Course Identification
Chemical Bonding: a Computational Perspective
Lecturers and Teaching Assistants
Prof. Gershom Martin
Course Schedule and Location
Wednesday, 14:15 - 16:00, FGS, Rm 5
27/10/2021
Field of Study, Course Type and Credit Points
Chemical Sciences: Lecture; Elective; Regular; 2.00 points
Attendance and participation
Estimated Weekly Independent Workload (in hours)
Syllabus
- Wavefunction ab initio theory – a very quick introduction
- Hartree-Fock theory and hence molecular orbitals: exact in mean-field approximation
- Electron correlation: nature’s ‘chemical glue
- Many-body perturbation theory
- Configuration interaction (CI) and the size-extensivity problem
- Coupled cluster theory: the gold standard
- Natural orbitals: generalization of molecular orbitals for correlated methods
- Density functional theory: semiempirical methods done right
- Kohn-Sham theory
- LDA: exact for homogenous electron gas (HEG)
- GGA and meta-GGA functionals: moving beyond the HEG
- Hybrid functionals: de facto standard for practical molecular applications
- Double hybrids: blurring the line between WFT and DFT
- Density analysis
- QTAIM or Quantum Theory of Atoms in Molecules (“Bader analysis”): chemical bonding from the perspective of the electron density
- Hirshfeld (stockholder) analysis
- Orbital analysis
- Natural population analysis
- Mulliken and why it is worse than useless
- Frontier orbital analysis
- Atomic partial charges: the bigger picture
- A very brief introduction to conceptual DFT
- Putting empirical concepts like the electron affinity on a solid foundation
- Covalent bonding from WFT and DFT perspectives
- The role of near-degeneracy correlation
- Noncovalent interactions from WFT and DFT perspectives
- Symmetry-adapted perturbation theory as a tool to interpret noncovalent interactions
- Analyzing different types of NCIs: hydrogen bonds, halogen bonds, cation-pi, pi-stacking, rare gas complexes,…
- Beyond electronic structure: Zero-point vibrational energy and thermal corrections
- Quasilinear and quasisymmetric molecules
- Relativistic corrections
- The Dirac equation for hydrogen-like atoms, and what its solution means
- Scalar relativistic effects
- Spin-orbit coupling
Learning Outcomes
* have an understanding of chemical bonding that transcends the simplistic MO picture
* be familiar enough with the main electronic structure methods to make an informed decision about the reliability of reported calculations