CHEM Pre PH.D Course

Department OF Chemistry
Pre Ph.D Course

2014
The course consists of a total of 16 units. Unit I & II are common for all students. Out of
remaining 14 units the candidate may choose relevant 8 units as recommended by the doctoral
committee.
Unit 1 General research Methodology:
(i)
Scientific approach to problem solving Definition, principles and strategies of scientific
approach to problem solving Submission of a research proposal to doctoral committee for
evaluation)
(ii)
Literature survey for pursuing research in chemistry methods
(iv) Presenting the research:
Presentation of the research proposal, thesis writing
Unit II (iii)
Analytical techniques (PG diploma in analytical techniques may be prescribed)

Elective units
Unit 1 Organic synthesis approaches:

Target oriented synthesis-principles of retrosynthetic analysis, Diversity oriented synthesisPrinciples and approaches
Unit 2 Asymmetric synthesis
Need, general principles and strategies for asymmetric synthesis
Unit 3 Chemical biology
Chemical biology, origin, scope, academic and industrial perspectives, descriptors for biological
relevance of an organic molecule, Lipinski rule, selected examples, challenges to synthetic
chemists.
Unit 4 Retrosynthetic Analysis
Unit 5 Bio-organic Chemistry
Biomimetics; Peptides and Proteins Chemistry; Supramolecular Chemistry.
Unit 6
Symmetry of Molecules
Concept of Symmetry in Molecules-Symmetry Operations & Symmetry Elements: Rotational
Axis of Symmetry and Types of Rotational Axes, Plane of Symmetry and types of Planes,
Improper Rotational Axis of Symmetry, Inversion Center and Identity Element
Unit 7
Extended Huckel Theory:
Mulliken populations, EH energies and Mulliken populations. Comparison with experimental
energies. Orbital Symmetry, Building of Interaction of diagrams. Construction of Walsh
diagrams and modelling potential energy surfaces. Rules for determining relative orbital
energies. Conjugation and Hyperconjugation. Self Consistent Theory of molecules: Roothan`s
equations, Semi-empirical SCF methods. Ab-initio MO calculations. Basis sets. The HartreeFock limit. Correlation energy, Koopmans theorem. Perturbation theory and configuration
interaction. Basis Set superposition error.
Unit 8
Potential Energy & Surfaces:
Valence Bond configuration mixing diagrams. Rules for mixing VB configurations. VBCM and
resonance theory. Reaction Profiles. Potential energy surfaces. Curve cro Model. Factors
governing barrier heights.Z-matrix specification, Input for Semi-empirical and ab-initio
programs. Molecular mechanics program. Analysis of output.
Unit 9
Thermodynamics and Statistical Mechanics
Unit 10
Reaction mechanisms of transition metal complexes:
Ligand substitution reactions: Energy profile of a reaction- Transition state of
Activated complex. Types
of substitution reactions ( SE,SN, SN1, SN2).
Ligand substitution reactions in octahedral complexes: Acid hydrolysis reactions, Factors
effecting Acid
Hydrolysis, Base Hydrolysis, Conjugate Base Mechanism, Evidences in favour
of SN1CB Mechanism.
Substitution reactions without Breaking Metal-Ligand bond.
Ligand Substitution reactions in Square-Planar complexes: Mechanism of Substitution in
SquarePlanar complexes- Trans-effect, Grienbergs Polarization theory and bonding theory Applications
of Trans-effect in synthesis of Pt (II) complexes.
Electron Transfer Reactions (or Oxidation-Reduction Reactions) in Coordination compounds:
Mechanism of One-electron Transfer Reactions: Atom
Unit 11
UNIT - III: CHEMICAL KINETICS & PHOTO CHEMISTRY 15 hrs
CHEMICAL KINETICS: Structure-Reactivity relationships-
Linear free energy
relationships. Hammett
equation The substituent constant( ) and exalted sigma values. The
Reaction constant ( ) and the
importance of rho value in arriving at the mechanism of reactions. Deviations
from Hammett
correlations. Taft equation and Taft four parameter equation. The Swain
Scott equation- Correlations
for nucleophillic reactions. The Edward equation. The reactivity-selectivity

principle and the
isoselectivty rule. The intrinsic barrier and Hammonds postulate.
PHOTO CHEMISTRY: Formation of excimers and exciplexes Quantum yields.
Electronically excited
states- singlet and triplet states. Uni molecular decay of the excited stateinternal conversion, inter
system crossing, fluorescence and phosphorescence. Principles of energy
transfer- photosensitization.
Flash photolysis and its applications .
Organic photochemistry. Photochemistry of alkenes: Cis-trans
isomerisation, di-- methane rearrangement. Photochemistry of carbonyl
compounds: i) Norrish type-I
reactions. Photoreduction and photooxidation.ii) Norrish type-II reactions.
Addition of carbonyl to carbon-carbon multiple bonds (Paterno-Buchi)
reaction. Barton reaction. Singlet oxygen photo oxidation and reactions
with C=C compounds. Ru(bpy)3
2+ as sensitizer for photo redox reactions.
Photochemical cleavage of water.
Unit 12
UNIT IV: MATERIALS SCIENCE AND MOLECULAR MODELING (15
hrs)
Preparative methods of inorganic solids: Ceramic, coprecipitation, sol-gel, chemical
vapor transport.
Characterization techniquesof inorganic solids: X-ray powder diffraction (XRD),
transmission electron
microscopy (TEM) and X-ray photoelectron spectroscopy (XPES).
Composites: Classification, fiber reinforced composites- influence of fiber
length.
Nanomaterials: preparation by sol-gel and hydrothermal methods,
characterization by powder XRDScherers equation and general applications.
Molecular modeling: QSAR parameters Physiochemical parametersLipophilicity - Electronic
parameters, Steric parameters, effect of electronic and steric parameters on
lipophilicity. Hansch
analysis, significance of slopes and intercepts in Hansch analysis. QSAR- 2D,
3D.
Case study on Pyranenamine. Achievements of QSAR Forecasting
biological activity, selection of proper substituents, bioisosterism, drug
receptor interactions and pharmacokinetic information Introduction to
database similarity SearchAlignment ; Alignment methods, Pair-wise
alignment ;Multiple Sequence Alignment Homology Modeling Energy
minimization methods Active site Identification Virtual Screening Small
molecule Building Docking Algorithms Docking Analysis
Unit 13
Unit-II: IR, Raman, NMR and ESR (15 hrs)
IR and Raman: Symmetry Based Selection Rules of Infrared and Raman
Symmetry Requirements
for Overtone, Binary and Ternary Combination Bands - Fermi Resonance .
Application of IR
spectroscopy in the structural elucidation of inorganic compounds and metal
complexes- Aquo, sulfato,
carbonato , nitro and carbonyl metal complexes.
Multinuclear NMR: Characteristic Nuclear Properties of 1H, 13C, 19F, 31P and 15N
- Reference
standards- Ranges of Chemical Shifts Use of Chemical Shifts and Coupling
Constants for the structure
determination of simple inorganic and Coordination Compounds containing
one or more of 1H, 13C, 19F,
31P and 15N nuclei
Unit 14
Unit-III: Supramolecules and Organo metallic Catalysis (15 hrs)
Supramolecular chemistryHost Guest chemistry : Definition and different types of
host and guests with examples types of non covalent interactions binding
constants of host guest complex and thermo dynamics involved in it
designing principles of host. Cation guest binding binding between metal
cations and macro cycles chelate and cryptate effects relationship
between cavity size of host and cation radius and stability of resultant
complexes binding of macro cycles having secondary binding sites Anion
guest binding different hosts for anionic guests capable of binding through
electro static interactions, hydrogen bonds, lewis acidic hosts enhancement
of binding strength using more than non covalent interactions Neutral guest
binding binding of neutral guest using hydrogen bonding, - stacking,
hydrophobic effect and charge transfer interactions simultaneous binding
of cation and anion guests cascade approach, individual binding sites and
zwitter ions approach present and future applications phase transfer
agents separation of mixtures molecular sensors switches and
molecular machinery.
Catalytic role of Organometallic Compounds: Oxidative addition and Reductive
Elimination :
Stereochemistry and Mechanism of Oxidative Addition Insertion Reactions
Hydrogenation of
Olefins Transfer Hydrogenation Hydrosilation of Olefins Isomerisation of
Olefins Ziegler
Natta Polymerization of Olefins Oligomerization of Butadiene . Alkene
Metathesis.

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CHEM Pre PH.D Course

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Department OF Chemistry

Pre Ph.D Course

Analytical techniques (PG diploma in analytical techniques may be prescribed)

Unit 1 Organic synthesis approaches:

Linear free energy

for nucleophillic reactions. The Edward equation. The reactivity-selectivity

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