Group Theory in Chemistry
Uses symmetry to predict spectra and orbital combinations.
Practise Analytical, Lab & Spectroscopy All Analytical, Lab & Spectroscopy topics
Uses symmetry to predict spectra and orbital combinations.
Practise Analytical, Lab & Spectroscopy All Analytical, Lab & Spectroscopy topics
Group theory applies the mathematics of symmetry to chemistry, using the character tables of point groups to classify orbitals, vibrations and electronic states. The reducible representation formed by atomic displacements or orbitals is reduced into irreducible representations, which show which vibrational modes are IR active, which are Raman active and which orbitals can combine. Selection rules then predict which transitions are allowed without detailed calculation. Atomic orbitals combine into molecular orbitals only when they belong to the same symmetry species. Group theory is therefore a powerful predictive tool in spectroscopy and bonding theory.
Key ideas: Use character tables: a vibration belongs to the irreducible representation that matches x, y or z for IR activity and to quadratic functions (xy, x2, and so on) for Raman activity. Number of times irreducible representation i occurs: n_i = (1/h) sum of (characters of reducible x characters of irreducible x class size). For H2O (C2v), three modes: 2 A1 and 1 B2, all IR and Raman active.
Common mistakes and connections: Students forget to subtract translations and rotations when counting vibrations, or confuse characters with eigenvalues. Group theory says what is allowed, not how intense a band is. Overtones and combinations follow different rules. A mode can be silent in both IR and Raman, such as the A1u torsion of ethane. Related to selection rules, molecular orbital symmetry and point groups.
Linear CO2 (point group D-infinity-h) has four vibrational modes, but its symmetry makes only two IR active, which group theory predicts without calculation. The interactive lesson shows this as a live animation or chart.
Linear CO2 has four vibrational modes, but group theory predicts only two IR-active fundamental bands.
Uses symmetry to predict spectra and orbital combinations.
Group Theory in Chemistry is a advanced topic in Analytical, Lab & Spectroscopy. It builds on beginner and intermediate topics, so review those first if needed.
Study these earlier topics in Analytical, Lab & Spectroscopy first: Harmonic Oscillator Model, Rigid Rotor Model, Molecular Symmetry.
The next topics in Analytical, Lab & Spectroscopy are Selection Rules and Franck-Condon Principle.
Yes. The interactive lesson includes a self-check question on Group Theory in Chemistry, and the Analytical, Lab & Spectroscopy quiz draws on every topic in this area.
Group Theory in Chemistry is topic 92 of 99 in Analytical, Lab & Spectroscopy.