Chemistry 245: Computational Chemistry
Lecture Schedule
Notes:
1) course introduction; syllabus
2) introduction to theory; examples of applications
3) in-class exercise: introduction to Spartan ‘08 (in-class assignment #1)
1) classical mechanics overview
2) force field terms
3) comparison of different force fields
4) in-class exercise: molecular mechanics in Spartan (in-class assignment #2)
* HW #1(a) assigned
1) quiz #1 and literature application discussion (J. Phys. Chem. A, 2004, 108, 621-627)
2) classical dynamics overview
3) MD and Monte Carlo simulations
4) applications: protein folding, NMR determination of protein structure
5) in-class exercise: simulating MD in Excel (in-class assignment #3)
* HW #1(a) due; HW #1(b) assigned
1) Schrödinger equation, Born-Oppenheimer approximation
2) LCAO approach
3) Hückel theory
4) in-class exercise: Hückel theory (in-class assignment #4)
5) Hartree-Fock theory introduction and Self-consistent field method
* HW #1(b) due
1) finish Hartree-Fock theory
2) semi-empirical methods overview
3) comparison of CNDO, INDO, NDDO formalisms and performance
4) geometry representations: Cartesian coordinates, z-matrices, symmetry
5) in-class exercise: writing z-matrices (in-class assignment #5)
* HW #2(b) assigned
1) quiz #2 and literature application discussion (J. Am. Chem. Soc., 1996, 118, 8920-8924)
2) basis sets (Gaussian functions, polarization & diffuse functions, effective core potentials)
3) practical issues: SCF convergence, symmetry
4) Hartree-Fock theory accuracy
5) in-class exercise: electrophilic aromatic substitution of toluene and nitrobenzene – verification of
substitution patterns via semi-empirical and Hartree-Fock calculations (in-class assignment #6)
* HW #2(b) due; HW #2(a) assigned
Molecular properties:
1) multipole moments and molecular electrostatic potential
2) partial atomic charges and atomic spin
3) ionization potentials; electron affinities
4) infrared spectra
5) in-class exercise: organometallic metal-carbonyl half-sandwich complexes (in-class assignment #7)
1) computing enthalpy, entropy, and free energy changes for reactions
2) isodesmic reactions
3) application: calculating heats of formation and relative stability of species
4) determining transition states
5) transition state theory, rate constants
6) kinetic isotope effects, transmission coefficients
7) in-class exercise: hydrogen atom transfer between organic molecules (in-class assignment #8)
* group sign-up for final project; HW #3 assigned
1) density functional theory overview
2) Hohenberg-Kohn theorems, Kohn-Sham methodology
3) exchange & correlation functionals
4) DFT performance and comparison with MO theory
5) application discussion: transition metal complexes (J. Phys. Chem. A, 2004, 108, 5479-5483)
1) quiz #3 and literature application discussion (Phys. Chem. Chem. Phys., 2005, 7, 2701-2705)
2) the process of solvation and solvation effects on reactions
3) continuum solvation models
4) mixed explicit/implicit solvation models
5) standard-state corrections
* HW #3 due; HW #4 assigned
1) calculation of pKa values and reduction potentials
2) calculation of partition coefficients
3) application discussion: pKa values with different solvation models (J. Phys. Chem. A, 2006, 110, 2493-
2499)
4) in-class exercise: determining pKa values with different solvation models (in-class assignment #9)
2) application discussion: empirical corrections to computed NMR spectra (J. Chem. Theory Comput.,
2006, 2, 1085-1092)
3) UV-Vis spectra and TD-DFT methods
4) open-shell molecules and unrestricted wave functions
5) in-class exercise: NMR spectra at different levels of theory (in-class assignment #10)
1) quiz #4 and literature application discussion (J. Org. Chem., 2003, 68, 6375-6386)
2) overview of QM/MM methods
3) QM/MM boundaries between space and atoms
4) application discussions (J. Am. Chem. Soc., 2004, 126, 7652-7664;
J. Am. Chem. Soc., 2005, 127, 1025-1037)
* HW #4 due