1

A) Matching the term with the related equation: 13%

𝜕
1) Planck equation for energy density in blackbody radiation, ρν a) 𝑖ℏ
𝜕𝑡

2) ̂ (𝑥, 𝑡)
Hamiltonan operator for time-dependent system, 𝐻 b) 2
x2  x

8 h  c 3
3) Standard deviation of observable x,  x c)
e h kT  1
h 2  n 2X nY2 n Z2 
4) Operator of momentum in x, p̂ x d)    
8m  a 2 b 2 c 2 

5) Hermitian property of operator  e)  i 
x
6) Angular frequency of simple harmonic motion, ω f) ∫ f* Â g = ∫ g* Â* f
2𝜋𝑐
7) Energy levels for particle in 3-dimensional cube g)
𝜆
8) length of wavevector, |k| = k h) Ek = hν – Φ
h
9) Normalization constant N in function Ψ = Nf (x) j) Δx Δp x 
4
10) Heisenberg uncertainty principle: k) 𝑁 = (∫ 𝑓(𝑥)∗ 𝑓(𝑥) 𝑑𝑥)−1⁄2
∞
11) Einstein Photoelectric effect ̂ 𝛹𝑑𝑥
m) Ω = ∫−∞ 𝛹 ∗ Ω

12) Wien’s displacement law : n) 2πν/c

ℎ𝑐
̂ o) λmaxT =
13) Expectation value of quantity represented by operator Ω
5𝑘

ANS: c a b e f(z) g d n k j h o m z) none of above

B) Theoretical Problems 42%

1. Functions of the form sin(nπx/L), where n = 1, 2, 3 ... , are wavefunctions in a region of length L
(between x = 0 and x = L). Show that the wavefunctions with n = 1 and 2 are orthogonal.
ANS: E7C.9(a)

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𝐿 𝜋
𝜋𝑥 2𝜋𝑥 𝐿 𝜋 𝜋
∫ 𝑠𝑖𝑛 ( ) 𝑠𝑖𝑛 ( ) 𝑑𝑥 = ( ) ∫ 𝑠𝑖𝑛(𝑦)𝑠𝑖𝑛(2𝑦)𝑑𝑦 𝑙𝑒𝑡 𝑦 = 𝑥 𝑑𝑦 = 𝑑𝑥
0 𝐿 𝐿 𝜋 0 𝐿 𝐿
𝐿 𝜋 cos 𝑦−cos 3𝑦 𝐿 𝜋 𝜋 𝐿 sin 3𝑦 𝜋
= ( ) ∫0 𝑑𝑦 = ( ) [∫0 cos 𝑦 𝑑𝑦 − ∫0 cos 3𝑦 𝑑𝑦] = ( ) [sin 𝑦 − ]
𝜋 2 2𝜋 2𝜋 3 0

𝐿 sin 3𝜋 1
= (sin 𝜋 − − sin 0 + sin0) = 0
2𝜋 3 3

2 1⁄2 2π𝑥
2. An electron in a region of length L is described by the normalized wavefunction 𝛹(𝑥) = ( ) sin ( )
𝐿 𝐿

in the range x = 0 to x = L; outside this range the wavefunction is zero. Evaluate <x>.
𝑳 𝑳 𝟐 𝟐𝝅𝒙 𝟐 𝟐𝝅𝒙
ANS: E7C.2(a) 〈𝒙〉 = ∫𝟎 𝚿(𝒙)∗ ∙ 𝐱 ∙ 𝚿(𝒙) 𝒅𝒙 = ∫𝟎 √ 𝐬𝐢𝐧 ( ) ∙ 𝒙 ∙ √ 𝐬𝐢𝐧 ( ) 𝒅𝒙
𝑳 𝑳 𝑳 𝑳

𝟐 𝐿 2𝜋𝑥
= ( ) ∫ 𝑥 ∙ 𝑠𝑖𝑛2 ( ) 𝑑𝑥
𝑳 0 𝐿
𝑳
𝟒𝝅𝒙 𝟒𝝅𝒙
𝟐 𝒙 𝟐 𝒙 𝐬𝐢𝐧 ( ) 𝐜𝐨𝐬 ( ) 𝟐 𝑳𝟐 𝑳𝟐 𝑳𝟐 𝐿
= ( )[ − 𝑳 − 𝑳 ] = ( )[ − + ]=
𝑳 𝟒 𝟐𝝅 𝟐𝝅 𝟐 𝑳 𝟒 𝟑𝟐𝝅 𝟐 𝟑𝟐𝝅 𝟐 2
𝟒( ) 𝟖 ( )
𝑳 𝑳 𝟎

3. Normalize (to 1) the wavefunclion e–ax in the range 0 ≤ x ≤ ∞, with a > 0.

∞ ∞
ANS: E7B.4(a) 𝟏 = ∫𝟎 (𝑵𝒆−𝒂𝒙 ) (𝑵𝒆−𝒂𝒙 )𝒅𝒙 = 𝑵𝟐 ∫𝟎 𝒆−𝟐𝒂𝒙 𝒅𝒙 =

𝑵𝟐 ∞ 𝒅𝒖
∫ 𝒆−𝒖 𝒅𝒖
𝟐𝒂 𝟎
𝒍𝒆𝒕 𝒖 = 𝟐𝒂𝒙 𝒅𝒙 =
𝟐𝒂

𝑵𝟐 −𝒖 ∞
𝑵𝟐 𝑵𝟐 −𝒂𝒙
𝟏= [−𝒆 ]𝟎 = (𝟎 − (−𝟏)) = 𝑵 = √𝟐𝒂 , 𝐚𝐧𝐝 𝚿(𝒙) = √𝟐𝒂𝒆
𝟐𝒂 𝟐𝒂 𝟐𝒂

4. For a particle in a box of length L and in the state with n = 3, at what positions is the probability density
a maximum? At what positions are the probability density zero?
2 1⁄2 3π𝑥 3𝜋𝑥
ANS: E7D.15(a) 𝛹3 (𝑥) = ( ) sin ( ) and P(𝑥) ∝ 𝛹3 (𝑥)2 ∝ 𝑠𝑖𝑛2 ( )
𝐿 𝐿 𝐿

The maxima and minima in P (x) correspond to , or

∂ 3𝜋𝑥 3𝜋𝑥 3𝜋𝑥 3𝜋 3𝜋 3𝜋𝑥 3𝜋𝑥 3𝜋 6𝜋𝑥

[𝑠𝑖𝑛2 ( )] = 2 sin ( ) 𝑐𝑜𝑠 ( ) ( ) = ( ) 2sin ( ) 𝑐𝑜𝑠 ( ) = ( ) sin ( )=0
∂x 𝐿 𝐿 𝐿 𝐿 𝐿 𝐿 𝐿 𝐿 𝐿
6𝜋𝑥 𝐿
So = 𝑛𝜋. Since 𝐿 ≠ 0 and 𝑥 = 𝑛 (6) , 𝑛 ∈ 𝑝𝑜𝑠𝑖𝑡𝑖𝑣𝑒 𝑖𝑛𝑡𝑒𝑔𝑒𝑟
𝐿
Maxima at x = L/6, 3L/6, 5L/6, amd Minima (or zero probability density) at x = L/3, 2L/3 besides 0, L

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5. Imagine a particle confined to move on the circumference of a circle ('a particle on a ring'), Such that its
position can be described by an angle 𝜙 in the range 0 ~ 2 π. The wavefunctions for this system are of

the form Ψ(𝜙) = e–imIϕ with mI an integer. Show that the wavefunctions with mI =+1 and +2 are

orthogonal.
(Hint: Note that (eix)* = e–ix, and that eix = cos x + i sin x.)
𝝅 ∗
ANS: E7C.1(a) [不計分] The functions are orthogonal if ∫𝟎 𝝍𝒎 (𝒙)∗ 𝝍𝒏 (𝒙)𝒅𝒙 = 𝟎 𝐒𝐢𝐧𝐜𝐞 (𝐞−𝐢𝐱 ) =

(𝐞+𝐢𝐱 ), 𝐚𝐧𝐝 𝐭𝐡𝐚𝐭 (𝐞−𝐢𝐱 ) = 𝐜𝐨𝐬 𝒙 − 𝒊 𝐬𝐢𝐧 𝒙.

𝟐𝝅 𝟐𝝅 𝟐𝝅
+𝒊𝝓 −𝒊𝟐𝝓 −𝒊𝝓
∫ (𝒆 ) (𝒆 )𝒅𝒙 = ∫ (𝒆 ) 𝒅𝒙 = ∫ (𝒄𝒐𝒔 𝝓 − 𝒊 𝐬𝐢𝐧 𝝓) 𝒅𝒙 = 𝟎
𝟎 𝟎 𝟎

6. Identify which of the following functions are eigenfunctions of the operator d2/dx2: (i) cos(kx), (ii)e𝑖𝑘𝑥,
(iii) kx, (iv) e−𝑎𝑥2.Give the corresponding eigenvalue where appropriate.
d2
ANS: (i) cos 𝑘𝑥 = –k2 cos kx an eigenfunction with an eigenvalue of (–k2)
d𝑥 2

d2
(ii) 𝑒 𝑖𝑘𝑥 = (𝑖𝑘)2 𝑒 𝑖𝑘𝑥 an eigenfunction with an eigenvalue of (–k2)
d𝑥 2

d2
(iii) 𝑘𝑥 = 0 = (0)𝑘𝑥 an eigenfunction with an eigenvalue of (0)
d𝑥 2

d2 2 2 2 2 2
(iv) e−𝑎𝑥 = 4𝑎2 𝑥 2 e−𝑎𝑥 − 2𝑎e−𝑎𝑥 = e−𝑎𝑥 (4𝑎2 𝑥 2 − 2𝑎) = 2𝑎(2𝑎𝑥 2 − 1)e−𝑎𝑥
d𝑥 2

Not an eigenfunction

C) Numerical Problems 45% ( )

1. Calculate the size of the quantum involved in the excitation of (a) an electronic oscillation of period 1.0
fs, (b) a molecular vibration of period 10 fs, (c) a pendulum of period 1.0 s. Express the results in joules
and kilojoules per mole.

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ANS: E7A.9(a)
E = hν = h /T, so (T = period = 1/ν) and ΔEm = NAΔE
(a) E = 6.626 × 10−34 J s / (1.0 × 10−15 s) = 6.626 × 10−19 J = 3.99 kJ mol−1
(b) E = 6.626 × 10−34 J s / (10 × 10−15 s) = 6.626 × 10−20 J = 39.9 kJ mol−1
(c) E = 6.626 × 10−34 J s / (1.0 s) = 6.626 × 10−34 J = 3.99 × 10−13 kJ mol−1

2. An electron is confined to a linear region with a length of the same order as the diameter of an atom
(about 100 pm). Calculate the minimum uncertainties in its position and speed.
ANS: E7C.5(b)

3. The intensity of the radiation from an object is found to be a maximum at 2000 cm–1. Assuming that the
object is a black body, calculate its temperature.
ANS: E7A.7(a)
According to Wien’s law : λmax T = hc / 5k = 2.88 × 10−3 m K
T = hc / (5k λmax) = (hc / 5k) ν̅𝑚𝑎𝑥 = (2.88 ×10−3 m K) × 2000 ×102 m−1 = 576 K

4. The work function for metallic rubidium is 2.09 eV. Calculate the kinetic energy and the speed of the
electrons ejected by light of wavelength 195 nm.
ANS: E7A.13(b)

Conservation of energy requires Ephoton = Φ + EK = hν = hc/λ, .so EK = hc / λ − Φ and

(ii) EK =

− (2.09 eV) × (1.60 × 10−19 J eV–1) = 6.84 × 10−19 J

and ν = (2(3.20 × 10−19 J / 9.11 × 10−31 kg)1/2 = 1.23 × 106 m s−1

2 1⁄2 2π𝑥
5. For an electron in a region of length L, the system described by wavefuntion 𝛹(𝑥) = ( ) sin ( ),
𝐿 𝐿

what is the probability of finding the electron between x = L/4 and x = L/2?
ANS: E7B.7(a)

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6. For an electron in a region of length L, the system described by 1-D wavefunction 𝜓𝑛 (𝑥 ) =

𝑛𝜋𝑥
𝐴 sin , the expectation value of total energy <E> can be derived from <E> =
𝑎

𝑎
∫0 𝜓𝑛 (𝑥 ) Ĥ 𝜓𝑛 (𝑥 ) d𝑥 . with

ℏ2 𝑑 2 (𝑛𝜋ℏ)2
Ĥ=− . Show that <E> = . What is the energy <E> at ground state for L =
2𝑚 𝑑𝑥 2 2𝑚𝑎2
100 pm?
ANS: HW1.6
𝑎 𝑎 2 1/2 𝜋𝑥 ℏ2 𝑑 2 2 1/2 𝜋𝑥
(a) 〈𝐸̂ 〉 = ∫0 𝜓𝑛 (𝑥) Ĥ 𝜓𝑛 (𝑥) d𝑥 = ∫0 ( ) sin (− ) () sin d𝑥
𝑎 𝐿 2𝑚 𝑑𝑥 2 𝑎 𝑎

ℏ2 𝑛𝜋 2
2
2 𝑎 𝑛𝜋𝑥 𝑑 𝑛𝜋𝑥 2 ℏ2 𝑎 𝑛𝜋𝑥 𝑛𝜋𝑥
= ( ) (− ) ∫0 𝑠𝑖𝑛 ( 2) 𝑠𝑖𝑛 d𝑥 = − ( ) ( ) (− ) ∫0 𝑠𝑖𝑛 𝑠𝑖𝑛 d𝑥
𝑎 2𝑚 𝑎 𝑑𝑥 𝑎 𝑎 𝑎 2𝑚 𝑎 𝑎

𝑛𝜋
2𝑛2 𝜋 2 ℏ2 𝑎 𝑛𝜋𝑥 𝑎 𝑎
=( 3 ) ( ) ∫ 𝑠𝑖𝑛2 𝑦𝑑𝑦 𝑤𝑖𝑡ℎ = 𝑦, 𝑥 = 𝑦, 𝑑𝑥 = ( ) 𝑑𝑦
2𝑚𝑎 𝑛𝜋 𝑎 𝑛𝜋 𝑛𝜋
0
𝑛𝜋
𝑛𝜋ℏ2 𝑦 𝑠𝑖𝑛(2𝑦) 𝑛𝜋ℏ2 𝑛𝜋 (𝑛𝜋ℏ)2
=( )[ − ] = ( )=
𝑚𝑎2 2 4 0
𝑚𝑎2 2 2𝑚𝑎2
(b) For ground state, n =1 , given that L = a = 100 pm

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2
(𝑛𝜋ℏ)2 1 𝑛ℎ 2 1 6.626×10−34 𝐽 𝑠
<E> = = ( ) = ( )
2𝑚𝑎2 8𝑚 𝑎 8(9.109×10−31 𝑘𝑔) 100×10−12 𝑚
−18
= 6.03 × 10 𝐽 𝑜𝑟 37.6 𝑒𝑉

n
Integral
0 1 2 3 4 5
 1/2 1/2 1/2
1   1 1   1 3   1
x n
exp -ax 2  dx      
0 2 a  2a 4  a3  2a2 8  a5  a2

exp -ax 2  dx
1/2 1/2 1/2
x n
 
  0
1  
  0
3  
  0
-
a 2  a3  4  a5 

x sin( 2a x ) x2 x sin2a x  cos 2a x 

 sin2 a x dx  2

4a
C  x sin2 a x dx  4

4a

8 a2
x3 x 2 sin2a x  sin2a x  x cos 2a x 
 x 2 sin2 a x dx  6

4a

8 a3

4 a2
sinn  m x sinn  m x
 sin(mx ) sin(nx )dx  2n  m 

2 n  m 
; m n

  2 if m  n a  mx   nx  a
dx  mn
0 sinmx  sinnx  dt  0 m  n  sin
0
 sin
a   a 

2
  2 if m  n a  mx   nx  a
0 cos mx cos nx  dt  0 m  n 0 cos  a  cos  a dx  2 mn
0 if m  0

 
if m  n m  n odd  nx   nx 
0 sinmx cos nx  dt  0
a
 sin  cos  dx  0
2m 0 a   a 

 m2  n2  if m  n m  n even