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Quantum Numbers and Orbitals

Jun 18, 2025

Overview

This lecture covers quantum numbers, their significance, application in electronic configurations, isoelectronic species, orbital energies, and magnetic moments in multi-electron atoms and ions.

Quantum Numbers and Orbitals

  • Quantum numbers (n, l, m, s) describe the state of electrons in atoms.
  • Principal quantum number n = energy level; n = 1, 2, 3, ...
  • Azimuthal quantum number l = shape of orbital; l = 0 to (n-1).
  • Magnetic quantum number m = orientation; m = -l to +l.
  • Spin quantum number s = spin direction; s = +1/2 or -1/2.
  • 4f orbital: n=4, l=3, allowed m values are -3 to +3.
  • Number of orbitals for given n: n²; for n=5, orbitals = 25.
  • Number of subshells for n: n.
  • Radial nodes = n - l - 1; angular nodes = l.
  • Degenerate orbitals have the same energy in hydrogen but not in multi-electron atoms.

Isoelectronic Species and Ionic Radii

  • Isoelectronic species = ions/atoms with the same number of electrons.
  • Examples: K⁺, Ca²⁺, Sc³⁺, Cl⁻ are isoelectronic.
  • For isoelectronic ions, ionic radius decreases with increasing nuclear charge.
  • Order (smallest to largest for K⁺, Ca²⁺, Cl⁻, S²⁻): Ca²⁺ < K⁺ < Cl⁻ < S²⁻.

Electronic Configuration

  • Electrons fill orbitals in order of increasing energy (Aufbau principle).
  • Half-filled and fully-filled subshells are exceptionally stable.
  • Cr and Cu show exceptions in electron configuration ([Ar] 3d⁵ 4s¹ for Cr).
  • Outer electron configuration determines chemical properties and magnetic moment.

Orbital Energy and Magnetic Moment

  • For hydrogen, all orbitals with same n have same energy.
  • In multi-electron atoms, energy: ns < np < nd < nf for a given n.
  • Magnetic moment depends on unpaired electrons: μ = √(n(n+2)) BM.
  • More unpaired electrons = higher magnetic moment.

Key Terms & Definitions

  • Isoelectronic species — Species with the same number of electrons.
  • Degenerate orbitals — Orbitals with equal energy.
  • Radial node — Region where electron probability is zero, depends on n and l.
  • Angular node — Plane or cone where probability is zero, equals l.
  • Aufbau principle — Rule for electron filling order by increasing energy.
  • Spin quantum number (s) — Quantum number describing electron spin (+1/2 or -1/2).
  • Magnetic moment — Measure of unpaired electrons, in Bohr Magneton (BM).

Action Items / Next Steps

  • Review key quantum number definitions and rules for allowed values.
  • Practice identifying isoelectronic species and ordering ionic radii.
  • Complete homework exercises on electron configurations and quantum numbers.