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9/3/2019Introduction to SpectroscopyDepartment of Chemistry,IIT(ISM) Dhanbad Studying the properties of matter through its interaction with differentfrequency components of the electromagnetic spectrum. The study of the interaction between radiation and matter as afunction of wavelength λ. Interaction with particle radiation or a response of a material to analternating field or varying frequency ν. Spectroscopy is a technique that uses the interaction of energy with asample to perform an analysis. Understand how light interacts with matter and how you can use thisto quantitatively understand your sample. Understand spectroscopy the way you understand other common toolsof measurement like the watch or the ruler. See that spectroscopy is a set of tools that you can put together indifferent ways to understand systems solve chemical problems.Department of Chemistry, IIT(ISM) Dhanbad1

9/3/2019 What is Spectrum? The data that is obtained from spectroscopy is called a spectrum. A spectrum is a plot of the intensity of energy detected versus thewavelength (or mass or momentum or frequency, etc.) of the energy. A plot of the response as a function of wavelength or more commonlyfrequency is referred as a spectrum. What is Spectrometry? It is the measurement of these responses. What is spectrometer? An instrument which performs such measurement.Reference Books1. Introduction to Spectroscopy, 3rd Edn, Pavia & Lampman2. Organic Spectroscopy – P S KalsiDepartment of Chemistry, IIT(ISM) Dhanbad Common types? Fluorescence Spectroscopy. X-ray spectroscopy and crystallography Flame spectroscopya) Atomic emission spectroscopyb) Atomic absorption spectroscopyc) Atomic fluorescence spectroscopy Plasma emission spectroscopy Spark or arc emission spectroscopy IR spectroscopy UV-Vis Spectroscopy Raman Spectroscopy NMR spectroscopy EPR Spectroscopy Photo thermal spectroscopy Thermal infra-red spectroscopy Mass SpectroscopyDepartment of Chemistry, IIT(ISM) Dhanbad2

9/3/2019 Infra-red spectroscopy The important parameters associated with electromagnetic radiation are:Energy (E): Energy is directly proportional to frequency, and inverselyproportional to wavelength, as indicated by the equation below. Frequency (ν) Wavelength (λ)E hνEFFECT OF ELECTROMAGNETIC RADIATION ON MOLECULESDepartment of Applied Chemistry, IIT(ISM)DhanbadApplications of IR SpectroscopyDepartment of Chemistry, IIT(ISM) Dhanbad3

9/3/2019Department of Applied Chemistry, IIT(ISM)Dhanbad Infrared radiation is largely thermal energy. It induces stronger molecular vibrations in covalent bonds, which can beviewed as springs holding together two masses, or atoms.Specific bonds respond to (absorb) specific frequenciesDepartment of Chemistry, IIT(ISM) Dhanbad4

9/3/2019Essential criteria for a molecule to be IR active:o Only those vibration modes are IR active that involve a change in dipolemoment,during vibration.o H2, N2, O2, Br2, Cl2, I2 etc and IR inactive, while CO, NO, CO2, etc are IR activeDepartment of Chemistry, IIT(ISM) DhanbadDepartment of Chemistry, IIT(ISM) Dhanbad5

9/3/2019Symmetric stretchingScissoringTwistingAsymmetric stretchingRockingWaggingDepartment of Chemistry, IIT(ISM) DhanbadDepartment of Applied Chemistry, IIT(ISM)Dhanbad6

9/3/2019Department of Applied Chemistry, IIT(ISM)DhanbadDepartment of Chemistry, IIT(ISM) Dhanbad7

9/3/2019Wavelength in m and wavenumber in cm-1 can be interconverted using the following expressionDepartment of Chemistry, IIT(ISM) DhanbadDepartment of Chemistry, IIT(ISM) Dhanbad8

9/3/2019Department of Chemistry, IIT(ISM) DhanbadSolved ProblemsDepartment of Chemistry, IIT(ISM) Dhanbad9

9/3/2019Solved ProblemsQ: Why IR spectra is always reported in wavenumbers (cm-1) and not in wavelength ( m)?Ans: The reason is, if reported in wavelength ( m) the mid-IR range comes in the range 25 m to 2.5 m which is equivalent to 400 to 4000cm-1 when reported inwavenumbers (cm-1). The reporting in wavenumber gives better resolution andmake identification of the spectral bands easier.Department of Chemistry, IIT(ISM) DhanbadDepartment of Applied Chemistry, IIT(ISM)Dhanbad10

9/3/2019Curio‐cityQ: Why there are so many small and medium bands in IR spectra of evencompounds with simple structure?Ans: The reason is presence of Overtones, combination bands and differencebands.Q: What are combination bands, Overtones and difference bandsAns: Some times two vibrations of different values ( 1 and 2) couple to give anew band whose frequency is 1 2. These bands are called combinationbands.During vibrational excitation from ground states to excited states some timesexcitation to higher energy states are also possible which are integralmultiples of fundamental vibration, . Hence new hands may appear at 2 ,3 , etc. These bands are called OvertonesSome times coupling of two different bands leads to new bands which aredifference between the frequencies of either bands. 3 1- 2. These bandsare called difference bands.Q: Why the bands are not sharp, but rather broad?Ans: This is because, some times, rotational frequencies couple with vibrationalfrequency, creating additional fine structure due to small transitions.Department of Chemistry, IIT(ISM) Dhanbad11

1. Introduction to Spectroscopy, 3rd Edn, Pavia & Lampman 2. Organic Spectroscopy – P S Kalsi Department of Chemistry, IIT(ISM) Dhanbad Common types? Fluorescence Spectroscopy. X-ray spectroscopy and crystallography Flame spectroscopy a) Atomic emission spectroscopy b) Atomic absorption spectroscopy c) Atomic fluorescence spectroscopy

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