Quantum Chemistry III — Density Functional Theory
Courses
Trade the 3N-dimensional wavefunction for the 3-dimensional density. Derive both Hohenberg-Kohn theorems, build the Kohn-Sham machinery as a mirror of your Hartree-Fock code, derive LDA from the electron gas, climb Jacob’s ladder — and map the failure modes (self-interaction, dispersion) every practitioner must know cold.
The density idea
plannedFrom 3N coordinates to 3: Thomas-Fermi as the brave, wrong first try.
- lessonWhy the density might be enoughplanned
- projectProject — Thomas-Fermi energy of an atomplanned
Hohenberg-Kohn
plannedBoth theorems, derived — proof by contradiction as an exercise format.
- lessonHK I: the density determines everythingplanned
- exercisesExercises — Derive the Hohenberg-Kohn theoremsplanned
- lessonHK II: the variational principle for densitiesplanned
Kohn-Sham
plannedThe fictitious system trick — your Fock derivation, mirrored.
- lessonKohn-Sham: exact in principle, practical in formplanned
- exercisesExercises — Derive the Kohn-Sham equationsplanned
- lessonEverything unknown in one corner: the exchange-correlation functionalplanned
LDA from the electron gas
plannedDerive ε_x ∝ ρ^(4/3), then run your own DFT next to your own HF.
- lessonThe homogeneous electron gas pays for everythingplanned
- exercisesExercises — Derive the LDA exchange energyplanned
- projectProject — Slater-Xα SCF for H₂ on a gridplanned
Jacob's ladder
plannedGGA, hybrids, meta-GGA, range separation — what B3LYP literally is.
- lessonGradients enter: GGA and PBE mechanicsplanned
- lessonHybrids: why exact exchange, how much, and the B3LYP recipeplanned
- lessonThe rest of the ladder, honestly pricedplanned
Where DFT lies
plannedSelf-interaction, dispersion, gaps — the failure modes every user must know cold.
- projectProject — H₂⁺ in HF vs LDA: one electron, two verdictsplanned
- lessonSelf-interaction and delocalization errorplanned
- lessonDispersion: the missing force and the +D patchesplanned
Time-dependent DFT
plannedExcited states from response: the Casida machinery, bridged to the existing pages.
- lessonLinear response and the Casida equationsplanned
- readingReading — Casida's Equationplanned