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Syllabus 2
Syllabus 2
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4.2 Rearrangement reactions of carbenes such as Wolff rearrangement, generation
and reactions of ylids by carbenoid decomposition.
4.3 Structure, generation and reactions of nitrene and related electron deficient nitrene
intermediates.
4.4 Hoffmann, Curtius, Lossen, Schmidt and Beckmann rearrangement reactions.
4.5 Arynes: generation, structure, stability and reactions. Orientation effect-
amination of haloarenes.
References
01. R. Bruckner, Advanced Organic Chemistry: Reaction Mechanism, Academic
Press, 2002.
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02. F.A. Carey, R.A. Sundberg, Advanced Organic Chemistry, Part B: Reactions and
Synthesis, 5th Edn., Springer, 2007.
03. W. Carruthers, I. Coldham, Modern Methods of Organic Synthesis, Cambridge
University Press, 2005.
04. J. March, M.B. Smith, March's Advanced Organic Chemistry: Reactions,
Mechanisms, and Structure, 6th Edn., Wiley, 2007.
05. A. Fleming, Frontier Orbitals and Organic Chemical Reactions, Wiley, 1976.
06. S. Sankararaman, Pericyclic Reactions-A Text Book, Wiley VCH, 2005.
07. R.T. Morrison, R.N. Boyd, S.K. Bhatacharjee, Organic Chemistry, 7th Edn.,
Pearson, 2011.
08. J. Clayden, N. Greeves, S. Warren, P. Wothers, Organic Chemistry, Oxford
University Press, 2004.
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CH2C07 CHEMICAL BONDING AND COMPUTATIONAL
CHEMISTRY
Credit: 4 Contact Lecture Hours: 72
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Unit 4: Computational Chemistry (18 Hrs)
(The units 4 and 5 have been designed to expose the students to the field of
computational chemistry, which has emerged as a powerful tool in chemistry
capable of supplementing and complementing experimental research. The
quantities which can be calculated using computational methods, how to prepare
the input to get these results and the different methods that are widely used to
arrive at the results are introduced here. Detailed mathematical derivations are
not expected. Though computer simulations form an important part of
computational chemistry, they are not covered in this syllabus.)
4.1 Introduction: computational chemistry as a tool and its scope.
4.2 Potential energy surface: stationary point, transition state or saddle point, local
and global minima.
4.3 Molecular mechanics methods: force fields-bond stretching, angle bending,
torsional terms, non-bonded interactions, electrostatic interactions. Mathematical
expressions. Parameterisation from experiments or quantum chemistry. Important
features of commonly used force fields like MM3, MMFF, AMBER and
CHARMM.
4.4 Ab initio methods: A review of Hartee-Fock method. Basis set approximation.
Slater and Gaussian functions. Classification of basis sets - minimal, double zeta,
triple zeta, split valence, polarization and diffuse basis sets, contracted basis sets,
Pople style basis sets and their nomenclature, correlation consistent basis sets.
4.5 Hartree-Fock limit. Electron correlation. Qualitative ideas on post Hartree-Fock
methods-variational method, basic principles of Configuration Inetraction(CI).
Perturbational methods-basic principles of Møller Plesset Perturbation Theory.
4.6 General introduction to semiempirical methods: basic principles and terminology.
4.7 Introduction to Density Functional Theory (DFT) methods: Hohenberg-Kohn
theorems. Kohn-Sham orbitals. Exchange correlation functional. Local density
approximation. Generalized gradient approximation. Hybrid functionals (only the
basic principles and terms need to be introduced).
4.8 Model Chemistry-notation, effect on calculation time (cost).
4.9 Comparison of molecular mechanics, ab initio, semiempirical and DFT methods.
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5.2 Identifying a successful GAMESS/ Firefly calculation-locating local minima and
saddle points, characterizing transition states, calculation of ionization energies,
Koopmans’ theorem, electron affinities and atomic charges.
5.3 Identifying HOMO and LUMO-visualization of molecular orbitals and normal
modes of vibrations using suitable graphics packages.
References
01. I.N. Levine, Quantum Chemistry, 6th Edn., Pearson Education, 2009.
02. D.A. McQuarrie, Quantum Chemistry, University Science Books, 2008.
03. R.K. Prasad, Quantum Chemistry, 3rd Edn., New Age International, 2006.
04. F.A. Cotton, Chemical Applications of Group Theory, 3rd Edn., Wiley Eastern,
1990.
05. V. Ramakrishnan, M.S. Gopinathan, Group Theory in Chemistry, Vishal
Publications, 1992.
06. A.S. Kunju, G. Krishnan, Group Theory and its Applications in Chemistry, PHI
Learning, 2010
07. E.G. Lewars, Computational Chemistry: Introduction to the Theory and
Applications of Molecular and Quantum Mechanics, 2nd Edn., Springer, 2011.
08. J.H. Jensen, Molecular Modeling Basics, CRC Press, 2010.
09. F. Jensen, Introduction to computational chemistry, 2 nd Edn., John Wiley & Sons,
2007.
10. A. Leach, Molecular Modelling: Principles and Applications, 2nd Edn., Longman,
2001.
11. J.P. Fackler Jr., L.R. Falvello (Eds.), Techniques in Inorganic Chemistry: Chapter
4, CRC Press, 2011.
12. K.I. Ramachandran, G. Deepa, K. Namboori, Computational Chemistry and
Molecular Modeling: Principles and Applications, Springer, 2008.
13. A. Hinchliffe, Molecular Modelling for Beginners, 2nd Edn., John Wiley & Sons,
2008.
14. C.J. Cramer, Essentials of Computational Chemistry: Theories and Models, 2nd
Edn., John Wiley & Sons, 2004.
15. D.C. Young, Computational Chemistry: A Practical Guide for Applying
Techniques to Real-World Problems, John Wiley & Sons, 2001.
Softwares
Molecular Mechanics:
1. Arguslab available from www.arguslab.com/
2. Tinker available from www.dasher.wustl.edu/ffe/
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Ab initio, semiempirical and dft:
1. Firefly / PC GAMESS available from http://classic.chem.msu.su/gran/gamess/
2. WINGAMESS available from http://www.msg.ameslab.gov/gamess/
Graphical User Interface (GUI):
1. Gabedit available from http://gabedit.sourceforge.net/
2. wxMacMolPlt available from http://www.scl.ameslab.gov/MacMolPlt/
3. Avogadro from http://avogadro.openmolecules.net/wiki/Get_Avogadro
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