← Part IV/Hydrogen Atom

5. Hydrogen Atom

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The most important exactly solvable problem in quantum mechanics: explains atomic structure, spectroscopy, and the periodic table.

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Historical Context

1913

Bohr Model

Niels Bohr proposes quantized electron orbits explaining hydrogen spectrum

Significance: First successful quantum model of the atom, predicted Rydberg formula

1926

Schrödinger Solves Hydrogen

Erwin Schrödinger derives exact solution using his wave equation

Significance: Confirmed Bohr's energy levels, revealed true wave nature of electrons

1947

Lamb Shift Discovery

Willis Lamb measures 1057 MHz splitting between 2s and 2p levels

Significance: Led to development of Quantum Electrodynamics (QED)

💡 Understanding the historical development helps contextualize why certain concepts emerged and how they fit into the broader quantum revolution.
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Video Lecture

Hydrogen Atom Solution - MIT OCW

Complete derivation of energy levels and orbitals by Barton Zwiebach

💡 Tip: Watch at 1.25x or 1.5x speed for efficient learning. Use YouTube's subtitle feature if available.

The Coulomb Potential

$$V(r) = -\frac{e^2}{4\pi\epsilon_0 r} = -\frac{ke^2}{r}$$

where $k = 1/(4\pi\epsilon_0) \approx 8.99 \times 10^9$ N·m²/C²

Hydrogen Atom Energy Levels

Coulomb Potential

Legend:

  • Blue curve - Potential energy V(x)
  • Cyan line - Selected energy level
  • Green curve - Wave function ψ(x) at that energy
  • Gray dashed - Other energy levels

Radial Equation

For $u(r) = rR(r)$:

$$-\frac{\hbar^2}{2m}\frac{d^2u}{dr^2} + \left[-\frac{ke^2}{r} + \frac{\hbar^2\ell(\ell+1)}{2mr^2}\right]u = Eu$$

Derivation of Hydrogen Energy Levels

Assumptions:

  • Electron mass m, proton assumed infinitely massive
  • Non-relativistic: v << c
  • Pure Coulomb potential (no QED corrections)
  • Single electron (no electron-electron repulsion)

Starting with:

$$\left[-\frac{\hbar^2}{2m}\nabla^2 - \frac{ke^2}{r}\right]\psi = E\psi$$

Energy Levels

$$E_n = -\frac{me^4}{2(4\pi\epsilon_0)^2\hbar^2}\frac{1}{n^2} = -\frac{13.6\text{ eV}}{n^2}$$

where $n = 1, 2, 3, \ldots$ is the principal quantum number

Key result: Energy depends only on $n$, not on $\ell$ or $m$

Calculating Hydrogen Energy Levels

BASIC

Problem: Calculate the energy required to ionize a hydrogen atom from its ground state (n=1) and from the first excited state (n=2).

Given:

  • Ground state: n = 1
  • First excited state: n = 2
  • Energy formula: E_n = -13.6 eV / n²
  • Ionization means moving electron to E = 0

Find: Ionization energies from n=1 and n=2

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Hydrogen Spectral Lines Calculator

Calculate wavelengths of photons emitted during electron transitions

Formula:

$$\lambda = \frac{hc}{E_\gamma} = \frac{1240 \text{ eV·nm}}{|E_{n_f} - E_{n_i}|}$$

Notes:

  • Lyman series (nf=1): UV wavelengths
  • Balmer series (nf=2): Visible wavelengths (410-656 nm)
  • Paschen series (nf=3): Infrared wavelengths
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Self-Check Question

Why does the hydrogen atom have degeneracy (multiple states with the same energy)?

Bohr Radius

Characteristic atomic size:

$$a_0 = \frac{4\pi\epsilon_0\hbar^2}{me^2} = 0.529 \text{ Å}$$

Ground state has peak probability density at $r = a_0$

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Video Lecture

Quantum Angular Momentum - Stanford

Leonard Susskind explains quantum numbers and angular momentum commutation relations

💡 Tip: Watch at 1.25x or 1.5x speed for efficient learning. Use YouTube's subtitle feature if available.

Quantum Numbers and Degeneracy

For each $n$:

  • $\ell = 0, 1, 2, \ldots, n-1$ ($n$ values)
  • For each $\ell$: $m = -\ell, \ldots, \ell$ ($2\ell + 1$ values)

Degeneracy:

$$g_n = \sum_{\ell=0}^{n-1}(2\ell+1) = n^2$$

Level $n$ has $n^2$ degenerate states (ignoring spin)

Calculating Degeneracy for n=3

BASIC

Problem: How many degenerate states does the n=3 energy level have in hydrogen? List all possible (ℓ, m) combinations.

Given:

  • Principal quantum number: n = 3
  • Allowed values: ℓ = 0, 1, ..., n-1
  • For each ℓ: m = -ℓ, -ℓ+1, ..., +ℓ

Find: Total number of states and all (ℓ, m) pairs

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Self-Check Question

A hydrogen atom is in the n=4 level. How many different states (ignoring spin) have this same energy?

Radial Wave Functions

$$R_{n\ell}(r) = \sqrt{\left(\frac{2}{na_0}\right)^3\frac{(n-\ell-1)!}{2n[(n+\ell)!]}}e^{-r/(na_0)}\left(\frac{2r}{na_0}\right)^\ell L_{n-\ell-1}^{2\ell+1}\left(\frac{2r}{na_0}\right)$$

where $L_q^p$ are associated Laguerre polynomials

First Few States

Ground state ($n=1, \ell=0, m=0$):

$$\psi_{100} = \frac{1}{\sqrt{\pi a_0^3}}e^{-r/a_0}$$

First excited state ($n=2$):

$$\psi_{200} = \frac{1}{4\sqrt{2\pi a_0^3}}\left(2-\frac{r}{a_0}\right)e^{-r/(2a_0)}$$
$$\psi_{21m} = \frac{1}{8\sqrt{\pi a_0^3}}\frac{r}{a_0}e^{-r/(2a_0)}Y_1^m(\theta,\phi)$$

Spectroscopic Notation

States labeled as $n\ell$:

$n$$\ell=0$$\ell=1$$\ell=2$$\ell=3$
11s
22s2p
33s3p3d
44s4p4d4f
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Self-Check Question

What does the spectroscopic notation '3d' represent?

Selection Rules

For electric dipole transitions:

$$\Delta\ell = \pm 1, \quad \Delta m = 0, \pm 1$$

No restriction on $\Delta n$

Radial Probability Distribution

Probability of finding electron between $r$ and $r + dr$:

$$P(r)dr = r^2|R_{n\ell}(r)|^2 dr$$

Factor $r^2$ from spherical volume element

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Video Lecture

Visualizing Spherical Harmonics

eigenchris - Beautiful 3D visualizations of hydrogen orbitals

💡 Tip: Watch at 1.25x or 1.5x speed for efficient learning. Use YouTube's subtitle feature if available.

Fine Structure

Small corrections lift degeneracy:

  • Relativistic correction: $\propto p^4$ term
  • Spin-orbit coupling: $\vec{L} \cdot \vec{S}$ interaction
  • Darwin term: From Dirac equation

Total fine structure splitting $\sim \alpha^2 E_n$ where $\alpha \approx 1/137$

Lamb Shift

QED correction splits $2s_{1/2}$ and $2p_{1/2}$ levels:

$$\Delta E_{\text{Lamb}} \approx 1057 \text{ MHz}$$

Due to vacuum fluctuations

Hydrogen-like Ions

For nuclear charge $Z$ (He⁺, Li²⁺, etc.):

$$E_n = -13.6Z^2/n^2 \text{ eV}$$
$$a = a_0/Z$$
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Real-World Applications of Hydrogen Atom Physics

1. Atomic Spectroscopy

Astronomy & Metrology

The hydrogen spectrum provides precise calibration for astronomical observations and laboratory measurements. The Balmer series lines are visible in stars and galaxies.

Examples:

  • Determining stellar compositions and velocities via Doppler shifts
  • Measuring redshifts of distant galaxies (Hubble expansion)
  • Atomic clocks using hydrogen maser transitions (10⁻¹⁵ accuracy)

2. Quantum Computing & Atomic Physics

Quantum Technology

Hydrogen-like atoms (ions) serve as qubits and test beds for quantum theory. Rydberg atoms with high n provide controllable quantum systems.

Examples:

  • Trapped ion qubits using Mg⁺, Ca⁺, Sr⁺ (hydrogen-like)
  • Rydberg atom quantum simulators
  • Precision tests of QED via Lamb shift measurements

3. Astrophysics & Cosmology

Cosmology

21 cm hyperfine line from ground state hydrogen maps the universe. Recombination era (z~1100) left cosmic microwave background.

Examples:

  • Radio astronomy: mapping galactic hydrogen clouds
  • Probing dark ages (first stars) via 21 cm cosmology
  • Understanding Big Bang nucleosynthesis and recombination

4. Chemistry & Molecular Modeling

Computational Chemistry

Hydrogen atom solutions form basis of quantum chemistry. Orbital shapes determine molecular bonding and reactivity.

Examples:

  • Density Functional Theory (DFT) for molecular simulations
  • Understanding chemical bonds (σ, π) from orbital overlap
  • Predicting molecular spectra and photochemistry

5. Fusion Energy Research

Energy

Understanding hydrogen and deuterium quantum states critical for magnetic and inertial confinement fusion.

Examples:

  • ITER tokamak design (hydrogen isotope plasmas)
  • Diagnostic spectroscopy in fusion reactors
  • Neutral beam injection energy calculations
💡 Understanding real-world applications helps connect abstract quantum concepts to tangible technology and motivates further study.

Summary

Key Equations

$$E_n = -\frac{13.6 \text{ eV}}{n^2}$$
$$a_0 = 0.529 \text{ Å}$$
$$g_n = n^2$$
$$\lambda = \frac{1240 \text{ eV·nm}}{E_{\gamma}}$$

Key Concepts

  • Coulomb potential leads to 1/n² energy scaling
  • Energy depends only on n (accidental degeneracy)
  • Each level has n² degenerate states (ℓ, m)
  • Bohr radius sets atomic size scale
  • Selection rules: Δℓ = ±1, Δm = 0, ±1
  • Fine structure and Lamb shift from QED
  • Basis for all atomic and molecular physics