Quantum Chemistry and Chemical Kinetics

Schrodinger equation, postulates of quantum mechanics, operators and commutation relations, discussions of solutions of the Schrodinger equation to some model systems – particle in a box, harmonic oscillator, rigid rotor, hydrogen atom.

The variation theorem, linear variation principle, perturbation theory (first order and non – degenerate), application of variation method and perturbation theory to helium atom, ordinary and generalized angular momentum, eigen functions and  eigen values for angular momentum, operator using ladder operators, addition of angular momenta, spin, antisymmetry and Pauli’s exclusion principle.

Huckel theory of conjugate systems, bond and charge density calculations. Applications to ethylene, butadiene, cyclopropenyl radical, cyclobutadiene. Introduction to extended huckel theory.

Pre requisite: Factors affecting rate of chemical reactions, comparison between order and molecularity, units of rate constants for different orders of reactions.                    

Scope, laws of chemical kinetics, order of reaction and determination of order of reaction, methods of determining rate laws, differential and integrated form of rate expression (1^st, 2^nd …….n^th order), rate expression for opposing, parallel and consecutive reactions; collision theory of reaction rates, steric factor, activated complex theory, comparison between collision theory and activated-complex theory.

Unimolecular gas reactions, dynamics of unimolecular reactions (Lindemann, Hinshelwood and Rice-Ramsperger – Kassel-Marcus RRKM theories); primary and secondary salt effects-influence of ionic strength and dielectric constant on reactions involving (i) ions  (ii) dipoles (iii) ion and dipole, fast reactions (a brief idea).

Steady state approximation in reaction mechanisms; kinetic and thermodynamic control of the reactions; chain reactions – thermal and photochemical reactions, dynamic chain (mechanism of hydrogen-bromine and hydrogen-chlorine reactions), decomposition of ethane, pyrolysis of acetaldehyde; oscillatory reactions – Belousov-Zhabotinsky reaction; enzyme catalysis – Michaelis-Menten kinetics.

Self Study:  Factors affecting enzyme catalyzed reactions, effect of pH on enzymes