Quantum Chemistry and Spectroscopy

Teacher

Dr. Ashish Kumar Sahoo

Category

Core Courses

Course Attendees

Still no participant

Course Reviews

Still no reviews

Course Name : Quantum Chemistry and Spectroscopy

Code(Credit) : CUTM 1480 (3-2-1)

Course Objectives

  • To impart knowledge about quantum mechanical principles and understanding as well as predicting different microscopic phenomena.
  • To understand the covalent nature of bonding and their theoretical background and correlation to practical aspects.
  • To have a sound understanding of different spectroscopic techniques and photochemistry.

Course Outcomes

           COs                    Course outcomes Mapping COs with POs (High-3, Medium-2, Low-1)
           CO1 Students will gain knowledge on different aspects of quantum chemistry and its applicability in different bonding behavior of atoms.                PO1 (3)
           CO3  

Develop skill to identify, predict and analyze different types of interactions of radiation with matter which is crucial for research purposes.

          PO1(3), PO3 (3).
 

           CO4

 

Gain problem-solving skills from spectroscopic data

 

                PO3(3)

Course Syllabus

Module 1

 Quantum Chemistry Postulates of quantum mechanics, quantum mechanical operators, Schrödinger equation and its application to free particle and “particle-in-a-box” (rigorous treatment), quantization of energy levels, Heisenberg Uncertainty principle; wavefunctions, probability distribution functions, nodal properties,  Extension to two and three dimensional boxes, separation of variables, degeneracy. Qualitative treatment of simple harmonic oscillator model of vibrational motion:   Setting up of Schrödinger equation and discussion of solution and wavefunctions. Vibrational energy of diatomic molecules and zero-point energy.

Assignment 1: Discussion of Moorse Potential energy diagram from vibrating molecule

Angular momentum: Commutation rules, quantization of square of total angular momentum and z-component. Rigid rotator model of rotation of diatomic molecule. Schrödinger equation, transformation to spherical polar coordinates. Separation of variables. Spherical harmonics. Discussion of solution. Qualitative treatment of hydrogen atom and hydrogen-like ions: setting up of Schrödinger equation in spherical polar coordinates, radial part, quantization of energy (only final energy expression). Average and most probable distances of electron from nucleus.Setting up of Schrödinger equation for many-electron atoms (He, Li). Need for approximation methods. Statement of variation theorem and application to simple systems(particle-in-a-box, harmonic oscillator, hydrogen atom).

Assignment 2: Determination of energy of Hydrogen atom using Variation principle
Assignment 3: Apply Schrodinger's equation to He+ atom

Practice:
Eigen systems: Geometrical Interpretation (v-lab)
Geometry Optimization using ab-initio quantum calcuations (v-lab)

 Module 2

Chemical bonding: Covalent bonding, valence bond and molecular orbital approaches, LCAO-MO treatment of H2+.  Bonding and antibonding orbitals. Qualitative extension to H2. Comparison of LCAO-MO and VB treatments of H2 (only wavefunctions, detailed solution not required) and their limitations.

Refinements of the two approaches (Configuration Interaction for MO, ionic  terms in VB). Qualitative description of LCAO-MO treatment of homonuclear and heteronuclear diatomic molecules (HF, LiH). Localised and non-localised molecular orbitals treatment of triatomic (BeH2, H2O) molecules. Qualitative MO theory and its application to AH2 type molecules.

Assignment 4: Apply MO theory to AH2 type molecules e.g. CO2.

 Module 3

 Molecular Spectroscopy:

Interaction of electromagnetic radiation with molecules and various types of spectra; Born-Oppenheimer approximation.

Rotation spectroscopy: Selection rules, intensities of spectral lines, determination of bond lengths of diatomic and linear triatomic molecules, isotopic substitution.

 Assignment 5: Determine the isotopic mass of carbon using IR data.

Module 4

 Vibrational spectroscopy: Classical equation of vibration, computation of force constant, amplitude of diatomic molecular vibrations, anharmonicity, Morse potential, dissociation energies, fundamental frequencies, overtones, hot bands, degrees of freedom for polyatomic molecules, modes of vibration, the concept of group frequencies. Vibration-rotation spectroscopy: diatomic vibrating rotator, P, Q, R branches.

Assignment 6: Assign group frequencies to different functions groups of molecules

Practice:

Calculation of Vibrational Frequency of Molecules and Visualization of Normal Modes (V-lab)

Instrumentation and working principles of solutions infra red (IR) or (vibrational) spectroscopy (v-lab)

 Module 5

Raman and Electronic Spectroscopy

Raman spectroscopy: Qualitative treatment of Rotational Raman effect; Effect of nuclear spin, Vibrational Raman spectra, Stokes and anti-Stokes lines; their intensity difference, rule of mutual exclusion.

Electronic spectroscopy: Franck-Condon principle, electronic transitions, singlet and triplet states, fluorescence and phosphorescence, dissociation and predissociation, calculation of electronic transitions of polyenes using free electron model.

Assignment 7: Explain why the intensity of transition are different in spite of equal probability among energy levels.
Assignment 8:Exemplify the concept of predissociation from Franck-Condon's principle

Practice:
Study the 200-500 nm absorbance spectra of KMnO4 and K2Cr2O7 (in 0.1 M H2SO4) and determine the λmax Calculate the energies of the two transitions in different units (J mol-1, kJ mol-1, cm-1, eV).

Study the pH-dependence of the UV-Vis spectrum (200-500 nm) of K2Cr2O7.

Record the 200-350 nm UV spectra of the given compounds (acetone, acetaldehyde,2-propanol, acetic acid) in water. Comment on the effect of structure on the UVspectra of organic compounds.

Module 6

Nuclear Magnetic Resonance (NMR) spectroscopy: Principles of NMR spectroscopy, Larmor precession, chemical shift and low resolution spectra, different scales, spin-spin coupling and high resolution spectra, interpretation of PMR spectra of organic molecules.

Electron Spin Resonance (ESR) spectroscopy: Its principle, hyperfine structure, ESR of simple radicals.

Assignment 9: Deduce the ESR spectrum of methyl radical

Practice:

Nuclear magnetic resosnace spectrocopy and evaulation of simple 1H NMR spectra of select organic compounds (v-lab)

Module 7

Photochemistry

Characteristics of electromagnetic radiation, Lambert-Beer’s law and its limitations, physicalsignificance of absorption coefficients.

Laws, of photochemistry, quantum yield, actinometry, examples of low and high quantum yields, photochemical equilibrium and the differentialrate of photochemical reactions, photosensitised reactions, quenching.  Role of photochemical reactions in biochemical processes, photostationary states, chemiluminescence.

Assignment 10: Deduce the kinetics of photochemical reaction between hydrogen and chlorine
Practice:
Verify Lambert-Beer’s law and determine the concentration of CuSO4/KMnO4/K2Cr2O7 in a solution of unknown concentration

Determine the amount of iron present in a sample using 1,10-phenathroline.

Determine the dissociation constant of an indicator (phenolphthalein).

Study the kinetics of interaction of crystal violet/ phenolphthalein with sodium hydroxide.

Reference Books:

Banwell, C. N. & McCash, E. M. Fundamentals of Molecular Spectroscopy 4th Ed. Tata McGraw-Hill: New Delhi (2006).

Chandra, A. K. Introductory Quantum Chemistry Tata McGraw-Hill (2001).

House, J. E. Fundamentals of Quantum Chemistry 2nd Ed. Elsevier: USA (2004).

Lowe, J. P. & Peterson, K. Quantum Chemistry, Academic Press (2005).

Kakkar, R. Atomic & Molecular Spectroscopy, Cambridge University Press (2015).

Session Plan

Session 5

Extension to two and three dimensional boxes, separation of variables, degeneracy.

https://www.youtube.com/watch?v=jvvkomcmyuo

Session 6

Qualitative treatment of simple harmonic oscillator model of vibrational motion:   Setting up of Schrödinger equation and discussion of solution and wavefunctions.

https://ocw.mit.edu/courses/physics/8-03sc-physics-iii-vibrations-and-waves-fall-2016/syllabus/MIT8_03SCF16_Text_Ch1.pdf

https://www.youtube.com/watch?v=T7fRGXc9SBI

https://www.youtube.com/watch?v=HRcjtVa1LfM

https://www.youtube.com/watch?v=cx-qHZwsLqs

Session 8

Assignment 1: Flip class (1 hour)

Moorse potential energy curve and explanation

Session 9

Angular momentum: Commutation rules, quantization of square of total angular momentum and z-component.

https://ocw.mit.edu/courses/physics/8-01sc-classical-mechanics-fall-2016/week-11-angular-momentum/32.2-calculating-angular-momentum

Session 10

Rigid rotator model of rotation of diatomic molecule. Schrödinger equation, transformation to spherical polar coordinates.

https://ocw.mit.edu/courses/aeronautics-and-astronautics/16-07-dynamics-fall-2009/lecture-notes/MIT16_07F09_Lec05.pdf

https://www.youtube.com/watch?v=vfgbPXS9qcs

Session 11

Separation of variables. Spherical harmonics. Discussion of solution.

https://www.youtube.com/watch?v=lFJgqZ48yls

Session 12

Qualitative treatment of hydrogen atom and hydrogen-like ions: setting up of Schrödinger equation in spherical polar coordinates, radial part, quantization of energy (only final energy expression). Average and most probable distances of electron from nucleus.

https://ocw.mit.edu/courses/chemistry/5-112-principles-of-chemical-science-fall-2005/video-lectures/lecture-6-schroedinger-equation-for-h-atom/

Session 13

Setting up of Schrödinger equation for many-electron atoms (He, Li).

https://www.youtube.com/watch?v=Y3ME_pRaemA

Session 14

Need for approximation methods. Statement of variation theorem and application to simple systems(particle-in-a-box, harmonic oscillator, hydrogen atom).

http://vallance.chem.ox.ac.uk/pdfs/VariationPrincipleNotes.pdf

https://www.youtube.com/watch?v=bsEET6vBxSQ

Session 15 (Assignment 2: Flip Class) 1 hour

Determination of energy of Hydrogen atom using Variation principle

 Session 16 (Assignment 3: Flip Class) 1 hour

Apply Schrodinger's equation to He+ atom

 Session 17: Practice 1 (2 hours)

Session 19

Session 21

Comparison of LCAO-MO and VB treatments of H2 (only wavefunctions, detailed solution not required) and their limitations.

https://www.youtube.com/watch?v=OkcD7tKre1c

Session 22

Refinements of the two approaches (Configuration Interaction for MO, ionic  terms in VB). Qualitative description of LCAO-MO treatment of homonuclear and heteronuclear diatomic molecules (HF, LiH). Localised and non-localised molecular orbitals treatment of triatomic (BeH2, H2O) molecules.

linearcombinationoftomicorbitals

https://www.youtube.com/watch?v=z-ZpR1RaawU

Session 23:(Assignment 4: Flip Class) (1 hour)

Apply MO theory to AH2 type molecules e.g. CO2.

Session 24

Molecular Spectroscopy:

Interaction of electromagnetic radiation with molecules and various types of spectra; Born-Oppenheimer approximation.

https://ocw.mit.edu/courses/chemistry/5-80-small-molecule-spectroscopy-and-dynamics-fall-2008/lecture-notes/08s_elecconfigs.pdf

Session 25

Rotation spectroscopy: Selection rules, intensities of spectral lines, determination of bond lengths of diatomic and linear triatomic molecules, isotopic substitution.

Rotational spectra

https://www.youtube.com/watch?v=QsHH4AntocM

Session 26 (Assignment 5: Flip Class) (1 hour)

Determine the isotopic mass of carbon using IR data.

Session 27

Vibrational spectroscopy: Classical equation of vibration, computation of force constant,amplitude of diatomic molecular vibrations, anharmonicity, Morse potential, dissociation energies,

https://ocw.mit.edu/courses/chemistry/5-61-physical-chemistry-fall-2007/lecture-notes/lecture35.pdf

https://www.youtube.com/watch?v=_TmevMf-Zgs

Session 28

fundamental frequencies, overtones, hot bands, degrees of freedom for polyatomic molecules, modes of vibration, concept of group frequencies. Vibration-rotation spectroscopy: diatomic vibrating rotator, P, Q, R branches.

https://ocw.mit.edu/courses/chemistry/5-61-physical-chemistry-fall-2007/lecture-notes/lecture35.pdf

Session 29: (Assignment 6: Flip Class) (1 hour)

Identification the group frequencies of functional groups of given molecules

 Session 30 Practice 2 (2 hours)

Calculation of Vibrational Frequency of Molecules and Visualization of Normal Modes

V lab link:

http://ccnsb04-iiith.vlabs.ac.in/exp5/Introduction.html?domain=Computer%20Science&lab=Computer%20Systems%20Organization%20lab

 Session 31: Practice 3 (2 hours)

Instrumentation and working principles of solutions infra red (IR) spectroscopy(v-lab)

V lab link:

http://ccnsb06-iiith.vlabs.ac.in/exp7/Introduction.html?domain=%20Chemical%20Sciences&lab=Physical%20Chemistry%20Lab

Session 32

Raman spectroscopy: Qualitative treatment of Rotational Raman effect; Effect of nuclear spin, Vibrational Raman spectra, Stokes and anti-Stokes lines; their intensity difference, rule of mutual exclusion.

Raman spectroscopy 1

Raman spectroscopy 2

https://www.youtube.com/watch?v=SsIYDEma_cU

https://www.youtube.com/watch?v=iO2_YTZH82w

Session 33

Electronic spectroscopy: Franck-Condon principle, electronic transitions, singlet and triplet states, fluorescence and phosphorescence, dissociation and predissociation, calculation of electronic transitions of polyenes using free electron model.

https://ocw.mit.edu/courses/chemistry/5-61-physical-chemistry-fall-2017/lecture-notes/MIT5_61F17_lec30_lec31.pdf

https://www.youtube.com/watch?v=_2etUR5WByE

Session 34: (Assignment 7: Flip Class) (1 hour)

Explain why the intensity of transition are different in spite of equal probability among energy levels.

 

Session 35: (Assignment 8: Flip Class) (1 hour)

Exemplify the concept of predissociation from Franck-Condon's principle

 Session 36: Practice 4 (2 hours)

Study the 200-500 nm absorbance spectra of KMnO4 and K2Cr2O7 (in 0.1 M H2SO4) and determine the λmax Calculate the energies of the two transitions in different units (J mol-1, kJ mol-1, cm-1, eV).

https://www.youtube.com/watch?v=6VkOKpvEyP8

 Session 37: Practice 5 (2 hours)

pH effects on absorption spectra: pKa determination by spectrophotometric method

V Lab link:

http://mas-iiith.vlabs.ac.in/exp9/Introduction.html?domain=%20Chemical%20Sciences&lab=ABSORPTION%20SPECTROSCOPY%20VIRTUAL%20LAB

 Session 38: Practice 6 (2 hours)

Record the 200-350 nm UV spectra of the given compounds (acetone, acetaldehyde,2-propanol, acetic acid) in water. Comment on the effect of structure on the UVspectra of organic compounds.

https://www.youtube.com/watch?v=s5uIVQGFDE4

Session 39

Nuclear Magnetic Resonance (NMR) spectroscopy: Principles of NMR spectroscopy, Larmor precession, chemical shift and low resolution spectra, different scales, spin-spin coupling and high resolution spectra, interpretation of PMR spectra of organic molecules.

https://ocw.mit.edu/courses/chemistry/5-61-physical-chemistry-fall-2017/lecture-notes/MIT5_61F17_lec30_lec31.pdf

https://www.youtube.com/watch?v=ywR6aLpfjl0

https://www.youtube.com/watch?v=TJhVotrZt9I

https://www.youtube.com/watch?v=PmYwYUQw-Rw

Session 40

Session 41: (Assignment 9: Flip Class) (2 hours)

Deduce the ESR spectrum of methyl radical

 Session 42: Practice 7 (2 hours)

Nuclear magnetic resosnace spectrocopy and evaulation of simple 1H NMR spectra of select organic compounds (v-lab)

V lab link:

http://ccnsb06-iiith.vlabs.ac.in/exp5/Introduction.html?domain=%20Chemical%20Sciences&lab=Physical%20Chemistry%20Lab

Session 43

Characteristics of electromagnetic radiation, Lambert-Beer’s law and its limitations, physicalsignificance of absorption coefficients.

Beer-Lamberts law

https://ocw.mit.edu/courses/chemistry/5-61-physical-chemistry-fall-2017/lecture-videos/electronic-spectroscopy-and-photochemistry/

https://www.youtube.com/watch?v=FWCN_uI5ygY

Session 44

Laws, of photochemistry, quantum yield, actinometry, examples of low and high quantum yields, photochemical equilibrium and the differential rate of photochemical reactions,

photochemistry 1

photochemistry 2

actinometry

Kinetics_of_photochemical_reactions

https://www.youtube.com/watch?v=h0Ae1IggsuM

Session 45

photosensitised reactions, quenching.  Role of photochemical reactions in biochemical processes, photostationary state.

photosensitized

Kinetics_of_photochemical_reactions

https://ocw.mit.edu/courses/chemistry/5-61-physical-chemistry-fall-2017/lecture-videos/electronic-spectroscopy-and-photochemistry/

Session 47 (Assignment 10: Flip Class) (2 hours)

Deduce the kinetics of photochemical reaction between hydrogen and chlorine.

 Session 48: Practice 8 (2 hours)

Verify Lambert-Beer’s law and determine the concentration of

CuSO4/KMnO4/K2Cr2O7 in a solution of unknown concentration

https://www.youtube.com/watch?v=ur-KnVKQO4w

 Session 49: Practice 9 (2 hours)

Study the kinetics of iodination of propanone in acidic medium.

https://www.youtube.com/watch?v=kVm43n1MdUI

 Session 50: Practice 10 (2 hours)

 Session 51: Practice 11 (2 hours)

Determine the dissociation constant of an indicator (phenolphthalein).

https://www.youtube.com/watch?v=LxgZsMhuyNM

 Session 52: Practice 12 (2 hours)

Study the kinetics of interaction of crystal violet/ phenolphthalein with sodium hydroxide.

https://www.youtube.com/watch?v=tcv5Xk9ZXpg

Case Studies

Case Studies

Our Main Teachers

Dr. Ashish Kumar Sahoo has 3 years of teaching experience in undergraduate as well as postgraduate level. His areas of interest are in Advanced Physical Chemistry and Material Chemistry. Dr. Sahoo has a number of international publications. His research interest semiconducting materials in both pure as well as interstitially dopped and making use of simple […]