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Chemical Sciences PAPER II

1. Quantum Chemistry  :  Planck’s quantum theory, wave – particle duality.  Uncertainty Principle, operators and commutation relations;  postulates of quantum mechanics and Schrodinger equation; free particle, particle in a box, degeneracym, harmonic oscillator, rigid rotator and the hydrogen atom.  Angular momentum, including spin; coupling of angular momenta including spin-orbit coupling.

2. The variation method and perturbation theory : Application to the helium atom, antisymmetry and Exclusion Principle, Siater determinantal wave functions.  Terms symbols and spectroscopic states.

3. Born – Oppenheimer approximation, Hydrogen molecule ion.  LCAO – MO and VB treatments of the hydrogen molecule; electron density, forces and their role in chemical binding.  Hybridisation and valence MO3 of H2O, NH3 and CH4.  Hudket pl-electron theory and its applications to ethylene, butadience and benzene.  Idea of sell-consistent fields.

4. Group theoretical representations and spectrosconic selection rules for vibrational, electronic, vibronic and Raman spectroscopy.  MO treatment of large molecules with symmetry.

5. Spectroscopy  :  Theoretical treatment of rotational, vibrational and electronic spectroscopy.  Principles of magnetic resonance, Mossbauer and photoelectron spectroscopy.

6. Thermodynamics  :  First law of thermodynamics, relation between Cp and Cv; enthaipies of physical and chemical changes; temperature dependence of enthaipies.  Second law of thermodynamics, entropy, Gibbs-Helmoholtz equation.  Third law of thermodynamics and calculation of entropy.

7. Chemical Equilibrium  :  Free energy and entropy of modng, partial molar  quantities, Gibbs – Duhern equation.  Equilibrium constant, temperature – dependence of equilibrium constant, phase diagram of one – and two – component systems, phase rule.

8. Ideal and Non-ideal eciuiions, Excess functions, activities, concept of hydration number; activities in electrolytic solutions; mean ionic activity coefficient; Debye – Huckel treatment of dilute electrolyte solutions.

9. Electrochemistry :  Electrochemical cell reactions, Nernst equation, Electrode Kinetics, electrical doubie layer, electode / electrolyte interface, Batteries, primary and secondary Fuel Cells, corrosion and comosion prevention.

10. Surface Phenomena :  Surface tension, adscrption on solids, electrical phenomena at interfaces, including electrokinetic, micelles and reverse micelles; solubilization, micro-emulsions.  Application of photoelectron spectroscopy.  ESCA and Auger spectroscopy to the study of surfaces.