2304154
Atomic Physics
Montian Tianprateep
Department of Physics
Chulalongkorn University
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Atomic Spectra of Gases: Emission Spectra
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Atomic Spectra of Gases: Absorption Spectra
Emission
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1.
Bohr’s Model
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Bohr’s Model of Hydrogen Atom: Postulates
𝐻 : 1 electron and 1 proton The electron moves in circular orbits around the proton.
Only certain electron orbits are stable. (stationary states)
The atom emits/absorbs radiation (photon) when the
electron makes a transition.
𝐸 − 𝐸 = ℎ𝑓
The electron’s orbital angular momentum is quantized.
𝑚 𝑣𝑟 = 𝑛ℏ; 𝑛 = 1,2,3, ⋯
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Bohr’s Model of Hydrogen Atom: Energy Levels
𝐸 =𝐾+𝑈
For 𝑈: 𝑈 = =−
For 𝐾: 𝐾 = 𝑚 𝑣 = ← = or 𝑣 =
𝑘 𝑒
𝐸=−
2𝑟
From 𝑚 𝑣𝑟 = 𝑛ℏ
𝑛 ℏ
𝑟 = =𝑛 𝑎
𝑚 𝑘 𝑒
𝑘 𝑒 1 13.6 𝑒𝑉
𝑎 : Bohr radius 𝐸 =− =−
2𝑎 𝑛 𝑛
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Bohr’s Model of Hydrogen Atom: Spectrum Line Series
𝐸 − 𝐸 = ℎ𝑓
𝐸 −𝐸 𝑘 𝑒 1 1
𝑓= = −
ℎ 2𝑎 ℎ 𝑛 𝑛
1 𝑓 𝑘 𝑒 1 1 1 1
= = − =𝑅 −
𝜆 𝑐 2𝑎 ℎ𝑐 𝑛 𝑛 𝑛 𝑛
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Bohr’s Model of Hydrogen Like Atom:
𝐻𝑒 , 𝐿𝑖 , 𝐵𝑒
𝑎
𝑟 =𝑛
𝑍
+𝑍𝑒
𝑘 𝑒 𝑍
𝐸 =−
2𝑎 𝑛
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EX42.1: Electronic Transitions in Hydrogen
(A) The electron in a hydrogen atom makes a transition from the 𝑛 = 2 energy
level to the ground level (𝑛 = 1). Find the wavelength and frequency of the emitted
photon.
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EX42.1: Electronic Transitions in Hydrogen
(A) The electron in a hydrogen atom makes a transition from the 𝑛 = 2 energy
level to the ground level (𝑛 = 1). Find the wavelength and frequency of the emitted
photon.
Solution
1 1 1 3𝑅
=𝑅 − =
𝜆 1 2 4
4 4 𝑐 3.00 × 10 𝑚/𝑠
𝜆= = 𝑓= =
3𝑅 3(1.097 × 10 𝑚 ) 𝜆 1.22 × 10 𝑚
= 1.22 × 10 𝑚 = 122 𝑛𝑚 = 2.47 × 10 𝐻𝑧
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EX42.1: Electronic Transitions in Hydrogen
(B) In interstellar space, highly excited hydrogen atoms called Rydberg atoms have
been observed. Find the wavelength to which radio astronomers must tune to
detect signals from electrons dropping from the𝑛 = 273 level to the 𝑛 = 272 level.
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EX42.1: Electronic Transitions in Hydrogen
(B) In interstellar space, highly excited hydrogen atoms called Rydberg atoms have
been observed. Find the wavelength to which radio astronomers must tune to
detect signals from electrons dropping from the𝑛 = 273 level to the 𝑛 = 272 level.
Solution
1 1 1
=𝑅 − = 9.88 × 10 𝑅
𝜆 272 273
1 1
𝜆= =
9.88 × 10 𝑅 9.88 × 10 (1.097 × 10 𝑚 )
= 0.922 𝑚
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EX42.1: Electronic Transitions in Hydrogen
(C) What is the radius of the electron orbit for a Rydberg atom for which 𝑛 = 273?
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EX42.1: Electronic Transitions in Hydrogen
(C) What is the radius of the electron orbit for a Rydberg atom for which 𝑛 = 273?
Solution
𝑟 = 𝑛 𝑎 = 273 (0.0529 𝑛𝑚)
= 3.94 𝜇𝑚
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EX42.1: Electronic Transitions in Hydrogen
(D) How fast is the electron moving in a Rydberg atom for which 𝑛 = 273?
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EX42.1: Electronic Transitions in Hydrogen
(D) How fast is the electron moving in a Rydberg atom for which 𝑛 = 273?
Solution
𝑘 𝑒 (8.99 × 10 𝑁. 𝑚 /𝐶 ) 1.60 × 10 𝐶
𝑣= =
𝑚 𝑟 (9.11 × 10 𝑘𝑔)(3.94 × 10 𝑚)
= 8.01 × 10 𝑚/𝑠
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EX42.1: Electronic Transitions in Hydrogen
What if radiation from the Rydberg atom in part (B) is treated classically? What is
the wavelength of radiation emitted by the atom in the 𝑛 = 273 level?
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EX42.1: Electronic Transitions in Hydrogen
What if radiation from the Rydberg atom in part (B) is treated classically? What is
the wavelength of radiation emitted by the atom in the 𝑛 = 273 level?
Solution
1 𝑣 8.02 × 10 𝑚/𝑠
𝑓= = =
𝑇 2𝜋 𝑟 2𝜋(3.94 × 10 𝑚)
= 3.24 × 10 𝐻𝑧
𝑐 3.00 × 10 𝑚/𝑠
𝜆= =
𝑓 3.24 × 10 𝐻𝑧
= 0.927 𝑚
The wavelength, classically calculated, is slightly difference for higher values of 𝑛.
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2.
Quantum Model
Time-Independent Schrödinger Equation: Hydrogen
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Atom
Spherical polar coordinate (𝑟, 𝜃, 𝜙)
ℏ 𝑑 𝜓 𝑘 𝑒
− + 𝑈𝜓 = 𝐸𝜓 𝑈 𝑟 =−
2𝑚 𝑑𝑥 𝑟
ℏ 𝜕 𝜓 𝜕 𝜓 𝜕 𝜓
− + + + 𝑈𝜓 = 𝐸𝜓
2𝑚 𝜕𝑥 𝜕𝑦 𝜕𝑧
In spherical polar coordinate
𝜓 𝑟, 𝜃, 𝜙 = 𝑅 𝑟 𝑓 𝜃 𝑔(𝜙)
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Time-Independent Schrödinger Equation: Hydrogen
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Atom
𝜓 𝑟, 𝜃, 𝜙 = 𝑅 𝑟 𝑓 𝜃 𝑔(𝜙)
Because of 𝑅(𝑟)
𝑘 𝑒 1 13.6 𝑒𝑉
𝐸 =− =−
2𝑎 𝑛 𝑛
𝑛 = 1,2, ⋯ , ∞: principal quantum number
Because of 𝑓(𝜃)
ℓ = 0,1,2, ⋯ , (𝑛 − 1): orbital quantum number
Because of 𝑔(𝜙)
𝑚ℓ = −ℓ, , ⋯ , ℓ: orbital magnetic quantum
number
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Wave Function for Hydrogen: 1s State
Wave function for 1s state
1 /
𝜓 (𝑟) = 𝑒
𝜋𝑎
Probability of finding the electron in the shell:
𝑃 𝑟 𝑑𝑟 = 𝜓 𝑑𝑉 = 𝜓 4𝜋𝑟 𝑑𝑟
Radial probability density function for 1s state
𝑃 𝑟 = 𝜓 4𝜋𝑟
4𝑟 /
𝑃 𝑟 = 𝑒
𝑎
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EX42.3: The Ground State of Hydrogen
(A) Calculate the most probable value of 𝑟 for an electron in the ground state of
the hydrogen atom.
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EX42.3: The Ground State of Hydrogen
(A) Calculate the most probable value of 𝑟 for an electron in the ground state of
the hydrogen atom.
4𝑟
Solution 𝑃 𝑟 = 𝑒 /
𝑎
𝑑𝑃 𝑑 4𝑟
= 𝑒 / =0
𝑑𝑟 𝑑𝑟 𝑎
/
𝑑 𝑑
𝑒 𝑟 +𝑟 𝑒 / =0
𝑑𝑟 𝑑𝑟 How to
2𝑟𝑒 / + 𝑟 −2/𝑎 𝑒 / =0 define 𝑎 ?
2𝑟 1 − (𝑟/𝑎 ) 𝑒 / =0
1 − 𝑟/𝑎 =0 → 𝑟=𝑎
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EX42.3: The Ground State of Hydrogen
Calculate the probability that the electron in the ground state of hydrogen will be
found from 𝑟 = 0 to 𝑟 = ∞.
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EX42.3: The Ground State of Hydrogen
Calculate the probability that the electron in the ground state of hydrogen will be
found from 𝑟 = 0 to 𝑟 = ∞.
4𝑟
Solution 𝑃 𝑟 = 𝑒 /
𝑎
4𝑟 /
𝑃 𝑟 𝑑𝑟 = 𝑒 𝑑𝑟
𝑎
/
2𝑟 2𝑟
= −𝑒 + +1
𝑎 𝑎
=1
Normalization
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EX42.3: The Ground State of Hydrogen
(B) Calculate the probability that the electron in the ground state of hydrogen will
be found outside the Bohr radius.
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EX42.3: The Ground State of Hydrogen
(B) Calculate the probability that the electron in the ground state of hydrogen will
be found outside the Bohr radius.
4𝑟
Solution 𝑃 𝑟 = 𝑒 /
𝑎
4 2𝑟
𝑃= 𝑃 𝑟 𝑑𝑟 = 𝑟 𝑒 / 𝑑𝑟 𝑧=
𝑎
𝑎
4 𝑧𝑎 𝑎 1
= 𝑒 𝑑𝑧 = 𝑧 𝑒 𝑑𝑧
𝑎 2 2 2
1
=− 𝑧 + 2𝑧 + 2 𝑒
2
= 5𝑒 = 0.677 𝑜𝑟 67.7%
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EX42.3: The Ground State of Hydrogen
Find the average value of r for the electron in the ground state.
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EX42.3: The Ground State of Hydrogen
Find the average value of r for the electron in the ground state.
Solution 4𝑟 /
𝑃 𝑟 = 𝑒
𝑎
4𝑟 /
𝑟 = 𝑟𝑃 𝑟 𝑑𝑟 = 𝑟 𝑒 𝑑𝑟
𝑎
4 /
= 𝑟 𝑒 𝑑𝑟
𝑎
4 3! 3
= = 𝑎
𝑎 2 2
𝑎
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Wave Function for Hydrogen: 2s State
Wave function for 2s state
1 1 𝑟 /
𝜓 (𝑟) = 2− 𝑒
4 2𝜋 𝑎 𝑎
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Wave Function for Hydrogen: Other States
2 𝑛−ℓ−1 ! / ℓ
𝜓 ℓ 𝑟, 𝜃, 𝜙 = 𝑒 𝜌ℓ 𝐿 ℓ 𝜌 ⋅ 𝑌ℓ (𝜃, 𝜙)
𝑛𝑎 2𝑛 𝑛 + ℓ !
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3.
Atomic Quantum
Numbers
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Principal Quantum Number (𝑛)
𝑛 = 1,2,3, ⋯ , ∞
For Hydrogen atom
𝑘 𝑒 1 13.6 𝑒𝑉
𝐸 =− =−
2𝑎 𝑛 𝑛
For Hydrogen like atom (1 electron)
𝑘 𝑒 𝑍 13.6 𝑒𝑉 𝑍
𝐸 =− =−
2𝑎 𝑛 𝑛
For many electrons atom
13.6 𝑒𝑉 𝑍 − 𝑛
𝐸 =−
𝑛
𝑛 : number of electrons in the inner-shell
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Orbital Quantum Number (ℓ): Angular Momentum
Since a particle orbits in circle, its angular momentum becomes important.
Bohr’s Model Quantum Model
The electron’s orbital angular momentum is quantized.
𝐿 = 𝑚 𝑣𝑟 = 𝑛ℏ; 𝑛 = 1,2,3, ⋯ 𝐿= ℓ(ℓ + 1) ℏ
ℓ = 0,1,2, ⋯ , (𝑛 − 1)
𝐿 = 0: Electron cloud is a spherical shape.
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Orbital Magnetic Quantum Number (𝑚ℓ ): Angular
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Momentum in Z-Direction
𝐿 = 𝑚ℓ ℏ
𝑚ℓ = −ℓ, −ℓ + 1, ⋯ , 0, ⋯ , ℓ − 1, ℓ
𝐿 𝑚ℓ
cos 𝜃 = =
𝐿 ℓ ℓ+1
ℓ=2
Zeemann Effect
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Spin Magnetic Quantum Number (𝑚ℓ ):
3 1
𝑆= 𝑠(𝑠 + 1) ℏ = ℏ; 𝑠=
2 2
1
𝑆 =𝑚 ℏ 𝑚 =±
2
𝜇⃑ : Spin magnetic momentum
𝑒 Stern and Gerlach
𝜇⃑ =− 𝑆⃑ Experiment
𝑚
𝑒ℏ
𝜇⃑ , =±
2𝑚
⃑ Spin angular momentum
𝑆:
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EX42.4: Space Quantization for Hydrogen
Consider the hydrogen atom in the ℓ = 3 state. Calculate the magnitude of 𝐿, the
allowed values of 𝐿 , and the corresponding angles 𝜃 that 𝐿 makes with the z axis.
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EX42.4: Space Quantization for Hydrogen
Consider the hydrogen atom in the ℓ = 3 state. Calculate the magnitude of 𝐿, the
allowed values of 𝐿 , and the corresponding angles 𝜃 that 𝐿 makes with the z axis.
Solution
The magnitude of 𝐿 𝐿= ℓ(ℓ + 1) ℏ = 3(3 + 1) ℏ = 2 3 ℏ
The allowed values 𝐿 = −3ℏ, −2ℏ, −ℏ, 0, ℏ, 2ℏ, 3ℏ
of 𝐿
3 2
The corresponding cos 𝜃 = ± = ±0.866 cos 𝜃 = ± = ±0.577
2 3 2 3
angles 𝜃 1 0
cos 𝜃 = ± = ±0.289 cos 𝜃 = ± =0
2 3 2 3
𝜃 = 30.0°, 54.7°, 73.2°, 90.0°, 107°, 125°, 150°
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Pauli’s Exclusion Principle & Hunds Rule
No two electrons in the same atom can have
the same set of quantum numbers.
When an atom has orbitals of equal energy, the
order in which they are filled by electrons is
such that a maximum number of electrons
have unpaired spins.
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Shell 𝑛 1 2
Subshell ℓ 0 0 1
Orbital 𝑚ℓ 0 0 1 0 -1
𝑚𝑠 ↑↓ ↑↓ ↑↓ ↑↓ ↑↓
Shell 𝑛 3
Subshell ℓ 0 1 2
Orbital 𝑚ℓ 0 1 0 -1 2 1 0 -1 -2
𝑚𝑠 ↑↓ ↑↓ ↑↓ ↑↓ ↑↓ ↑↓ ↑↓ ↑↓ ↑↓
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Allowed Electron Transitions
Selection rule: Using Bohr’s model Quantum model
conservation of angular
momentum
Electron has to emit or
absorb photon for
transition.
𝐿 for photon = 1
Δℓ = ±1
and
Δ𝑚ℓ = 0, ±1
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4.
X-Ray Generation
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X-Ray Generator
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X-Ray Spectra
Bremsstrahlung: short wavelength depends on
generating voltage.
Characteristic x-rays: use for describing the
type of material.
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Bremsstrahlung Characteristic X-ray
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Name of Characteristic X-Ray Peaks
Destination energy level
Initial energy level
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Estimating the Energy of an X-Ray
Estimate the energy of the characteristic x-ray emitted from a tungsten target
when an electron drops from an M shell (𝑛 = 3 state) to a vacancy in the K shell
(𝑛 = 1 state). The atomic number for tungsten is 𝑍 = 74.
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Estimating the Energy of an X-Ray
Estimate the energy of the characteristic x-ray emitted from a tungsten target
when an electron drops from an M shell (𝑛 = 3 state) to a vacancy in the K shell
(𝑛 = 1 state). The atomic number for tungsten is 𝑍 = 74.
Solution
13.6 𝑒𝑉 𝑍 − 𝑛
𝐸 =−
𝑛
𝐸 ≈ − 74 13.6 𝑒𝑉 = −7.4 × 10 𝑒𝑉
13.6 𝑒𝑉 74 − 9
𝐸 ≈− ≈ −6.4 × 10 𝑒𝑉
3
ℎ𝑓 = 𝐸 − 𝐸 ≈ −6.4 × 10 𝑒𝑉 − −7.4 × 10 𝑒𝑉 = 68 𝑘𝑒𝑉
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5.
Laser Generation
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Stimulated Absorption
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Types of Emission
Spontaneous emission Stimulated emission
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Lasers
Laser: Light Amplification by Stimulated Emission of Radiation
Coherent light (same phase and
wavelength)
Very narrow range of wavelengths
Small angle of divergence
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Important Factors for Generating Lasers
Stimulated emission
Population inversion
Meta-stable state
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