COMPUTATIONAL CHEMISTRY

Introduction, Scope of computational chemistry.

Molecular mechanics / force field methods, the force field energy, advantages and limitations of molecular mechanics methods.

Electronic Structure Methods: The Schrödinger equation, molecular Hamiltonian, Born-Oppenheimer approximation, self-consistent field theory, Koopmans’ theorem, Hartee-Fock theory, restricted and unrestricted Hartree-Fock, the variation principle, SCF techniques, Rootham-Hall equation, semi-empirical methods: AM1, MNDO-PM3, limits and advantages of semi-empirical methods.

Excited slater determinants, Configuration Interaction (CI), Multi-configuration Self-consistent Field (MCSCF), Complete Active Space Self-consistent Field (CASSCF), Møller-Plesset perturbation theory, Coupled Cluster (CC) methods, density functional theory, local density methods, gradient corrected methods, hybrid methods.

slater and Gaussian type orbitals,split-valence sets, polarization and diffuse functions,classification of basis sets, even- and well-tempered basis sets, Pople style basis sets, Dunning-Huzinga basis sets, correlation consistent basis sets, extrapolation procedures, effective core potential basis sets. 

Introduction to Potential Energy Surface(PES), local minimum, global minimum, and saddle point, convergence criteria, transition structures, frequency calculations, zero-point corrections, thermo chemistry, Intrinsic Reaction Coordinate (IRC) analysis(giving suitable example), calculation of activation and reaction enthalpies, isodesmic and isogyric reactions.

Relative stabilities of cyclopropane, oxirane, azirane and phosphirane; aromaticity indices: Julg concept, aromatic stabilization energies (ASE), nucleus independent chemical shift (NICS) values, magnetic susceptibility exaltation, ¹H NMR chemical shift values of cyclopropenium cation, cyclopentadienyl anion, cyclobutadiene (antiaromatic) and benzene, electron affinity, electrophilicity and nucleophilicity indices, chemical potential.

Application of DFT to thermodynamic properties, geometrics, charges (e.g.- glycine cation), dipole moment, electrostatic potential (acetyl chloride & acetamide), calculation of NMR parameters in transition metal complexes, application of Hybrid-DFT to Homogenous catalysis.

Phase Transformations: Definition and significance. Structural properties and optical properties of ZnS, Hydrostatic Pressure and Phase Transformation: Effects on the structural properties, Phase transformations under hydrostatic pressure. Calculation of pressure-dependent energy profiles.

Descriptors for Phase Transformation: Determination of transition pressures and temperatures, Analysis of structural changes, such as bond lengths, angles, and coordination environments under pressure, Calculation of bandgap and density of states, for different phases. Optical Properties: Calculation of absorption spectra and refractive index. Phase Diagram and Phase Stability: Construction and interpretation, Phase stability and phase coexistence regions, Thermodynamic factors governing phase transformations.