CY 5011 - Transition Metal and Organometallic Chemistry
Transition Metal Chemistry
Structure, bonding and properties of transition metal ligand complexes – ligand, coordination, geometry, coordination number, isomerism (recapitulation); HSAB concept, thermodynamic stability, successive and overall stability constants, Irving-William series, chelate and macrocyclic effect.
Theories of bonding - VBT, CFT and their limitations; d-orbital splitting in octahedral, JT-distorted octahedral, square planar, square pyramidal, trigonal bipyramidal, and tetrahedral complexes; CFSE for d1 to d10 systems, pairing energy, low-spin and high-spin complexes and magnetic properties; LFT, and molecular orbital (MO) theory of selected octahedral and tetrahedral complexes.
Electronic Spectra - UV-Vis, charge transfer, colors, intensities and origin of spectra, interpretation, term symbols and splitting of terms in free atoms, selection rules for electronic transitions, Orgel and Tanabe-Sugano diagram, calculation of Dq, B, C, Nephelauxetic ratio.
Reaction mechanisms - substitution reactions in octahedral and square planar complexes, trans effect and its influence, water exchange, anation and base hydrolysis, stereochemistry, inner and outer sphere electron transfer mechanism.
Lanthanides and Actinides - contraction, coordination, optical spectra and magnetic properties.
Valence electron count (16/18 electron rules); structure and bonding in mono and polynuclear metal carbonyls; substituted metal carbonyls and related compounds; synthesis and reactivity of metal carbonyls; vibrational spectra of metal carbonyls; dinitrogen and dioxygen as ligands in organometallic compounds.
Types of M-C bonds; synthesis and reactivity of metal alkyls, carbenes, alkenes, alkynes, and arene complexes; metallocenes and bent metallocenes; isolobal analogy.
Reactions of organometallic complexes: Substitution, oxidative addition, reductive elimination, insertion and deinsertion; Catalysis - Hydrogenation, Hydroformylation, Monsanto process, Wacker process, alkene polymerization.
CY 5012 - Main Groupand Bio-inorganic Chemistry
Main Group Chemistry
Structure and bonding in polyhedral boranes and carboranes, styx notation; Wade’s rule; electron count in polyhedral boranes; synthesis of polyhedral boranes; isolobal analogy; boron halides; phosphine-boranes; boron heterocycles; borazine.
Silanes, silicon halides, silicates, silicones, silanols; germanium, tin and lead organyls; silenes, germenes and stannenes; phosphorous halides, acids and oxyacids of phosphorous, phosphazenes; sulphur halides, oxo acids of sulpur; structural features and reactivity of reactivity of S-N heterocycles.
Synthesis and reactivity of organo-lithium, -beryllium and -magnesium compounds; calixarines, cryptands and crown ethers in complexation chemistry.
Preparation and reactivity of aluminium organyls; carbalumination, hydroalumination; chemistry of Ga(I) and In(I); reduction of Al, Ga and In organyls; germanium, tin and lead organyls.
Transition elements in biology - their occurrence and function, active-site structure and function of metalloproteins and metalloenzymes with various transition metal ions and ligand systems; O2 binding properties of heme (haemoglobin and myoglobin) and non-heme proteins hemocynin & hemerythrin), their coordination geometry and electronic structure, co-operativity effect, Hill coefficient and Bohr Effect; characterization of O2 bound species by Raman and infrared spectroscopic methods; representative synthetic models of heme and non-heme systems.
Electron transfer proteins - active site structure and functions of ferredoxin, rubridoxin and cytochromes, and their comparisons. Vitamin B12 and cytochrome P450 and their mechanisms of action.
Metals in medicine - therapeutic applications of cis-platin, radio-isotopes (e.g., Tc & I2) and MRI agents.
Toxicity of metals - Cd, Hg and Cr toxic effects with specific examples.
CY 6011 - Solid State Chemistry
Crystal Structure: Crystalline and amorphous solids; crystal systems, point groups: methods of characterizing crystal structure - Powder x-ray diffraction, electron and neutron diffraction; types of close packing - hcp and ccp, packing efficiency, radius ratios; polyhedral description of solids; structure types -NaCl, ZnS, Na2O, CdCl2, wurtzite, nickel arsenide, CsCl, CdI2, rutile and Cs2O, perovskite ABO3, K2NiF4, spinels.
Preparative methods: Solid state reaction, chemical precursor method, co-Precipitation, sol-gel, metathesis, self-propagating high temperature synthesis, ion exchange reactions, intercalation / deintercalation reactions; hydrothermal and template synthesis; High pressure synthesis
Methods of Single Crystal Growth: Solution growth; Melt Growth-Bridgeman, Czochralski, Kyropoulus, Verneuil; Chemical Vapour Transport; Fused Salt Electrolysis; Hydrothermal method; Flux Growth
Thermal analysis: TGA, DTA, DSC
Electrical properties: Band theory of solids -metals and their properties; semiconductors - extrinsic and intrinsic, Hall effect; thermoelectric effects (Thomson, Peltier and Seebeck); insulators - dielectric, ferroelectric, pyroelectric and piezoelectric properties; ionic conductors.
Magnetic properties: Dia, para, ferro, ferri, and antiferro magnetic types; soft and hard magnetic materials; select magnetic materials such as spinels, garnets and perovskites, hexaferrites and lanthanide-transition metal compounds; magnetoresistance.
Optical properties: Luminescence of d- and f- block ions; structural probes; up and down conversion materials.
Superconductivity: Basics, discovery and high Tc materials.
Additional Topics: Amorphous materials, zeolites, fullerenes and nanocrystalline solids.
CY 5013 - Conceptual Organic Chemistry and Introductory Biochemistry
Conceptual Organic Chemistry:
Review of basic concepts of inductive effect, electromeric effect, resonance effect, hyperconjugation, the formalism of curved arrow mechanisms.
Relationship between thermodynamic stability and rates of reactions - kinetic versus thermodynamic control of product formation – Hammond postulate - kinetic isotope effects with examples - catalysis by acids and bases and nucleophiles with examples from acetal, cyanohydrin and ester formation and hydrolysis reactions - solvent effect, bulk and specific solvent effects - examples of solvent effect from SN2 substitution and E2 elimination reaction - introduction to carbon acids, pKa of weak acids. Concept of aromaticity, delocalization of electrons - Hückel’s rule, criteria for aromaticity, examples of neutral and charged aromatic systems – annulenes - NMR as a tool for aromaticity - anti- and homo-aromatic systems. Mechanism of electrophilic and nucleophilic aromatic substitution reactions, with examples.
Introduction to molecular symmetry and chirality – examples from common objects to molecules – axis, plane, center, alternating axis of symmetry. Stereoisomerism – definition based on symmetry and energy criteria – configuration and conformational stereoisomers. Center of chirality – molecules with C, N, S based chiral centers – absolute configuration - enantiomers – racemic modifications - R and S nomenclature using Cahn-Ingold-Prelog rules – molecules with a chiral center and Cn – molecules with more than one center of chirality – definition of diastereoisomers – constitutionally symmetrical and unsymmetrical chiral molecules - erythro, threo nomenclature – E and Z nomenclature – out/in isomers.
Axial, planar and helical chirality – examples – stereochemistry and absolute configuration of allenes, biphenyls and binaphthyls, ansa and cyclophanic compounds, spiranes, exo-cyclic alkylidenecycloalkanes.
Topicity and prostereoisomerism – topicity of ligands and faces, and their nomenclature – NMR distinction of enantiotopic/diastereotopic ligands. Conformational analysis of acyclic and cyclic systems – substituted n-butanes – cyclohexane and its derivatives – decalins –fused and bridged bicyclic systems – conformation and reactivity some examples – chemical consequence of conformational equilibrium - Curtin-Hammett principle.
Chemistry of Bio-molecules: Basic aspects of structure and classification of carbohydrates, lipids, amino acids, proteins and nucleic acids. Flow of genetic information, nature of genetic code, replication of DNA, transcription and translation, regulation of gene expression.
Metabolism: Bioenergetics, thermodynamic considerations, redox potentials, bioenergetic principles. Catabolism and anabolism; Enzymes involved, catalytic mechanism and regulatory steps in glycolysis, TCA cycle, mitochondrial electron transport and oxidative phosphorylation
CY 5014 - Reactive Intermediates and Concerted Reactions
C-X bond (X = C, O, N) formations through the intermediacy of
CY 6013 - Modern Synthetic Methodology in Organic Chemistry
Oxidation: Metal based and non-metal based oxidations of (a) alcohols to carbonyls (Chromium, Manganese, aluminium, silver, ruthenium. DMSO, hypervalent iodine and TEMPO based reagents). (b) phenols (Fremy’s salt, silver carbonate) (c) alkenes to epoxides (peroxides/per acids based), Sharpless asymmetric epoxidation, Jacobsen epoxidation, Shi epoxidation.(d) alkenes to diols (Manganese, Osmium based), Sharpless asymmetric dihydroxylation, Prevost reaction and Woodward modification, (e) alkenes to carbonyls with bond cleavage (Manganese, Osmium, Ruthenium and lead based, ozonolysis) (f) alkenes to alcohols/carbonyls without bond cleavage (hydroboration-oxidation, Wacker oxidation, selenium, chromium based allylic oxidation) (g) ketones to ester/lactones (Baeyer-Villiger)
Reduction: (a) Catalytic hydrogenation (Heterogeneous: Palladium/Platinum/Rhodium/Nickel etc; Homogeneous: Wilkinson). Noyori asymmetric hydrogenation. (b) Metal based reductions using Li/Na/Ca in liquid ammonia, Sodium, Magnesium, Zinc, Titanium and Samarium (Birch, Pinacol formation, McMurry, Acyloin formation, dehalgenation and deoxygenations) (c) Hydride transfer reagents from Group III and Group IV in reductions. (i) NaBH4 triacetoxyborohydride, L-selectride, K-selectride, Luche reduction; LiAlH4, DIBAL-H, and Red-Al,; Trialkylsilanes and Trialkylstannane, Meerwein-Pondorff-Verley reduction) (ii) Stereo/enantioselectiviey reductions (Chiral Boranes, Corey-Bakshi-Shibata)
Modern Synthetic Methods: Baylis-Hillman reaction, Henry reaction, Nef reaction, Kulinkovich reaction, Ritter reaction, Sakurai reaction, Tishchenko reaction and Ugi reaction. Brook rearrangement; Tebbe olefination. Metal mediated C-C and C-X coupling reactions: Heck, Stille, Suzuki, Negishi and Sonogashira, Nozaki-Hiyama, Buchwald-Hartwig, Ullmann coupling reactions, directed ortho metalation.
Stereoselective Transformations: Stereoselective synthesis of tri- and tetra-substituted olefins; Synthetic applications of, Claisen rearrangement and its variants, aza-Cope rearrangement (Overman rearrangement), ene reaction (metallo-ene; Conia ene); Prins reaction,
Construction of Ring Systems: Different approaches towards the synthesis of three, four, five and six-membered rings; photochemical approaches for the synthesis of four membered rings, oxetanes and cyclobutanes. Diels-Alder reaction (inter- and intramolecular), ketene cycloaddition (inter- and intramolecular), Pauson-Khand reaction, Bergman cyclization; Nazarov cyclization, cation-olefin cyclization and radical-olefin cyclization, inter-conversion of ring systems (contraction and expansion); construction of macrocyclic rings, ring closing metathesis.
Retrosynthetic Analysis: Basic principles and terminology of retrosynthesis, synthesis of aromatic compounds, one group and two group C-X disconnections, one group C-C and two group C-C disconnections, amine and alkene synthesis, important strategies of retrosynthesis, functional group transposition, important functional group interconversions
Protecting groups: Protection and deprotection of hydroxy, carboxyl, carbonyl, carboxy amino groups and carbon-carbon multiple bonds; chemo- and regioselective protection and deprotection; illustration of protection and deprotection in synthesis.
CY 6019 - Spectroscopy-Applications in organic and inorganic Chemistry
NMR phenomenon, spin ½ nuclei, (1H, 13C, 31P and 19F), 1H NMR, Zeeman splitting, effect of magnetic field strength on sensitivity and resolution, chemical shift d, inductive and anisotropic effects on d, chemical structure correlations of d, chemical and magnetic equivalence of spins, spin-spin coupling, structural correlation to coupling constant J, first order patterns. Second order effects, examples of AB, AX and ABX systems, simplification of second order spectrum, selective decoupling, use of chemical shift reagents for stereochemical assignments. 13C NMR, introduction to FT technique, relaxation phenomena, NOE effects, 1H and 13C chemical shifts to structure correlations. Study of dynamic processes by VT NMR, restricted rotation (DMF, DMA, biphenyls, annulenes), cyclohexane ring inversion, degenerate rearrangements (bullvalene and related systems). Multinuclear NMR of B, Al, Si, F and P nuclei; structure and dynamics of representative inorganic molecules, deriving activation and thermodynamic parameters; application of NMR to magnetism and magnetic susceptibility measurements of paramagnetic metal complexes.
Electronic spectroscopy, basic principle, electronic transitions in organic, inorganic and organometallic molecules and application to structure elucidation.
Electron paramagnetic resonance (EPR) spectroscopy of inorganic compounds with unpaired electrons - determination of electronic structure, Zeeman splitting, g-values, hyperfine and super hyperfine coupling constants, practical considerations of measurements, and instrumentation.
Infrared and Raman spectroscopy of simple inorganic molecules, predicting number of active modes of vibrations, analysis of representative spectra of metal complexes with various functional groups at the coordination sites; application of isotopic substitution, organic functional group identification through IR spectroscopy.
Mass spectrometry, basic principles, ionization techniques, isotope abundance, molecular ion, fragmentation processes of organic molecules, deduction of structure through mass spectral fragmentation, high resolution MS, soft ionization methods, ESI-MS and MALDI-MS, illustrative examples from macromolecules and supramolecules, studies of inorganic/coordination and organometallic representative compounds.
Mossebauer spectroscopy - Mossebauer effect, recoilless emission and absorption, hyperfine interaction, chemical isomer shift, magnetic hyperfine and quadruple interaction and interpretation of spectra.
Structure elucidation problems using the above spectroscopic techniques.
CY 5015 - Equilibrium and Statistical Thermodynamics
Concept of entropy, reversible and irreversible processes, Clausius inequality, Free energies, Criteria of spontaneity.
Fundamental equations for open systems, Partial molar quantities and chemical potential, Gibbs-Duhem equation, Real gases and fugacity.
Thermodynamics of ideal and non-ideal solutions: Liquid-liquid solutions, liquid-solid solutions, multicomponent systems and excess thermodynamic properties, Activity of ideal, regular and ionic solutions.
Strong electrolytes, Debye-Huckel limiting law and its extensions, activity coefficients and ionic strength, Applications of Debye-Huckel Theory.
Thermodynamic equation of state.
Phase behavior of one and two component systems, Ehrenfest classification of phase transitions.
Concept of ensembles, Canonical ensemble, Boltzmann distribution, Thermodynamic quantities and canonical partition function. Grand canonical ensemble, Fermi-Dirac and Bose-Einstein distributions.
Molecular partition functions, Translational, rotational and vibrational partition functions.
Ideal monoatomic and diatomic gases, Classical partition functions, thermodynamic properties, Equipartition theorem, Chemical equilibrium.
Real gases, intermolecular potential and virial coefficients. Debye and Einstein theory of heat capacity of solids. Structure and thermal properties of liquids, Pair correlation functions.
Linear response theory, Irreversible processes, Onsager's law, Entropy production, Non-equilibrium stationary states.
CY 5016 - Chemical Kinetics
Theories of Reaction Rates: Potential energy surfaces-adiabatic and non-adiabatic curve crossing Processes- transition state theory- activation/thermodynamic parameters. Various theories of Unimolecular reactions (Lindemann- Christiansen hypothesis; Hinshelwood, RRK and RRKM theories; non RRKM behavior)
Elementary Reactions in Solutions: Influence of solvent properties on rate. Different types of molecular interactions in solution. Diffusion and activation controlled reactions.
Kinetics in the Excited State: Jablonski diagram. Kinetics of Unimolecular and bimolecular photophysical and photochemical processes. Resonance energy transfer rates-Fluorescence quenching kinetics in solution and gas phase.
Fast Reaction Kinetics: Relaxation methods, Stopped flow method, Laser Flash Photolysis, flow tube methods, and Laser based experimental techniques. Experimental set up for Unimolecular decomposition studies. State to state dynamics. Molecular beam studies.
Electrode Kinetics: Metal/solution interface- Dependence of electrochemical reaction rate on overpotential-current density for single step and multi-step processes-Influence of electrical double layer on rate constants. Activation and diffusion controlled processes- Marcus kinetics and quadratic dependence of Gibbs free energies-electron transfer processes involving organic and inorganic compounds. Different types of overpotentials- polarization behavior-Mechanism of hydrogen evolution and oxygen reduction in acid and alkaline media- Experimental methods for elucidation of reaction mechanism.
CY 6015 - Surface, Interfaces, Dispersed Systems and Macromolecules
Surfaces and interfaces: Types of interfaces. Liquid surfaces: Microscopic picture of interfaces; curved interfaces; Young -Laplace and Kelvin equations; capillary condensation; surface tension; measuring surface tension. Solid-liquid interfaces: Contact angle and wetting, Gibbs adsorption isotherm. Solid surfaces: External and internal surfaces; Bulk and surface structure of FCC, BCC and HCP metals; Notation of surface structures; Relaxation and reconstruction of surfaces; homogeneous and heterogeneous surfaces. Solid-gas interfaces: Types of adsorption; Adsorption isotherms – Langmuir, Tempkin and BET. Determination of surface area of adsorbents; temperature dependence of adsorption isotherms.
Dispersed systems: Types of dispersions; Spontaneous self-organization; Surfactants: structure of surfactants in solution; critical micellation concentration (CMC); temperature dependence; influence of chain length and salt concentration; surfactant parameter. Emulsions: macro- and micro-emulsions; aging and stabilization of emulsions; Phase behaviour of microemulsions. Colloids, vesicles, lipid bilayer membrane: structure and properties, monolayers, liquid crystals, foams and aerosols.
Macromolecules: Introduction, Classification, Nomenclature, Viscosity, Molecular weight determination, Flory-Huggins theory, Amorphous and semicrystalline states, glass transition and related theories, melt transition, viscoelasticity, Maxwell-Voight models, Rubber elasticity – thermodynamic theories.
CY 5017 - Principles Of Quantum Mechanics
Review of vectors and vector spaces, matrices and determinants, eigenvalues and eigenvectors, similarity transformations, ordinary differential equations- first and second order.
Solution of differential equations by power series method: solutions of Hermite equation in detail. Orthogonality properties and recurrence relations. Introduction to the solutions of Legendre and Laguerre differential equations, Spherical Harmonics. Introduction to Fourier series and Fourier transforms, convolution theorem.
Solution of the Schrodinger equation for exactly solvable problems such as particle-in-a- box, particle-in-a-ring, harmonic oscillator and rigid rotor. Tunneling, one dimensional potential barriers and wells.
Postulates of quantum mechanics, wave functions and probabilities, operators, matrix representations, commutation relationships. Hermitian operators, Commutators and results of measurements in Quantum Mechanics. Eigenfunctions and eigenvalues of operators and superposition principle. States as probability distributions and expectation values. The expansion of arbitrary states in terms of complete set.
Angular momentum, commutation relationships, basis functions and representation of angular momentum operators, Coupling (addition) of angular momenta, Clebsch-Gordan coefficients and Wigner-Eckart theorem.
Solution of the Schrodinger equation for the hydrogen atom, radial and angular probability distributions, atomic orbitals and electron spin, Pauli’s exclusion principle and Aufbau principle.
The time dependent Schrödinger equation. Co-ordinate and momentum space representation of operators and eigenstates; Properties of eigenstates – single-valuedness, double differentiability, continuity, boundedness / square integrability. Discrete and continuous distributions; Unitary evolution and reversibility. Schrodinger and Heisenberg representations. Projections and irreversibility.
Time-independent perturbation theory, degenerate states, variational method, Hellmann-Feynman theorem Spectra and structure of helium atom, term symbols for atoms.
CY 5018 - Quantum Chemistry And Group Theory
Born-Oppenheimer approximation, hydrogen molecule ion, hydrogen molecule: valence bond and molecular orbital methods: Detailed calculations for energies and overlaps.
Polyatomic molecules and hybridisation. Conjugated pi-systems and Huckel theory, frontier orbital theory, configuration interaction.
Hartree-Fock method, self-consistent field method and derivation of Hartree-Fock, Roothaan Equations.
Polyatomic basis sets, Gaussian, double-zeta and polarized basis sets, population analysis and dipole moments. The Thomas-Fermi model of the atom.
The metallic bond. Bloch theory, free electron and tight binding model. Effective crystal field Hamiltonian: Steven's equivalent operator method.
Electric and magnetic properties of molecules. Introduction to multipole expansion, dipole moments, static polarizability and hyperpolarizability, magnetic susceptibility, vector functions and vector potential: shielding constants, spin-spin coupling and hyperfine interactions.
The concept of groups, symmetry operations and symmetry elements in molecules, matrix representations of symmetry operations, point groups, irreducible representations and character tables.
Great orthogonality theorem and its proof.
Application of group theory to atomic orbitals in ligand fields, molecular orbitals, hybridization.
Classification of normal vibrational modes, selection rules in vibrational and electronic spectroscopy. Woodward-Hoffmann rules.
CY 6017 - Principles of Molecular and Magnetic Resonance Spectroscopy
Interaction of radiation with matter, Einstein coefficients, time dependent perturbation theory, transition probability, transition dipole moments and selection rules, factors that control spectral linewidth and lineshape. Beer-Lambert law and absorbance.
The rigid diatomic rotor, energy eigenvalues and eigenstates, selection rules, intensity of rotational transitions, the role of rotational level degeneracy, the role of nuclear spin in determining allowed rotational energy levels. Classification of polyatomic rotors and the non-rigid rotor.
Vibrational spectroscopy, harmonic and anharmonic oscillators, Morse potential, mechanical and electrical anharmonicity, selection rules. The determination of anharmoncity constant and equilibrium vibrational frequency from fundamental and overtones. Normal modes of vibration, G and F matrices, internal and symmetry coordinates.
Electronic transitions, Franck-Condon principle. Vertical transitions. Selection rules, parity, symmetry and spin selection rules. Polarization of transitions. Fluorescence and phosphorescence.
Raman spectroscopy, polarizability and selection rules for rotation and vibrational Raman spectra.
Expression for Hamiltonian/Energy - Zeeman interaction, torque exerted by a magnetic field on spins, equation, its solution and the physical picture of precession. Thermal equilibrium, Curie susceptibility. Expressions for MR spectral sensitivity. Approach to equilibrium, Bloch equations, the rotating frame, Steady state (continuous wave) and Transient (pulsed) experiments, solutions of classical master equation. Absorption and dispersion in cw and pulse experiments, the complex Fourier transform. Field modulation in cw MR and derivative EPR lineshapes.
The spin Hamiltonian, isotropic and anisotropic interactions.
The EPR Hamiltonian. Theory of g-factors in EPR, transition metal complexes, rare earth complexes. Theory of hyperfine interactions in π−type free radicals, McConnell relation. The NMR Hamiltonian, shifts and couplings.
The Solomon equations and cross-relaxation, the Overhauser effect, steady state NOE, sensitivity enhancement, transient NOE, interatomic distance information.
The spin echo. Vector picture and algebraic expressions for effect on spin evolution under field inhomogeneities, chemical shifts and homonuclear/heteronuclear couplings, the basis of heteronuclear decoupling.
Polarization transfer. Selective Population Inversion, INEPT and RINEPT, sensitivity enhancement and spectral editing.
CY 5022 - Inorganic Chemistry Laboratory
Qualitative and quantitative estimations, synthesis, separation, purification, characterization and property measurements of inorganic compounds with an emphasis on different techniques of reaction set-up (air-sensitive, moisture-sensitive etc.). Exposure to various spectroscopic characterization techniques.
CY 5019 - Organic Chemistry Laboratory
Separation of two-component mixtures of organic compounds. Synthesis and isolation of organic compounds with an emphasis on different techniques of reaction set-up (air-sensitive, moisture-sensitive etc.), separation / purification (extraction, Soxhlet extraction, recrystallization, distillation, column chromatography) and monitoring of reaction by TLC. Structure determination of the isolated pure compounds by NMR spectroscopy, IR Spectroscopy and Mass spectrometry.
CY 5024 - Physical Chemistry Laboratory
Experiments on thermodynamics, kinetics, catalysis, electrochemistry, spectroscopy, photochemistry and macromolecules.
CY 5021 - Computational Chemistry & Experimental Magnetic Resonance
Bound-state ab initio quantum mechanical & density functional calculations, understanding of basis set types and sizes, computational scalability, Hartree-Fock and Post-Hartree-Fock calculations for determining electronic energies and associated molecular properties, electronic structure and thermochemical properties, geometry optimization, study of reaction mechanism, transition-state optimizations
Molecular Force-field calculations
Magnetic resonance experiments for physicochemical characterization of molecular systems
CY 6021 - Project
Objectives: To introduce students to research in various areas of chemistry by engaging them to carry out a project under the supervision of a faculty for two semesters during the third and fourth semesters.
Course content: Depends upon the type of project taken up by the student.
CY 6102 - Advanced Bioinorganic Chemistry
Essential and trace metal ions in biology and their distribution, thermodynamic and kinetic factors for the presence of selected metal ions; bioligands- amino acids, proteins, nucleic acids, nucleotides and their potential metal- binding sites; special ligands - porphyrins, chlorin and corrin.
Enzymes- Nomenclature and classification, chemical kinetics, the free energy of activation and the effects of catalysts kinetics of enzyme catalyzed reactions- Michaelis-Menten constant- effect of pH, temperature on enzyme reactions, factors contributing to the catalytic efficiency of enzymes.
O2 binding and activation by heme, non-heme and copper proteins – MMO & RNR, tyrosinase; DβM, PHM, Cytochrome c oxidase.
Iron transport and storage proteins in bacterial and mammalian systems – siderophores, transferrin, ferritin.
Electron transport proteins – redox properties, organic- redox protein cofactors – FAD, NAD, FMN, ubiquinone; blue copper proteins, cytochromes, iron- sulfur proteins – rubredoxin, ferridoxins, HIPIP; electron transport chain (ETC) in respiration, nitrogen-fixation and photosynthesis.
Nitrogen-cycle enzymes: Mo in N, and S-metabolism by Mo-pterin cofactors and Mo-Fe-cofactors. NOx reductases, sulfite oxidase, xanthine oxidase, nitrogenase, P and M- clusters in nitrogenase, transition-metal-dinitrogen complexes and insights into N2 binding, reduction to ammonia.
Mn in photosynthesis and O2 evolution: Photosystem I and II – chlorophyll, oxygen evolving complex (OEC), 4Mn-cluster and O2 evolution.
Non-redox enzymes with Mg, Zn, Ni: urease, peptidases and phosphatases and their structure and function. Carbonic anhydrase and carboxy peptidase.
Applied bioinorganic chem–metals in medicine, anti-cancer agents–cisplatin, radiopharmaceuticals (Tc), diagnostic (Gd in MRI) and therapeutic agents. Toxicity of Hg, Cd, Pb and As and chelation therapy.
CY 6103 - Chemistry of Crystalline Inorganic Solid State Materials
Synthesis, structure, properties, structure-property correlations and potential applications of crystalline inorganic solid state materials.
Superconductors – (Ba,K)BiO3, Cuprates, LnFeAsO, MgB2, CaC6
CMR materials – La1-xSrxMnO3
Ferroic compounds – BaTiO3, PbTiO3, Bi4Ti3O12, SrRuO3
Photoluminescent materials – Lanthanide compounds
Porous materials – zeolites, AlPO, MeAlPO, SAPO.
Organic-inorganic hybrid materials – Ruddlesden-Popper (RNH3)2An-1MX3n+1 series of metal halides, MOF compounds
Ionic Conductors – NASICON, AgI, NaAl11O17
Thermoelectric materials – NaxCoO2, AgSbTe2, CoSb3, Y14MnSb11
Compounds for intercalation and redox reactions – LiCoO2, LiVS2, NASICON, Chevrel phases
Other relevant examples from recent literature
CY 6104 - Molecular Clusters
Introduction to molecular clusters
Main-group clusters: Geometric and electronic structure, three-, four- and higher connect clusters, the closo-, nido-, arachno-borane structural paradigm, Wade-Mingos and Jemmis electron counting rules, clusters with nuclearity 4-12 and beyond 12. Structure, synthesis and reactivity.
Transition-metal clusters: Low nuclearity metal-carbonyl clusters and 14n+2 rule, high nuclearity metal-carbonyl clusters with internal atoms. Structure, synthesis and reactivity. Capping rules, isolobal relationships between main-group and transition metal fragments, metal-ligand complexes vs heteronuclear cluster.
Main-group-Transition-metal clusters: Isolobal analogs of p-block and d-block clusters, limitations and exceptions.
Clusters having interstitial main group elements, cubane clusters and naked or Zintl clusters.
Molecular clusters in catalysis, clusters to materials, boron-carbides and metal-borides.
Illustrative examples from recent literature.
CY 6105 - Supramolecular Chemistry
Definition of supramolecular chemistry. Nature of binding interactions in supramolecular structures: ion-ion, ion-dipole, dipole-dipole, H-bonding, cation-p, anion-p, p-p, and van der Waals interactions.
Synthesis and structure of crown ethers, lariat ethers, podands, cryptands, spherands, calixarenes, cyclodextrins, cyclophanes, cryptophanes, carcerands and hemicarcerands., Host-Guest interactions, pre-organization and complimentarity, lock and key analogy. Binding of cationic, anionic, ion pair and neutral guest molecules.
Crystal engineering: role of H-bonding and other weak interactions.
Self-assembly molecules: design, synthesis and properties of the molecules, self assembling by H-bonding, metal-ligand interactions and other weak interactions, metallomacrocycles, catenanes, rotaxanes, helicates and knots.
Molecular devices: molecular electronic devices, molecular wires, molecular rectifiers, molecular switches, molecular logic.
Relevance of supramolecular chemistry to mimic biological systems: cyclodextrins as enzyme mimics, ion channel mimics, supramolecular catalysis etc.
Examples of recent developments in supramolecular chemistry from current literature
CY 6106 - Organometallic Chemistry for Organic Synthesis
Review of formalisms such as oxidation state, 18-electron rule, classes of ligands, structure and bonding. Review of reaction mechanisms, ligand substitution, oxidative addition, reductive elimination, migratory insertion, hydride elimination, transmetallation, nucelophilic and electrophilic attack on the ligands coordinated to metals.
Organo zinc and copper reagents, preparation using transmetallation, functionalized zinc and copper reagents, synthetic applications in conjugate addition and allylic and propargylic substitution reactions.
Organo tin reagents, hydrostannation reaction and synthetic utility of vinylstannanes and allylstannanes in addition and substitution reactions.
Organoboron and aluminium reagents, alkyl and aryl derivatives, synthesis and examples of applications in C-C bond forming reactions.
Organotitanium and zirconium reagents, metallocene complexes in C-C bond forming reactions. Addition to enynes and diynes, hydrozirconation, metallocycle formation and their synthetic utility.
Metal (W, Cr, Rh, Ru, Mo) carbene complexes, Fischer, Schrock and Grubbs type carbene complexes, comparison of their stability and reactivity, reactions of Fischer carbene complexes and their synthetic utility, Dötz reaction, simple and cross metathesis reactions, ring opening, ring closing metathesis in organic synthesis, examples from macrocycles synthesis. Copper and rhodium based carbene and nitrene complexes, cyclopropanation, Rh catalysed C-H insertion and aziridination reactions including asymmetric version. Introduction to N-heterocyclic carbene metal complexes.
Metal (Fe, Cr, Mo, Ni, Co, Rh) carbonyl compounds in organic synthesis. C-C bond forming. Cyclooligomerization of alkenes, enynes and alkynes, Vollhardt reaction. Carbonylation and decarbonylation reactions and hydroformylation reaction.
Metal (Fe, Pd) ene, diene and dienyl complexes, metal complexes as protecting groups, activation towards nucleophilic addition reaction and rules governing such additions, synthetic utility. p-allyl palladium, nickel and iron complexes, synthesis and their synthetic utility. Various Wacker type oxidation and cyclization reactions including asymmetric version.
Metal (Co, Zr) alkyne complexes, protection of triple bond, C-C bond forming reactions such as Pauson-Khand reaction, alkyne cyclotrimerization and oligomerization reaction.
Metal (Cr, Fe, Ru) arene complexes, synthesis and structure. Activation of arene nucleus and side chain. Nucleophilic substitution and addition of arene.
Metal (Rh, Ir) catalyzed C-H activation reactions and their synthetic utility.
CY 6107 - Heterocyclic Chemistry
Nomenclature and classification of heterocycles
Structure, preparation and reactions of a) heterocyclic analogues of cyclopropane, cyclobutane, cyclopentadiene and benzene containing one or more heteroatoms (azeridine, oxirane, thiirane, oxaziridine, azetidine, azetidinone, oxetane, oxetanone, thietane, pyrrole, furan, thiophene, 1,2- and 1,3-azoles, triazoles, pyridine, pyryliums, diazines, triazine and their oxy-derivatives); b) fused heterocycles containing one or more heteroatoms (indoles, benzofurans, benzothiophene, benzanellated azoles, quinolines, isoquinolines, benzopyrones)
Heterocycles in natural products, medicine and materials.
CY 6108 - Medicinal Chemistry
Concept and definition of Pharmacophore. Pharmacodynamics and Pharmacokinetics –. Drug targets: enzymes and receptors. Competitive, non-competitive and allosteric inhibitors, transition-state analogs and suicide substrates. Nucleic acids as drug targets: reversible DNA binding agents, DNA alkylating agents and DNA strand breakers. ADMET of drugs: Factors affecting Absorption, Distribution, Metabolism, Elimination and Toxicity.
Drug Discovery, Design and Development. Structure-activity relationships: Strategies in drug design. QSAR and combinatorial synthesis. Optimization of drug-target interactions and access to drug targets. Pro-drugs and drug delivery systems.
Illustration of drug development through specific examples: a) Antibacterials: sulfonamides and penicillins b) Antivirals: case studies with inhibitors of reverse transcriptase (nucleoside reverse transcriptase- and non-nucleoside reverse transcriptase inhibitors) and protease inhibitors. c) Anticancer agents: antimetabolite-based approaches, those which affect signaling pathways or structural proteins such as tubulin. Drug resistance, Drug synergism and combination therapy.
CY 6109 – Photochemistry
Principles and concepts: An overview of: Laws of photochemistry, Beer-Lambert law, electronic energy levels, atomic and molecular term symbols, singlet-triplet state, intensity and strength of electronic transition, selection rules for electronic transition, Jablonski diagram and photophysical processes, Franck-Condon principle.
Excited state lifetime, steady state and time resolved emission, factors affecting excited state energy: solvent effect, TICT.
Excited state kinetics, quantum yield expressions, excimer and exciplex, kinetics of luminescence quenching: static and dynamic, Stern-Volmer analysis, deviation from Stern-Volmer kinetics. Photoinduced electron transfer rates, free energy dependence of electron transfer on rate, Photoinduced energy transfer, FRET, rate and efficiency calculation of FRET.
Methods: Measurement of fluorescence and phosphorescence and lifetimes. Introduction to time-resolved techniques for absorption and emission measurements, detection and kinetics of reactive intermediates. Examples of low temperature matrix isolation of reactive intermediates.
Reactions: Photochemistry of alkene, cis-trans isomerization, photocycloaddition reactions of alkene, photochemical electrocyclic and sigmatropic reactions, di-pi-methane rearrangment, electron transfer mediated reactions of alkene. Photochemistry of carbonyl compounds, Norrish type I and type II reactions, enone and dienone cycloadditions. Photochemistry of aromatic systems, electron transfer and nucleophilic substitution reactions. Photochemistry of nitro, azo and diazo compounds. Photochemistry involving molecular oxygen, generation and reactions of singlet oxygen. Photo-fragmentation reactions (Barton, Hofmann-Loffler-Freytag)
Fluorescence based sensors – examples of molecular and supramolecular systems. Conversion of solar energy to chemical and other forms of energies, solar photovoltaic cell, basic principle and design of the cell.
CY 6110 - Stereoselective Synthesis of Natural Products
Broad classification of natural products. Isolation, biosynthesis and stereo/enantio-selective synthesis of representative examples from the domain of Alkaloids, Steroids, Terpenes, Hormones, Pheromones, Macrolides, Penicillins and Prostaglandins. Synthesis of lead molecules based on natural products for different therapeutic areas.
CY 6111 - Electron Spectroscopy
Photoelectric effect: Need for electron spectroscopy, basic principles of electron spectroscopy, classification of various spectroscopic techniques, history.Photoelectron spectroscopy: Electron energy analysis; photon sources -- UV, X-ray, synchrotron; vacuum - angular dependence - cross section and its determination; valence and core photoemission - Koopmans’ theorem; final state effects; photoelectron diffraction; band structure- holography- circular dichroism - supersonic molecular beam spectroscopy - coincidence studies. Applications of photoelectron spectroscopy – catalysis, surface structure. Size dependence of electronic structureAuger electron spectroscopy: introduction - instrumentation - classification of various transitions - quantification - applications.
Electron energy loss spectroscopy: Franck and Hertz experiment -- instrumentation -selection rules-theory - studies on molecules - surface states - high resolution spectroscopy - adsorption and catalysis –applications.
Related techniques: Inverse photoemission - multiphoton ionization - electron momentum spectroscopy - photoionization-photodetachment - zero kinetic energy photoelectron spectroscopy - spin resolved photoemission - recent advances in instrumentation-brighter photon sources. Several of form of infra-red spectroscopy, viz., transmission, diffuse reflectance (DRIFT), reflection-absorption (RAIRS) and multiple internal reflection (MIR).
CY 6112 - Surface Chemistry and Catalysis
Surface phenomena: Structure of clean surfaces; Notation of surface structure; Structure of adsorbate layers; Stepped surfaces; Surface relaxation and reconstruction; Dynamics and energetics of surfaces.
Heterogeneous Catalysis: Adsorption isotherms, surface area, pore size and acid strength measurements; Porous solids; Catalysis by metals, semiconductors and solid acids; Supported metal catalysts; Catalyst preparation, deactivation and regeneration. Model catalysts: Ammonia synthesis; Hydrogenation of carbon monoxide; Hydrocarbon conversion.
Instrumental methods of catalyst characterization: Diffraction and thermal methods; spectroscopic and microscopic techniques.
CY 6113 - Chemistry of Macromolecules
Basic concepts - classification, nomenclature, molecular weights, molecular weight distribution, glass transition, degree of crystallinity, morphology, and viscosity-molecular weight, mechanical property - molecular weight relationships.
Molecular weights and Methods of determination, molecular weight distribution, size and shape of macromolecules. Intrinsic viscosity, Mark-Houwink relationship.
Chain structure and configuration, conformation, size of an ideal chain (freely jointed chain and other models), Real chains, Flory theory.
Thermodynamics of polymer solutions.
Molecular motion (self-diffusion, hydrodynamic radius, Rouse Model, Zimm Model, entangled polymer dynamics and de Gennes reptation model).
Glass transition temperature – elementary theories and methods of determination. Variation of glass transition with structure.
Rubber elasticity - concepts, thermodynamic equation of state. Elementary theories of viscoelasticity (Maxwell, Voight).
Mechanisms and Methods of Polymerization - Step (condensation) polymerization - Description - Reactivity Functional Groups - Kinetic and thermodynamic considerations - Molecular weight distribution. Chain polymerization, controlled radical polymerizations (INIFERTER, ATRP, RAFT, SET). Living Polymerizations. Ziegler-Natta and metathesis polymerizations.Selected Applications
CY 6114 - Chemical And Electrochemical Energy Systems
Available energy options, their advantages and disadvantages. Environmental effects, comparative evaluation of energy options and energy needs.
Fossil fuels: petroleum, natural gas and coal - Origin, processing and production of value added products - available current conversion technologies.
Nuclear Energy: Principles of Fission - Fission reactors, U enrichment and processing of spent fuels. Nuclear reactor kinetics and control - nuclear fusion - magnetic and other confinement - evaluation of the option of nuclear energy.
Electrochemical power sources - theoretical background on the basis of thermodynamic and kinetic considerations.
Primary cells - various types, especially magnesium and aluminium based cells - magnesium reserve batteries.
Secondary cells: classification based on electrolyte type, temperature of operation on the basis of electrodes - chemistry of the main secondary batteries - Batteries for electric vehicles - present status.
Fuel cells - classification - chemistry of fuel cells - detailed description of hydrogen/oxygen fuel cells - methanol - molten carbonate solid polymer electrolyte and biochemical fuel cells.
Solar energy conversion devices - photovoltaic cells - photoelectrochemical cells - semiconductor electrolyte junctions photocatalytic modes for fuel conversion process - photobiochemical options.
Hydrogen as a fuel - production (thermal, electrolysis, photolysis and photoelectrochemical) storage and applications of hydrogen storage.
Other methods of energy conversion: processes especially in the form of storage as chemical energy.
CY 6115 - Chemistry of the Earth’s Atmosphere
Introduction to the Earth’s Atmosphere:
Evaluation of the Earth’s atmosphere – Layers of atmosphere – Pressure and Temperature variations – Scaling of atmospheric processes.
Role of Chemical Compounds on Ozone budget:
Chemical composition of the Earth’s atmosphere – Compounds containing Sulfur, Nitrogen, Carbon, Halogens – Atmospheric Ozone – Ozone loss – role of the chemical compounds – Atmospheric lifetimes – Theories – Determination of the lifetimes – Laser Induced Fluorescence Studies (LIF measurements) – Cavity Ring Down method; Radicals in the Earth’s atmosphere – Ozone generation – Global warming – Global Warming Potential (GWP) – Ozone Depletion Potential (ODP)
Chemistry of Troposphere and Stratosphere:
Troposphere – Chemistry of hydroxyl radicals – Photochemical cycles of NO2, NO and O3 – Chemistry of NOx and carbon monoxide – Methane – Tropospheric reservoir molecules – H2O2, CH3OOH, HONO, PAN, Role of VOC and NOx in the ozone formation – Chemistry of VOCs – sulfur compounds – nitrogen compounds;
Stratosphere – Chapman mechanism – HOx cycle – Halogen cycles – Antarctic ozone hole – Polar stratospheric clouds – Heterogeneous stratospheric chemistry – Global sulfur and carbon cycles – Role of H2O in both troposphere and the stratosphere.
Atmospheric Radiation and Photochemistry:
Radiation – Terrestrial and solar radiation – Energy balance for Earth and Atmosphere – Radiative flux – Actinic flux; Photochemistry – Absorption of radiation by atmospheric gases – Absorption by O2 and O3 – Photolysis rate as a function of altitude – Photodissociation of O3, NO2.
Aerosols and Other Physical Processes:
Aerosols – formation – Size distribution – Chemical composition – thermodynamics of aerosols; Nucleation – Classical theory of homogeneous nucleation – Experimental measurement of nucleation rates – heterogeneous nucleation; Wet and dry deposition.
CY 6116 - Advanced Solution Thermodynamics
Ideal and non-ideal solutions, activity and activity coefficients, mixing and excess properties of liquid-liquid mixtures. Theories of solutions of electrolyte and non-electrolyte liquids: van Laar theory, van der Waals theory, Scatchard-Hildebrand theory, Lattice theory, Prigogine Cell theory, Flory equation of state theory, Prigogine-Flory-Patterson theory, Extended Real Associated Solution model and Kirkwood-Buff theory.
Modern experimental techniques: determination of vapour-liquid equilibrium by static and dynamic methods, heat capacity and heat of mixing by calorimeters, and determination of volumetric, transport, acoustic and optical properties of liquid-liquid mixtures. Thermodynamic relations of excess Gibbs energy, excess entropy, excess enthalpy, excess volume, viscosity deviation, excess heat capacity and excess compressibility. Partial molar properties, their physical significance and methods of their determination. Study of non-ideal behaviour of various types of solutions: nonpolar + nonpolar, polar + nonpolar, polar + polar, and mixtures with hydrogen-bond formation and charge transfer complexes; interpretation in terms of molecular interactions.
Empirical and semi-empirical formulas, theoretical expressions, correlations, group contribution methods and computational models for the prediction of thermodynamic properties of liquids and liquid mixtures.
CY 6117 - Advanced Optical Spectroscopy
Overview of basic concepts: Light-matter interaction, Einstein coefficients, introduction to lasers, transition dipole moment, selection rules for electronic transitions, Jablonskii diagram, fluorescence and phosphorescence, kinetics of unimolecular and bimolecular processes.
Advanced concepts: Theory of nonradiative transitions, spin-orbit coupling and singlet-triplet transitions, polarized light absorption and emission: fluorescence anisotropy, solvation dynamics, energetics and dynamics of bimolecular processes like excimer and exciplex formation, resonance energy transfer, mechanisms of fluorescence quenching, introduction to non-linear spectroscopy.
Techniques and instrumentation: Uv-Vis spectrophotometry, steady-state fluorimetry, lasers as excitation sources, time-resolved fluorimetry, transient absorption spectroscopy, surface plasmon spectroscopy, evanescent wave spectroscopy, multiphoton spectroscopy, single-molecule spectroscopy, fluorescence correlation spectroscopy.
Applications: Microscopy (optical, phase-contrast, confocal, FLIM). Applications in biology and analytical chemistry.
CY 6118 - Experimental Methods in Chemistry
Vacuum and Gas Pressure: Concepts of vacuum (Low, medium, high and ultra-high vacuum; vacuum pumps and gauges; pressure measurements; ); kinetic theory concepts (molecular density; mean free path of particles in the gas phase; incident molecular flux on surfaces; gas exposure; sticking coefficient; surface coverage; variation of parameters with pressure).
Over layers and Diffraction: Two-dimensional lattice; reciprocal space; over layer structure; low energy electron diffraction (LEED).
Imaging and Depth Profiling: Basic concepts in surface imaging; secondary electron microscopy (SEM); secondary Auger microscopy (SAM); scanning probe microscopy (SPM); scanning tunneling microscopy (STM); transmission electron microscopy (TEM); surface imaging; depth profiling. Associated techniques of microscopy and spectroscopy.
Chemical Analysis: Non-destructive techniques: Wavelength and energy dispersive X-ray fluorescence spectroscopy (WDS and EDS); X-ray absorption spectroscopy (XANES and EXAFS); secondary ion mass spectrometry (SIMS); temperature programmed desorption (TPD); thermal desorption spectroscopy (TDS). Destructive techniques: Atomic absorption spectroscopy (AAS); inductively coupled plasma-atomic emission spectroscopy (ICP-AES).
Electroanalytical Techniques: Voltametry; coulometry; amperometry; potentiometry; polarography; electrolytic conductivity; impedance spectroscopy.
Separation Methods: Normal and reversed phase liquid chromatography (NP- & RP-LC); Gas Chromatography (GC); GC-MS; High Performance Liquid Chromatography (HPLC); Size-Exclusion Chromatography (SEC); Ion Chromatography (IC).
Reading assignments on: Quantitative measurements: Limit of detection, limit of quantification, sensitivity, calibration, interferences, sampling; Laboratory practice, laboratory automation.
CY 6119 - Group Theory and Molecular Spectroscopy
The complete nuclear permutation and permutation – inversion group, molecular symmetry groups, Double groups, point group symmetry, representation and character tables. The molecular Hamiltonain and its symmetry. Nuclear spin statistics. Examples of application of MS group to non-rigid molecules and molecular complexes.
General formalism for molecular Hamiltonians in curvilinear coordinates –Podolsky transformation, Echart-Sayvetz. Rotational – vibrational Hamiltonians with emphasis on coupling terms for semirigid diatomic and polyatomic molecules. The Wilson – Howard – Darling - Dennison and the Watson Hamiltonians. Contact transformation and the derivation of effective rotational Hamiltonians for vibrational degrees of freedom. Coriolis and centrifugal coupling. Advanced theory of line intensities for infrared and Raman Spectra. Symmetry of ro-vibronic wave function and introduction to vibrational – rotational spectra of non-rigid molecules and molecular complexes
CY 6120 - Molecular and Statistical Reaction Dynamics and Scattering
Transition state Theory – Thermodynamics formulation; micro-canonical and variational transition state theory; flexible transition states. Unimolecular reaction dynamics, RRK and RRKM models, thermal activation, density of state. State preparation and intra molecular vibration energy distribution; stochastic master equation approach dynamical approaches to unimolecular reaction rates.
Electron transfer reactions, Marcus model. Statistical density operator for molecular states and the equations of motion for chemical system; Chemical reactions in solutions, diffusion equation, Kramer’s and Grote –Hynes models. Quantum theory of reaction rates – flux-flux correlation function approach. Kubo formalism Quantum transition state theory.
Potential energy surface, bimolecular reaction, elementary quantum dynamics. Microscopic reversibility and detailed balance. Different forms for intermolecular potentials. Statistical sampling for simulations. The Metropolis Monte Carlo method; finite difference methods such as verlet algorithm and predictor-corrector methods. Introduction to quantum Monte Carlo. Procedure. Introduction to time-correlation and autocorrelation functions.
Molecular Scattering (elementary aspects only):
Bimolecular collisions, collision number two-body classical scattering. Cross sections, intermolecular potentials, import parameter principle of microscopic reversibility. Quantum theory of scattering: particles in central potentials partial waves, Born approximation optical theorem. Formal time independent scattering theory. The S matrix. The Lippmann – Schwinger equation – for structureless particles. Rate of change of observables, collision rates in ensembles and the relaxation equation. The wave (Moller) operator and time dependent collision theory, time reversal and reciprocity
CY 6121 - Advanced Electronic Structure and Density Functional Theory for Molecules
The Hartree – Fock method, derivation and interpretation of HF equations, Roothaan equations. Basis sets – Gaussian and Slater type orbitals Independent electron pair approximation, coupled cluster approximation, cluster expansion of a wave function. Configuration interactions. Many body approach Moller – Plesset perturbation theory. Diagrammatic representation, one particles perturbation. Static electric and magnetic properties of molecules and multiple expansions.
Density matrices, reduced density operators, Thomas – Fermis model, Hobenberg – Kohn theorem. Chemical potential. Hardness and softness, Kohn – Sham method – basic principles, local density and Xa approximation, spin density functional and local spin density approximation. Exchange correlation energy-functional. Introductory account of popular functionals – B3LYP and MPW1PW91.
Simple applications of density functional theory for electronic structure.
Electrons in the periodic lattice. Bloch states and Wannier functions.
Dynamics of interacting quantum spin systems in the presence of external fields – Ising and Heisenberg Hamiltonians. Theory of Ferromagnetism. Quantum phase transitions.
CY 6122 - Numeric Methods for Computational Chemistry
Introduction to C Programming:
Variables and arithmetic expressions, Symbolic Constants, Input and Output, Arrays and functions, Data types, arithmetic, relational and logical operators, simple control-flow statements, classes and modules and ability to write small programs in C for computations such as function evaluation and elementary linear algebra.
Introduction to FORTRAN programming:
Constants and variables, arithmetic, input and output statements, control statements (Do, Go To If statements) , arrays, subprograms (Functions and subrountines), modules and ability to write small programs for computations such as function evaluation and elementary linear algebra.
Numerical interpolation, Polynomial and cubic spline interpolation, extrapolation of data.
Numerical first and second derivatives, error analysis and Richardson’s method.
Non-linear equations and roots of polynomials, Newton-Raphson method, secant method and Bairstow method.
Numerical integration: Gaussian quadrature—Gauss-Hermite and Gauss-Legendre intervals; applications form quantum chemistry with Gaussian orbitals
Linear algebra: Householder reduction and LU decompositions, matrix inversion, determinant evaluation and eigenvalues and eigenvectors of hermitian (complex) and symmetric (real) matrices.
Iterative methods for large-scale eigen value problems – Lanczos recursion, Arnoldi algorithm and Davidson’s method. Or Fast Fourier transform, Fourier transform of real data in two and three dimensions.
Introduction to finite basis representation and discrete variable. Simple applications from computational chemistry and spectroscopy.
CY 6101 - Magnetic Resonance Imaging
Introduction to Magnetic Resonance - Principles of Spatial encoding in Magnetic Resonance - application of magnetic field gradients - Larmor frequency as a function of position - frequency encoding - the generation of profiles in NMR and ESR experiments run in the presence of gradients
Combination of frequency encoding with phase encoding for 2D imaging; ‘field of view’ in phase and frequency directions; the basic Fourier imaging experiment (‘spin warp imaging’) - gradient echoes; spin echo imaging; chemical shift selective imaging
Reciprocal space (k space) description of imaging experiments - parallel, radial and single pass raster techniques
Slice selection for 2D imaging - shaped pulses and slice profiles; slice thickness as a function of selective pulse bandwidth and slice gradient; gradient trimming for magnetization refocusing; multiple slice selection
3D Fourier imaging with two phase encode gradients; Echo Planar Imaging
Metabolite imaging; Diffusion weighted imaging; flow imaging
Materials and in vivo applications
Multiple Quantum (mq) imaging - point scan in k space with phase encoding alone; combination of mq phase encode with sq frequency encode for line scans in k space; applications to polymers, solution state and lyotropics
Spectral-Spatial imaging - chemical shift imaging (csi); mq-csi
NMR Imaging of solids - stray field imaging (STRAFI); projection reconstruction imaging
CW ESR imaging
Volume selective spectroscopy
CY 6998 - Electrochemical Approaches to Functional Supramolecular Systems
The course embodies a combined approach of supramolecular chemistry with electrochemistry that has produced a wealth of interesting functions and devices and their practical applications in energy conversion technology, advanced materials and diagnostics. The objective of the course is to bring forth the current electrochemical research applied to multi-component chemical systems with a special attention to properties and functions. The course, structured for ~ 40 lectures during an even semester, will cater to Ph. D as well as M. Sc / M. Tech graduate students (in a limited sense to B. Techs) who wish to explore the frontiers of electrochemistry with materials and nanosciences.
The essential features of the syllabus are the following:
(1) Analytical electrochemistry
Fundamental Concepts in Analytical Electrochemistry
Mass transport, Linear diffusion, Fick’s laws and diffusion coefficient, The charged interface, Potential step and potential sweep experiments, Reactions controlled by rate of electron transfer and activated complex theory
Electrode Types and Study of Electrode Reactions:
Carbon electrodes, Semiconductor film electrodes, Microelectrodes, Ultra-micro electrodes, Ion-selective electrodes, Porous electrodes and non uniform reaction rates, Hydrodynamic/Rotating disk electrodes, Semiconductor electrodes and electrical capacitance
Cyclic voltammetry in reversible, quasi-reversible and irreversible systems, Study of reaction mechanisms, Surface modification in charge transfer and interfacial activity Electron transfer in DNA and biosystems
Spectro-Electrochemical and Spectroscopic Techniques:
Impedance Spectroscopy, Scanning Electrochemical Microscopy, Electrochemical AFM and STM, , Electrochemical Quartz Crystal Microbalance
Electrochemical Materials and Sensors:
Electroactive Fullerenes, Carbon Nanotubes, Biomolecules, Controlled Potential Techniques, Electrochemical synthesis of nanomaterials, nanowires and conducting polymers, Functional nanoparticles as catalysts and sensors, MOSFETS and ISFETS, Solid state molecular devices
Electrochemical Energy Systems:
Photo-electrochemistry, Monitoring photolytic intermediates, Electroluminescence and devices and sensors, Electro - chemiluminescence, Digital simulation of electrochemical problems, Sample BASIC programs
Fuel cells: Electrode materials, Diagnostic tools in fuel
cell research, Determination of injection efficiency and
electron diffusion length under steady state condition,
Small-amplitude time-resolved methods, Organic solar cells
1. Allen J. Bard and Larry R. Faulkner, Electrochemical
Methods: Fundamentals and Applications, 2nd edition 2001,
John Wiley & Sons