Chapter 6: Electronic Structure of Atoms
Chemistry: The Central Science · 15th Global Edition · Brown et al.
■ Chapter Overview
This chapter explains how electrons are arranged in atoms using quantum theory. It begins with the nature of
light, then develops the quantum-mechanical model of the atom, and concludes with electron configurations and
their relationship to the periodic table.
Section Topic
6.1 The Wave Nature of Light
6.2 Quantized Energy and Photons
6.3 Line Spectra and the Bohr Model
6.4 The Wave Behavior of Matter
6.5 Quantum Mechanics and Atomic Orbitals
6.6 Representations of Orbitals
6.7 Many-Electron Atoms
6.8 Electron Configurations
6.9 Electron Configurations and the Periodic Table
6.1 The Wave Nature of Light
Electromagnetic radiation (radiant energy) includes visible light, X-rays, microwaves, and radio waves — all
travel at c = 2.998 × 108 m/s in a vacuum.
Key Wave Properties
• Wavelength (λ) — distance between two adjacent peaks (or troughs); units: nm, Å, µm etc.
• Frequency (ν) — number of complete cycles passing a point per second; unit: s−1 (Hz).
• Amplitude — height of the wave peak (related to intensity/brightness).
Core Equation: λν = c
Longer λ → lower ν | Shorter λ → higher ν (inverse relationship)
Electromagnetic Spectrum (shortest → longest λ)
Gamma rays Highest energy; wavelengths ~ size of atomic nuclei
X-rays λ ~ 0.1–10 nm; used in medical imaging
Ultraviolet (UV) λ ~ 10–400 nm; causes sunburn
Visible light λ ~ 400–750 nm (violet → red)
Infrared (IR) λ ~ 750 nm–1 mm; felt as heat
Microwaves λ ~ 1 mm–1 cm; used in ovens & radar
Radio waves λ > 1 cm; longest, lowest energy
✎ All EM radiation travels at the same speed c regardless of wavelength.
6.2 Quantized Energy and Photons
Blackbody Radiation — Planck's Quantum Theory (1900)
• Heated solids emit radiation; colour depends on temperature (hotter = shorter λ).
• Classical physics failed to explain this — led to quantum theory.
• Max Planck proposed: atoms can emit/absorb energy only in discrete chunks called quanta.
E = hν (energy of one quantum)
h = Planck's constant = 6.626 × 10−34 J·s
Energy is quantized: only whole-number multiples of hν are allowed (hν, 2hν, 3hν …)
Photoelectric Effect — Einstein's Photon Theory (1905)
• Light striking a clean metal surface can eject electrons — but ONLY if frequency ≥ a minimum threshold.
• Increasing intensity (brightness) does NOT help if ν is below threshold — only more photons, not higher
energy ones.
• Einstein extended Planck's idea: light behaves as a stream of photons, each carrying energy E = hν.
• Work function: minimum energy needed for an electron to escape the metal surface.
• Einstein won the 1921 Nobel Prize in Physics for this explanation.
Ephoton = hν = hc/λ
Higher frequency (shorter λ) = more energetic photons = more likely to eject electrons.
Wave–Particle Duality of Light
• Light shows wave behaviour (interference, diffraction) AND particle behaviour (photoelectric effect).
• The appropriate model depends on the experiment being performed.
6.3 Line Spectra and the Bohr Model
Spectra — Two Types
Continuous spectrum All wavelengths present (e.g. white light through a prism → rainbow)
Line spectrum Only specific wavelengths present (e.g. H, Ne discharge tubes)
Line spectra puzzled scientists — each element produces a unique set of lines → like a fingerprint.
Rydberg Equation (describes H atom lines)
1/λ = RH(1/n12 − 1/n22)
RH = 1.097 × 107 m−1 (Rydberg constant); n1 and n2 are positive integers, n2 > n1
Bohr's Model of the Hydrogen Atom (1913)
• Electrons move in fixed circular orbits around the nucleus at specific allowed radii.
• Electrons in an allowed orbit do NOT radiate energy → atoms are stable.
• Energy is emitted or absorbed ONLY when an electron jumps between allowed orbits (as a photon).
En = −2.18 × 10−18 J × (1/n2)
n = 1, 2, 3, … (principal quantum number)
n = 1: ground state (lowest energy, most stable) | n > 1: excited states
n = ∞: electron completely separated (E = 0, reference state)
Emission vs Absorption
∆E < 0 (nf < ni) Electron falls to lower level → photon EMITTED (∆E = hν = −∆E)
∆E > 0 (nf > ni) Electron jumps to higher level → photon ABSORBED
∆E formula ∆E = −2.18×10−18 J × (1/nf2 − 1/ni2)
Limitations of the Bohr Model
• Works only for hydrogen (one-electron atoms/ions); fails for multi-electron atoms.
• Doesn't explain WHY electrons stay in orbits without spiralling into the nucleus.
• Treats electrons as particles in fixed orbits — incompatible with wave-particle duality.
• Key legacy: introduced the idea that electrons exist in discrete, quantized energy levels.
6.4 The Wave Behavior of Matter
de Broglie's Hypothesis (1924)
If light (a wave) can behave like particles, can particles behave like waves? De Broglie said YES.
λ = h / (mv) (de Broglie wavelength of matter)
m = mass (kg), v = velocity (m/s), h = Planck's constant
For large objects (e.g. golf ball): λ is immeasurably tiny → wave nature unobservable.
For electrons: λ is comparable to X-ray wavelengths → wave nature IS observable.
• Electrons diffract through crystals — proving their wave nature (confirmed experimentally).
• Electron microscopes exploit matter waves → magnification up to 3,000,000× (far beyond optical
microscopes).
Heisenberg's Uncertainty Principle (1927)
• Electrons exhibit wave–particle duality → impossible to know both position AND momentum exactly at the
same time.
∆x · ∆(mv) ≥ h/(4π)
∆x = uncertainty in position | ∆(mv) = uncertainty in momentum
More precisely we know position → less precisely we know momentum, and vice versa.
Consequence: we CANNOT describe the exact path of an electron around a nucleus.
✎ The uncertainty principle is a fundamental law of nature, NOT a limitation of instruments.
6.5 Quantum Mechanics and Atomic Orbitals
In 1926, Schrödinger developed his wave equation, treating the electron like a standing wave. Solutions give
wave functions (ψ) that describe the electron.
• ψ itself has no direct physical meaning.
• ψ2 = probability density (electron density) — tells the probability of finding the electron at any point in space.
• An orbital is an allowed wave function with a specific energy, shape, and orientation.
Three Quantum Numbers Describe Each Orbital
Principal quantum number n n = 1, 2, 3 … Controls SIZE and ENERGY of orbital. Higher n = larger
orbital, higher energy.
Angular momentum number l l = 0 to (n−1). Controls SHAPE. l = 0 → s, l = 1 → p, l = 2 → d, l = 3 → f
Magnetic quantum number ml ml = −l … 0 … +l. Controls ORIENTATION in space. Gives 2l+1 orbitals
per subshell.
Shells and Subshells
Electron shell All orbitals with the same n value
Subshell All orbitals with same n AND l values (labelled e.g. 3p, 4d)
Total orbitals in shell n2 (e.g. n=3 → 9 orbitals)
Max electrons in shell 2n2 (e.g. n=3 → 18 electrons)
Subshell sizes: s=1 orbital | p=3 orbitals | d=5 orbitals | f=7 orbitals
Max electrons: s=2 | p=6 | d=10 | f=14
Energy in Hydrogen vs Many-Electron Atoms
• Hydrogen: all subshells of the same n have the SAME energy (e.g. 3s = 3p = 3d).
• Many-electron atoms: subshell energies split due to electron–electron repulsions → ns < np < nd < nf.
6.6 Representations of Orbitals
s Orbitals (l = 0)
• Spherically symmetric (same in all directions around the nucleus).
• For 1s: one peak in radial probability; 0 nodes. For 2s: two peaks, 1 node. For 3s: three peaks, 2 nodes.
• General rule for ns orbital: number of peaks = n; number of radial nodes = n − 1.
• Size increases with n; all s orbitals shown as spheres in contour representation.
p Orbitals (l = 1)
• Dumbbell-shaped (two lobes), one lobe on each side of the nucleus.
• Three p orbitals per subshell (ml = −1, 0, +1) → labelled px, py, pz.
• Each has a nodal plane through the nucleus where ψ2 = 0.
• All three p orbitals of a subshell have the same shape and energy but different orientations.
d Orbitals (l = 2)
• Five d orbitals per subshell (ml = −2, −1, 0, +1, +2).
• Four orbitals (dxy, dxz, dyz, dx²−y²) have four-lobed 'clover' shapes in coordinate planes.
• dz² has two lobes along z-axis plus a doughnut ring in the xy-plane.
• All five d orbitals are degenerate (same energy) in the same subshell.
f Orbitals (l = 3)
• Seven f orbitals per subshell; even more complex shapes — not drawn in detail at this level.
• Important for lanthanide and actinide electron configurations.
Nodes
Node Region where ψ = 0 (zero probability of finding electron)
Radial nodes Spherical surfaces; number = n − l − 1
Angular (nodal planes) Flat planes; number = l
Total nodes (n − 1) total nodes per orbital
6.7 Many-Electron Atoms
Orbital Energies
• In many-electron atoms, orbitals in the same shell have DIFFERENT energies (unlike H).
• For a given n: E(s) < E(p) < E(d) < E(f) due to electron–electron repulsions and shielding.
• Orbitals within the SAME subshell (e.g. all three 2p orbitals) are degenerate (same energy).
Electron Spin — 4th Quantum Number
• Electrons behave as tiny spinning magnets with two possible spin states.
Spin magnetic quantum number ms = +½ or −½
Represented as ↑ (spin-up) or ↓ (spin-down) in orbital diagrams.
Pauli Exclusion Principle
No two electrons in an atom can have the same four quantum numbers (n, l, ml, ms).
Consequence: each orbital holds a MAXIMUM of 2 electrons — and they must have opposite spins.
MRI Application (Nuclear Spin)
• Nuclei (e.g. 1H) also have spin states; placed in a magnetic field, the two states have different energies.
• Radiofrequency photons can flip nuclear spins → basis of NMR and MRI imaging.
6.8 Electron Configurations
The electron configuration describes how electrons are distributed among orbitals. The ground state is the
lowest-energy (most stable) arrangement.
Rules for Filling Orbitals
Aufbau principle Fill orbitals in order of increasing energy (lowest first).
Pauli exclusion principle Max 2 electrons per orbital; must have opposite spins.
Hund's rule When filling degenerate orbitals, put 1 electron in each first (all spin-up), then
pair up. Maximises unpaired electrons.
Orbital Diagrams for First 10 Elements
H (1) 1s1 — one unpaired electron
He (2) 1s2 — full 1s, zero unpaired
Li (3) 1s2 2s1 — starts new shell
Be (4) 1s2 2s2
B (5) 1s2 2s2 2p1 — first p electron
C (6) 1s2 2s2 2p2 — 2 unpaired (Hund's rule)
N (7) 1s2 2s2 2p3 — 3 unpaired (half-filled p)
O (8) 1s2 2s2 2p4 — 2 unpaired
F (9) 1s2 2s2 2p5 — 1 unpaired
Ne (10) 1s2 2s2 2p6 — full octet, noble gas
Condensed Electron Configurations
• Use the nearest noble gas of lower atomic number in square brackets = core electrons.
• Example: Na (11) = [Ne]3s1; Ca (20) = [Ar]4s2
• Core electrons: represented by the noble-gas symbol. Valence electrons: written after the brackets.
Transition Metals (d-block)
• After filling 4s, the 3d orbitals are filled from Sc (21) to Zn (30).
• General pattern: [Ar]4s23dx (with exceptions).
Anomalous configurations:
Cr (24): [Ar]4s13d5 — half-filled d subshell is especially stable
Cu (29): [Ar]4s13d10 — completely filled d subshell is especially stable
Lanthanides and Actinides (f-block)
• Lanthanides (57–70): 4f orbitals filling. Very similar properties; occur together in nature.
• Actinides (89–102): 5f orbitals filling. All radioactive; most not found in nature.
6.9 Electron Configurations and the Periodic Table
The periodic table's structure directly reflects electron configurations. Elements in the same group share the same
valence electron configuration.
Blocks of the Periodic Table
s-block (Groups 1–2) Outermost subshell = s orbital. Alkali metals (ns1) + alkaline earth metals
(ns2). 2 columns.
p-block (Groups 13–18) Outermost subshell = p orbital. 6 columns; max 6 electrons (ns2np1–6).
d-block (Transition metals) d orbitals filling; 10 columns. Principal quantum number of d = n−1 relative to
the period.
f-block (Lanthanides + Actinides) f orbitals filling; 14 columns. Placed below main table. 4f (lanthanides) and 5f
(actinides).
How to Write a Configuration from the Periodic Table
• 1. Find the element; move left to the nearest preceding noble gas → that is the [core].
• 2. Trace across the period: s-block first (gives nsx), then d-block (gives (n−1)dx), then p-block (gives npx).
• 3. Count electrons added; verify total = atomic number.
Example: Se (Z=34) → [Ar] → 4s2 → 3d10 → 4p4 → [Ar]4s23d104p4
Check: 18 (Ar) + 2 + 10 + 4 = 34 ✓
Valence vs Core Electrons
Valence electrons Outermost electrons; involved in chemical bonding. For main-group elements:
all outer-shell electrons. For transition metals: outermost s + d electrons (filled
d/f subshells are NOT valence).
Core electrons Inner electrons represented by the noble-gas core [symbol]; NOT involved in
bonding.
Anomalous Configurations — Summary
• Arise when half-filled or completely filled d or f subshells give extra stability.
• Most notable: Cr, Cu (in 3d series) and several heavier transition/f-block metals.
• These are minor departures — not of major chemical significance — but must be memorised.
■ Key Equations — Quick Reference
λν = c Wave equation: wavelength × frequency = speed of light
E = hν Energy of a photon (or quantum)
E = hc/λ Energy of photon from wavelength
En = −2.18×10−18/n2 J Energy levels of hydrogen atom
∆E = −2.18×10−18(1/nf2 − 1/ni2) Energy change during electronic transition
λ = h/(mv) de Broglie wavelength of a particle
∆x·∆(mv) ≥ h/(4π) Heisenberg uncertainty principle
Ephoton = hν = −∆E Energy of emitted/absorbed photon
Constants to memorise:
c = 2.998 × 108 m/s | h = 6.626 × 10−34 J·s | RH = 1.097 × 107 m−1
■ Concept Connections & Common Exam Points
Wave–particle duality Both light AND electrons show this. Light: photoelectric effect (particle).
Electrons: diffraction (wave).
Quantum numbers 4 in total: n (size/energy), l (shape), ml (orientation), ms (spin). Each orbital
needs unique set.
Orbital vs orbit Orbital = quantum-mechanical probability region (3D cloud). Orbit = Bohr's
circular path (incorrect for real atoms).
Ground vs excited state Ground: n=1 for H; lowest energy. Excited: any higher n; produced by
absorbing a photon.
Emission vs absorption Emission: electron drops → photon released. Absorption: photon absorbed →
electron jumps up.
Hund's rule shortcut Fill each empty orbital of a subshell first, then pair up. Count arrows pointing
same direction = number of unpaired e−.
Periodic table blocks s-block: Groups 1,2 | p-block: Groups 13–18 | d-block: transition metals |
f-block: lanthanides & actinides
Anomalous configs Cr = [Ar]4s13d5; Cu = [Ar]4s13d10 — half-filled/fully-filled d is extra stable.
Memory tip for orbital filling order: 1s → 2s → 2p → 3s → 3p → 4s → 3d → 4p → 5s → 4d → 5p → 6s
→ 4f → 5d → 6p …
Follow the periodic table left-to-right, top-to-bottom — it gives you the filling order automatically.
Notes compiled from Chemistry: The Central Science, 15th Global Edition, Brown et al. — Chapter 6