35Cl bond. Because the m
ass of a proton is about 1.7 x 10-27 kg, using k = 500 N m-1 gives
ω = 5.4 × 1014 S-1 (or 5.4 × 102 THz). It follows that the separati
on of adjacent levels is ћω = 5.7 × 10-20 J (57 zJ, about 0.36 e
V). This energy separation corresponds to 34 kJ mol-1, which is
chemically significant. The zero-point energy of this molecular
oscillator is about 3 zJ, which corresponds to 0.2 eV, or IS kJ m
ol-1.
 Illustration: The vibration of a diatomic molecule

•  The effective mass of is

• Which is close to the mass of the proton. The force constant of

the bond is k = 516.3 N m–1. It follows that μ in place of m,

or 563.4 THz. (use 1 N = 1 kg m s –2)

•  The separation of adjacent levels is

• Or 59.41 zJ, about 0.37 eV. This energy separation correspond

s to 36 kJ mol–1, which is chemically significant. The zero-poi
nt energy of this molecular oscillator is 29.71 zJ, which corres
ponds to 0.19 eV, or 18 kJ mol–1.
• The excitation of the vibration of the bond from one level to the
level immediately above requires 57 zJ. Therefore, if it is cause
d by a photon, the excitation requires radiation of frequency ν =
∆E/h = 86 THz and wavelength λ = c/ν = 3.5 μm. It follows that
transitions between adjacent vibrational energy levels of molec
ules are stimulated by or emit infrared radiation. We shall see i
n Chapter 13 that the concepts just described represent the starti
ng point for the interpretation of vibrational spectroscopy, an i
mportant technique for the characterization of small and large
molecules in the gas phase or in condensed phases.
 Self-test

• Suppose
  a hydrogen atom is adsorbed on the surface of a gold
nanoparticle by a bond of force constant k = 855 N m–1. Calcul
ate its zero-point vibrational energy.
ANS:

• Or 37.79 zJ, about 0.24 eV. This energy separation correspond

s to 22.7 kJ mol–1.
• The
  result implies that excitation requires radiation of frequen
cy = 90 THz, and wavelength 3.3 μm.
• It follows that transitions between adjacent vibrational energy
levels of molecules are stimulated by absorbing or emitting inf
rared radiation.
 But molecules are NOT harmonic oscillators!

 
• 如果分子真正表現為諧振子，那麼使原子分離的勢能將上
升到無窮大 , 。那將永遠無法將原子分開，而化學反應也
不會發生。
• 對雙原子分子而言，諧振子模型僅是一個很好的近似，但
只適用於低能量時。
• 更實際的雙原子分子的分子勢能曲線 ( 顯示為實線 ) 。與
諧振子模型的拋物線 ( 顯示為虛線 ) 。
• 此實線是稱為莫爾斯勢能 (Morse potential).

27
1 Solving the Schrodinger Equation for the Quantum Mechanical Harmonic Oscillator

Fig.s1
於二原子分子 , 位能 V(x) 為鍵
長 x 的函數 , 。選擇位能底部
的能量為零。紅色曲線描繪了
一個實際的位能值。黃色曲線
顯示諧波的位能 , 這是井底附近
真實的位能的良好近似值。 Xe
表示平衡鍵結長度。

28
 Taylor series

• 依微積分的泰勒級數定理 (Taylor series theorem) ，對於任

何解析和連續函數，我們可以將任意勢能函數 V(l) 寫為
平衡鍵長度 l0 的冪級數的擴展 (the power series for any ar
bitrary potential energy function V(l) as an expansion about th
e equilibrium bond ) 。

1  dV  1  d 2V 
V    V  0        0    2     0 
2

1!  d  0 2!  d 0
1  d 3V 
    0   ...
3
  3
3!  d  0

29
 • 由於勢能 V 在平衡鍵長時具有最小值 ( 亦即是位於“井底
” ) ，因此，第一階導數項是零。 ( first derivative term is zer
o)
 dV 
 
 d  0
=0

• 如果定義井底為能量的零點，那麼常數項也是零。 因此，
我們可以將勢能 V(ℓ) 寫為從拋物線項開始的冪級數。 (write
the potential energy as a power series beginning with the parabol
ic term. ) 1  dV  1  d 2V 
V    V  0     V(ℓ)
 0 =  2     0 
2

1!  d  0 2!  d 
0

1  d 3V 
    0   ...
3
  3
3!  d  0 30
• 圖中顯示更正確的雙原子分子勢能曲線的形式。
• 對於低能量振動 ( 靠近底部 ) ，拋物線曲線 ( 諧振子 ) 和分
子勢能曲線重疊。對於更高的能量，更準確的表示是扭曲
的拋物線。

31
• 如果諧振子是分子勢能曲
線的完美表示，那麼在沒
有無限能量的情況下，你
永遠不能將原子（或官能
團）拉開。需要紅色勢能
曲線形狀才能發生化學反
應： 藍色曲線的形狀為莫
爾斯勢能曲線 (Morse pote
ntial ) :

V (x) = D [1 – exp(– βx)]2 ,

 (b) The wavefunctions

• 比照盒子中的粒子一樣 , 進行簡諧運動的粒子被困在一個
對稱的井中 , 當粒子有足夠大的位移時獲得勢能上升到較
大的值 ( 並最終可上升到無窮大 ) 。
• 然而其中有兩個重要的區別。首先 , 由於勢能是依 x2 項
隨位移增加到無窮大 , 而不是突然地上升 , 因此在較大的
位移下 , 波函數接近零的速度比在盒中粒子的速度要慢。
其次 , 考慮到勢能的變化 , 振盪子的動能以更複雜的方式
與位移變化相依 , 波函數的曲率也以更複雜的方式進行變
化。
 (b) 波函數的形式

• 諧振子的波函數具有的細緻形式如下 :
Ψ(x) = N × (x 的多項式 ) × ( 鐘形高斯函數 ),
• 其中 N 是歸一化常數。高斯函數是形式為 exp(−x2) 的函
數 。波函數的精確形式是

• 其中因數 Hυ (y) 是稱為 Hermite 多項式

• Hermite polynomial is a specific polynomial in displacement y.
Hυ(y) Hermite polynomial

35
Hυ(y) is a Hermite polynomial, a specific polynomial in
the displacement.

36
 Simple Harmonic Oscillator (6)

If ε is a nonnegative odd integer, one or the other of the series

terminates. In particular for ε=1, 3, 5,…,(2υ+1),..with υ=0,1,2,3,…
respectively, some solutions of the Hermite equation are

ε= 2υ+1 1 3 5 7
H υ( y ) 1 y 1-2 y2 ( y -2 y3)/3

Label normalizable functions H ( y ) by the nonnegative integer υ

(the quantum number ).
H υ( y ) is known as the υ-th Hermite polynomial.
H υ( y ) is an even function of y if υ is even and odd if υ is odd.
even function: f ( y ) = f (- y )
odd function: f ( y ) = -f (- y )
 Simple Harmonic Oscillator (6)

The Hermite polynomials Hυ( y ) are solutions of the differential

equation: d2H  dH 
 2 y  2H   0
dy 2
dy
where υ is a nonnegative integer (the quantum number ). Hυ( y )
is generated by Rodrigue’s formula: d
H  y     1 e
 y2 e  y2 
dy

They satisfy the recursion relation:

Hυ+1( y ) = 2 y Hυ( y ) - 2υHυ-1( y )
Also H’υ( y ) = 2υH υ-1 (y)
An important integral for the orthogonality is

0 if '  
 H He

'
 y2
dy   
2  ! 
12
if '  
38
 Simple Harmonic Oscillator (6)

Q: If the generating function for Hermite polynomials Hυ( y ) are

given by:

H  y 
e 2x y -x   
2
x
 0 !
Find the first 4 hermite polynomials H0( y ), H1( y ), H2( y ), H3( y )

H  y   x2 x3
e 2x y -x 2
 x  H 0  y   H1 y  x  H 2  y   H3 y   ...
 0 ! 2! 3!
The Taylor expansion series for ez = 1 + z + z2/2! + z3/3! +… ;
Now
e 2x y -x  1  2x y- x 2  
2  2x y - x 
2 2

 2x y - x   ...
2 3

2! 3!
 1  2 y  x   2 y  1 x 
2 2
 2 y 3- 6 y  3
x  ...
3!
Comparing the two series, we have
H0( y )=1, H1( y )=2y, H2( y )=4y2-2, H3( y )= 8y3-12y

39
 Simple Harmonic Oscillator (7)

EXAMPLES OF HERMITE POLYNOMIALS AND SHO WAVEFUNCTIONS:

Suggests we substitute  ( y)  H ( y) exp(  y 2 / 2)
H0  y   1   0  y   N 0e  y2 / 2

H1  y   2 y   1  y   N1 2 ye  y2 / 2

H2  y  4 y  22
  2  y   N2  4 y  2 e
2  y2 / 2

H 3  y   8 y  12 y   3  y   N 3  8 y  12 y  e
3 3  y2 / 2

Ψ υ(x ) = Nυ Hυ (α1/2 x) exp (-αx2/2)

N0, N1, N2, … Nυ are normalization constants 1/4
1  
N   1/2  
Hυ(y ) is a polynomial of degree yυ
 2 !   
40
Hermite Polynomial

41
Hermite Polynomial

42
Harmonic Oscillator
Harmonic Oscillator

44
Hermite polynomial

• The normalized wavefunctions f

or the first five states of a harmo
nic oscillator.
• Note that the number of nodes i
s equal to v and that alternate w
avefunctions are symmetrical or
antisymmetrical about y = 0 (zer
o displacement).
 Hermite polynomial

• 例如，因為 H0 (y) = 1 ，波函數為基態 ( 最低能態，用 v =

0) 的諧振子是

• 由此得出概率密度是鐘形高斯函數

• 波函數和概率分佈如圖所示。
• 這兩條曲線在零位移時都有最大的值 ( 在 x = 0), 因此它
們與古典圖像相符 , 顯示粒子由於在其平衡位置的不斷波
動而產生的零點能量。
• 振盪子的第一個激發態 (v = 1 的狀態 ) 的波函數是
• H1(y)= 2y
• 此函數具有零位移 (x = 0) 的節點，並且概率密度在 x = ±
α 處具有最大值 , 對應于 y = ±1 ( 如圖 ) 。應該再次解釋
我們得出的數學表達式。 。 ( 一些 Hermite 多項式是非常
簡單的函數！）：
• 對於方程式中的諧振子波函數，應該注意以下幾點：
1. 隨著位移的增加 ( 在任一個方向 ), 高斯函數非常強烈
地變為零 , 因此所有波函數在較大的位移下都接近零。
2. 指數 y2 與 成正比 , 因此大
質量和剛性彈簧的波函數衰減得更快。
3. 隨著 v 的增加 , Hermite 多項式在較大的位移 (xv) 下
變得更大 , 因此在高斯函數將其降至零之前 , 波函數會
隨 v 變大而變得更分散 :
• 圖中顯示了幾個波函數的形狀。圖中表示概率密度是基於
這些函數的平方。在高量子數下 , 諧振子波函數在古典運
動的轉捩點 (V(x) = E 的位置 , 因此動能為零 ) 附近具有
最大的振幅。
Fig. 7E.7 The probability distributions for the first five states of a harmonic
oscillator and the state with v = 20. Note how the regions of highest
probability (the regions of densest shading) move towards the turning points
of the classical motion as v increases.
50
 Gaussian form

• The wavefunctions for the quantum harmonic oscillator contai

n the Gaussian form which allows them to satisfy the necessar
y boundary conditions at infinity. In the wavefunction associat
ed with a given value of the quantum number υ, the Gaussian i
s multiplied by a polynomial of order υ called a Hermite polyn
omial. The expressions are simplified by making the substituti
on
 Gaussian function

•  The general form of a Gaussian function is

• The graph of this function is a symmetrical bell-shaped curve

centered on x = b; the function has its maximum values of a at
its center. The width of the function, measured at half its heigh
t, is ; the greater σ, the greater is the width at half-height. Also
showed in Graph here is a Gaussian function with b = 0 and =
1:
 • A Gaussian function is a bell-
shaped function of the form

• The graph of the Gaussian

function with f (x) = e–x2.

Fig. 8E.3
Gaussian function
 The Quantum Harmonic Oscillator

• To find the ground state solution of the Schrodinger equation f

or the quantum harmonic oscillator

• A trial solution for the wavefunction in the following form:

• by evaluating the second derivative gives

• Substituting this function into the Schrodinger equation:

• For this to be a solution to the Schrodinger equation for all val
ues of x, the coefficients of each power of x must be equal. Th
at gives us a method for fitting the boundary conditions in the
differential equation.
Example Problem 2

57
58
59
60
61
 7E.3 Quantum Harmonic Oscillator
2
p̂ x kx̂ 2
Ĥ  
2μ 2
 d
p̂x 
i dx
The Time-independent Schrödinger equation for the energy eigenstates of the SHO
is:
 d   x    x̂   x 
2 2 2 2
   E  x 
2  dx 2
2
Problem: still a linear differential equation but coefficients are not constants.

Simplify: replaced x to a new variable y,

 Simple Harmonic Oscillator (1)

The Schrödinger equation for the energy eigenstates of the SHO is:
 2 d 2  x  1 2
  kx   x   E  x 
2  dx 2
2
  2 d2 ω2  2 
 replace x  y     2  d y 2  2  y   E
 
 d 2
k 2  2 E
multiply by (2μ / β ℏ )   dy 2   2  2 y     2 
2

 
12
k  1 2
choose constant β as   2  or 2 
    k
2 E 2 E 2      
define    E  E    
  2
 k  k  2 k 2 
 d2 2
  d y 2  y   
  63
 Simple Harmonic Oscillator (2)

• Alternatively, replace x = α y, and dx = α dy

 2 d2 1 2 2
 2  2 d y 2  2 k y   E  replace x   y 
 
 d2 k  4 2 2  2 E

 d y2  2
y   2
 multiply by (2 μ α2 / ħ2)
 
1 4
 
2 2 14
  
2
    ω
k
Let       2   

  k   k  k
k
14
k and let 2  2
E 
y  x 2   x 2
  , then E  
  2
  
 d2 2
 d y 2  y   
 
 Simple Harmonic Oscillator (2)

• By choosing the dimensionless independent variable y as :

14
x k k
y   x 2  x
    
2 d 2  d 2
T̂   
2  dy
2 2
2 dy 2
1 2  2  2
V̂  k x  x  y
2 2 2
2
  
E  
2 k 2
 Figure 8.6

• (a) Potential energy curve for a classical harmonic oscillator.

(b) Allowed energy levels and wavefunctions for a quantum mechanic
al harmonic oscillator.
(c) Probability density functions as a quantum mechanical harmonic o
scillator.
8.4 The energy levels
(a) The form of the wavefunctions
Fig.7E.4
Fig.7E.5
Comment 8.2
This function has a node at zero displacement (x = 0), and the probabil
ity density has maxima at x = ±a, corresponding to y = ±l (Fig. 8.24).
Once again, we should interpret the mathematical expressions we have
derived. In the case of the harmonic oscillator wavefunctions in eqn 8.
28, we should note the following:
1. The Gaussian function goes very strongly to zero as the displaceme
nt increases (in either direction), so all the wavefunctions approach zer
o at large displacements.
2. The exponent y2 is proportional to x2 × (mk)l/2, so the avefunctions d
ecay more rapidly for large masses and stiff springs.
3. As v increases, the Hermite polynomials become larger at large disp
lacements, so the wavefunctions grow large before the Gaussian functi
on damps them down to zero: as a result, the wavefunctions spread ov
er a wider range as v increases.
• The shapes of several wavefunctions are shown in Fig. 8.25. The sh
ading in Fig. 8.26 that represents the probability density is based on
the squares of these functions. At high quantum numbers, harmonic
oscillator wavefunctions have their largest amplitudes near the turni
ng points of the classical motion (the locations at the kinetic energy
is zero). We see classical properties emerging in the correspondence
limit of high quantum numbers, for a classical particle is most likely
to be found at the turning points (where it travels most slowly) and i
s least likely to be found at zero displacement (where it travels most
rapidly).which V = E, so the kinetic energy is zero). We see classica
l properties emerging in the correspondence limit of high quantum n
umbers, for a classical particle is most likely to be found at the turni
ng points (where it travels most slowly) and is least likely to be fou
nd at zero displacement (where it travels most rapidly).
The normalized
wavefunctions for
the first five states
of a harmonic
oscillator. Note that
the number of
nodes is equal to v
and that alternate
wavefunctions are
symmetrical or
antisymmetrical
about y = 0 (zero
displacement).

75
• Fig. 7E.6
• The first few eigenfunctio
ns of the quantum mechan
ical harmonic oscillator ar
e plotted together with the
potential function. The am
plitude of the eigenfunctio
ns is shown superimposed
on the energy level.
Topic 7E Vibrational Motion 77
 Simple Harmonic Oscillator (5) Wavefunctions

High n state (n =30)

• Decaying wavefunction tunnels into classically forbidden region

• Spatial average for high energy wavefunction gives classical result:
another example of the CORRESPONDENCE PRINCIPLE
78
 Example 7E.3

• Example 8.3 Normalizing a harmonic oscillator wavefunction

• Find the normalization constant for the harmonic oscillator wavefun
ctions.
Method Normalization is always carried out by evaluating the integral
of |Ψ|2 over all space and then finding the normalization factor from
equation. The normalized wavefunction is then equal to N Ψ. In this
one-dimensional problem, the volume element is dx and the integrat
ion is from –∞ to +∞. The wavefunctions are expressed in terms of t
he dimensionless variable y = x / α, so begin by expressing the integ
ral in terms of y by using dx = α dy.
Example 8.3 Answer
 (b) The properties of oscillators

With the wavefunctions that are available, we can start calculating the
properties of a harmonic oscillator. For instance, we can calculate the
expectation values of an observable Q by evaluating integrals of the
type

(Here and henceforth, the wavefunctions are all taken to be normalized

to 1.) When the explicit wavefunctions are substituted, the integrals
look fearsome, but the Hermite polynomials have many simplifying
features. For instance, we show in the following example that the mean
displacement, <x>, and the mean square displacement,
<x2>, of the oscillator when it is in the state with quantum number ν
are
Example 8.4
Example 8.4 Ans
Self-test 8.7
Virial theorem
 Comment 8.3

An even function is one for which f(-x) =f(x); an odd function

is one for which f(-x) = –f(x). The product of an odd and even
function is itself odd, and the integral of an odd function over
a symmetrical range about x = 0 is zero.
 the correspondence principle
• An oscillator may be found at extensions with V > E that are forbidden by cl
assical physics, for they correspond to negative kinetic energy. For example,
it follows from the shape of the wavefunction (see the Justification below) th
at in its lowest energy state there is about an 8 per cent chance of finding an
oscillator stretched beyond its classical limit and an 8 per cent chance of find
ing it with a classically forbidden compression. These tunneling probabilities
are independent of the force constant and mass of the oscillator. The probabil
ity of being found in classically forbidden regions decreases quickly with inc
reasing ν, and vanishes entirely as ν approaches infinity, as we would expect
from the correspondence principle. Macroscopic oscillators (such as pendulu
ms) are in states with very high quantum numbers, so the probability that the
y will be found in a classically forbidden region is wholly negligible. Molec
ules, however, are normally in their vibrational ground states, and for them t
he probability is very significant.
 Summary of Harmonic Oscillator

1. The quantum SHO has discrete energy levels because of the

normalization requirement. E    1   ω   0,1,2,3. ..
   o
 2
2. There is ‘zero-point’ energy because of the uncertainty principle.
1
E o   ωo
2
3. Eigenstates are Hermite polynomials times a Gaussian.
 ( y )  H ( y ) exp(  y 2 / 2)
4. Eigenstates have definite parity because V (x) = V (-x). They can
tunnel into the classically forbidden region.
5. For large n (high energy) the quantum probability distribution
tends to the classical result. Example of the correspondence
principle.
6. Applies to any SHO, eg: molecular vibrations, vibrations in a solid
(phonons), electromagnetic field modes (photons), etc
90
 Summary of Harmonic Oscillator

• 值得注意的是在古典力學之簡諧振動能量大小是由振幅 Ao
決定 , ( 可為任意值 ), 而量子力學的能量是基頻 ωo 的半
整數倍數 , 是不連續的 E,    1   ω   0,1,2,3. ..
 o
 2
• 在波函數古典轉折點 (turning point) 處
ytp = (2υ+1) ½
機率並不為零，也就是說系統有可能存在於位能大於總能
量的區域 (Classical Forbidden Region) ，此現象稱為穿隧
效應 (tunneling effect) ，穿隧效應在許多物理及化學現象
中扮演著重要的角色 (STM, AFM) 。

91
Classical turning point ( 古典返轉點 ), xtp
error function, erf
• A
  standard normal distribution with mean μ and deviation σ, th
e probability density function (PDF) is

• These integrals cannot be expressed in terms of elementary fun

ctions, and are often said to be special functions.
• The error function: erf(x) gives the probability of normal distrib
ution of a random variable with mean μ = 0 and variance σ = 1/
2 falling in the range [–x, x].

• The cumulative distribution function (CDF) of erf(x) is :

 error function, erf

• For
  a generic normal distribution with as pdf, mean μ and deviati
on σ, the cumulative distribution function is

• The probability that a normal distribution lies in the range betwee

n (μ − nσ) and (μ + nσ) is given by
Table. 8.22