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Main Reference: Fundamentals of Molecular Spectroscopy Colin N Banwell and Elain M McCash Fourth Edition Tata McGraw-Hill Publishing Company Limited Reference book is imperative. Notes will refer to the book. Proforma of Molecular Spectroscopy Course Fakulti : Jabatan : Program Pengajian : Kod Kursus : Tajuk Kursus : Jam Kredit : Prasyarat / Keperluan Minimum Kursus : Objektif Kursus : Sains Kimia B.Sc. (Hons.) SCES2250 Spektroskopi Molekul 3 Kimia Fizik II
Sinopsis Kandungan Kursus :
Memberikan kefahaman tentang spektroskopi molekul sebagai alat utama untuk memahami struktur molekul dan sifat-sifatnya Spektroskopi putaran, getaran dan elektronik. Spektrum elektromagnet. Asas-asas spetroskopi. Spektrum putaran dan getaran molekul dwiatom dan poliatom. Kesan Raman; spektrum Raman putaran dan getaran. Keadaan elektron dalam molekul; teori kumpulan asas
untuk spektroskopi, pencirian keadaan elektron (term symbols). Peralihan elektron, spektroskopi elektronik, momen dwikutub peralihan. Pendafluor dan pendafosfor. Spektroskopi resonans magnet Sifat magnet elektron dan nucleus. Kelakuan electron dan nucleus dalam medan magnet: pengkuantuman momentum sudut, tenaga spin, taburan Boltzmann spin, pemagnetan makroskopik. Resonans magnet dan eksperimen. Parameter spectrum NMR: anjakan kimia, pengkupelan spin-spin dan masa relaksasi nucleus (T1 dan T2). Faedah medan magnet tinggi. Resonans dubel. Kesan relaksasi dan resonans dubel ke atas spectrum NMR karbon-13. Masa relaksasi T1 dan maklumat gerakan molekul. Kelakuan nukleus kuadrupol sebagai nukleus tak-magnet. . Skalamasa NMR; kesan fenomenon pertukaran ke atas spectrum NMR. Prinsip asas bagi NMR bagi keadaan pepejal, NMR dua-dimensi dan NMR mengimej.
Kaedah Penilaian :
Penilaian berterusan: 30% Peperiksaan: 70%
English Version Faculty : Department : Course programme: Course code: Science Chemistry B.Sc. (Hons.)
rotation and electronic spectroscopy. Electromagnetic spectrum. spin energy. The Raman effect.Course title: Credit hours: Pre-requisite: Course objective: Molecular Spectroscopy 3 Physical Chemistry II To give a fundamental understanding of molecular spectroscopy as the most important tool in understanding molecular structure and its characteristics Vibration. spin-spin coupling and nuclear relaxation time (T1 and T2). Magnetic properties of the electron and nucleus: spin angular momentum and magnetic moment. Basic principles of solid-state NMR. effect of exchange phenomena on NMR spectra. NMR time-scale. Double resonance. Behavior of electron and nucleus in magnetic field: space quantization of angular momentum. Electronic transition. Boltzmann distribution and macroscopic magnetization. transition dipole moment and electronic spectra. two-dimensional NMR and NMR imaging. Effect of nuclear relaxation and double resonance on carbon-13 NMR spectra. Fundamentals of spectroscopy. Magnetic resonance and experiment. Advantages of high magnetic field. Parameters in the NMR spectrum: chemical shift. Magnetic resonance spectroscopy. Elementary group theory for spectroscopy. Behavior of quadrupolar nuclei as non-magnetic nuclei. Relaxation time T1 and molecular motion. rotational and vibrational Raman spectra. Rotational and vibrational spectra of diatomic and polyatomic molecules. Synopsis of course content: . Fluorescence and phosphorescence. Electronic states in molecules and term symbols.
1-3) EMW of which visible light forms an obvious but very small part may be considered as a simple harmonic wave propagated from a source and traveling in a straight line except when refracted or reflected. These are broadly classified as: 1) rotation 2) vibration 3) redistribution of electrons. The three types of changes occur when molecules absorb EMW of differing energies.Grading: Continuous assessment: 30% Examination: 70% Other references: 1) Modern Spectroscopy J.2 What is EMW? (pg. When matter (molecules) absorb EMW. the molecules can undergo changes. Michael Hollas Second Edition Wiley 2) Molecular Spectroscopy John M Brown Oxford Science Publications 3) Physical Chemistry P W Atkins Oxford Other Spectroscopy/Physical Chemistry books available in the library 1 1. . 1.1 Introduction to Spectroscopy Electromagnetic Spectrum Molecular spectroscopy may be defined as the study of the interaction between electromagnetic waves (EMW) and matter (atoms or molecules).
cs. This is defined as: R !1 / P Using appropriate units for c (cms-1) and P (cm).uwindsor. giving a generalized connotation of energy. both waves are perpendicular to each other.ca/schurko/animations/emwave/emwave. it would be easy to convert from Hz to wavenumber and vice versa.Diagram1. a widely used unit is the wavenumber (cm-1).htm EMW consists of electric field and magnetic field parts. A bar above R indicate units in cm-1 .1: EMW EMW applet http://mutuslab. frequency etc. Q1: Write the equations of EMW: Basic wave equation is P!c/R where P is the wavelength in meters. c is the speed of light in ms-1 and R is the frequency in Hz (cycles s-1). In spectroscopy.
we need to understand that EMW exists in different energies. 300nm to cm-1 1. This can be conveniently expressed in terms of an EM spectrum.Q2: Convert ² 133MHz to cm-1.3 EMW spectrum (pg. Visible light spectrum . 400cm-1 to Hz. 5-9) To answer the question concerning the types of interaction that will occur when molecules absorb EMW.
electronic. soaking up all the energy available over the whole spectrum of EMW. when absorbed by a molecule will cause the molecule to rotate. This was found to be incompatible with reality. It is imperative that you understand. Max Planck published a revolutionary paper suggesting that energy of an oscillator is discontinuous and change of energy can happen by means of a jump between two energy states. Make sure you develop the sense of magnitude related to the spectrum. a molecule can also be thought to possess energy in quantized form ² rotation. for example that EM in the microwave region. vibration. 3-5) Initially matter was thought to be able to absorb energy in the form of EMW continuously. Q3: Write brief notes on the EM spectrum and how it interacts with matter: 1. Etotal = Erotation + Evibration + Eelectronic (ET = Er + Ev + Ee ) .4 Quantization of Energy (pg.Understand the EM spectrum presented (see a more lively EMW spectrum ² in folder). Extending this idea.
If we plot a graph of intensity of absorption vs. This is in Hz. R s is the frequency absorbed. It is then said that the matter has absorbed a photon of EMW. a transition is said to occur. (E ! hR s Where (E = En-Em. This transition can be described by an equation suggested by Planck. we get a spectrum with a peak at R s . . frequency.This is known as the Born Oppenheimer approximation. What are they? Q4: Draw a spectrum with absorption at R s . Matter absorbs EM energy in a quantized manner. Three types of transitions are shown in diagram1.2.2 : Transitions between two energy levels Upon absorption of EMW of a certain energy. The symbol for frequency in cm-1 is usually R s unless different symbols are noted to have units of cm-1. Best visualized via energy level diagram: Diagram1.
Energy (levels) (E) and wavefunctions (ƹ) associated with each energy levels. Solution to this equation basically gives two things. The basis of quantum mechanics is the Schrodinger equation. As an example. A Schrodinger equation for the kinetic and potential energy at play within the atom which consists of an electron and a proton is set up.In spectroscopy we can envisage the quantized energy levels as depicted below: Diagram1.3 : Magnitude of the different type of energy levels The physics that deals with quantized energies of molecules is quantum mechanics. It is then solved . lets jump straight into a real case ² the hydrogen atom.
Since hydrogen atom is an atom. A molecule. such as A-B on the other hand will have rotational and vibrational energy besides electronic energy.to give energy levels and wavefunction. the only energy it possesses is the electronic energy (besides the continuous translational energy). 2p etc. 3s. Q5: Why do atoms lack rotation and vibrational energies? Upon absorption of EM by a molecule. we have 1s. These wavefunctions are appropriately combined to result in atomic orbitals. Absorption of EM in the region of UV/Vis will cause electrons to be excited from one level to another. atomic orbitals (which are really combination of wavefunctions from the solutions of the schrodinger equation). corresponding to the energy absorbed. Thus. Each orbital is identified with an energy level represented (or labelled) by its quantum number. 2s. The details of this can be obtained from various Physical Chemistry texts. . we ask three questions: 1) The frequency of absorption 2) The line intensity 3) The linewidth of the spectral line.
18-20) Spectral line intensity is determined basically by three factors: a) Transition probability ² A rigorous quantum mechanical treatment of EM-matter interaction will produce what is known as the transition probability. If Rnm = 0 then there is no transition . T Q is the electric dipole moment operator. It is represented by: Tm Rnm ! ´] n * Q] dX Where ] n and ] m are wavefunctions of states n and m respectively.The frequency of the absorption can be read off the spectrum and the type of interaction depends on the value of the frequency (sense of magnitude? EM spectrum?) Q6: Draw a single line spectrum and illustrate the spectrum with labels appropriate to the three questions: Questions 2) and 3) will be answered below. The spectral line intensity is proportional to Rnm2.5 Spectral line intensity (pg. 1.
Understand this properly. and the upper one is lower in population. This will be discussed further for each type of interaction Q7: Write the Boltzmann distribution population ratio of two states m and n c) Concentration of sample or path length of sample ² works within the Beer Lambert Law: log Io/I = Icl Where I is the transmitted light intensity. whereas if Rmn <> 0. rotation. there can be a transition (allowed). c is the concentration of sample.6 Spectral linewidth (pg.chm.(forbidden). Good applets on this can be obtained from : http://www. if the lower state is of higher population. b) Population of states ² between two states. 17-18) There are 3 factors that effect line broadening: . This is also known as the gross selection rule for a transition. then the transition is very much favoured. Boltzmann distribution determines the relative population.edu/ChemistryApplets/#Spectrophotometr y 1. The transition probability will be rationalized later for each type of transition.davidson. l is the path length and I is molar absorption coefficient ( a function of frequency). vibration and electronic. Io is the incident light intensity.
each frequency overlapping with each other forming a gaussian envelope ² heterogeneous spectral line. (R ! 1 2TX There will always be broadening because X can never be infinite. This causes perturbation to the energy levels.ntnu. or moving relative to the detector. and lower on the left.tw/java/Doppler/Doppler. Can be reduced by taking spectrum in gas phase and lowering the pressure of gaseous samples .html c) Pressure broadening (collision broadening) Due to continuous collision between molecules/atoms. Broadening due to only one frequency ² homogeneous spectral line b) Doppler broadening ² due to Doppler shift ² based on Doppler effect Diagram1.a) Natural linewidth ² Heisenberg uncertainty principle.edu. The perceived frequency is higher on the right. This is natural in all spectroscopic measurements. Imagine molecules as source being stationary. thus broadening it ² more severe in liquid. you get many different frequencies centred around a mid frequency.phy. Molecules move randomly ² as a result. Doppler effect applethttp://www.4 : Doppler effect As an example: Sound waves emanating from an ambulance moving to the right.
2 Representation of Spectra ² practical aspects of spectroscopy (pg.html We shall only look into the first two at the moment.1 Absorption . .concordia.ca/facstaff/a-c/bird/c241/D2-part2. IR (optical) and microwave (non-optical) Q8: Draw the complete diagram of a basic optical absorption experiment complete with appropriate labels and explanation of the labels. 2.UV/Vis. 9-17) There are basically 3 types of spectroscopy experiments: 1) Absorption 2) Emission 3) Scattering Absorption spectrometer applet: http://artsci-ccwin.
2.2 Emission UV/Vis (optical) Q9: Draw the complete diagram of a basic optical emission experiment complete with appropriate labels and explanation of the labels. .
html . 2) Slit ² used to direct EMW to sample or to determine resolution. An applet demonstrating the action of a grating can be found at: http://www. slits also reduce the total intensity that could have been utilized.4a ² typical arrangement of an absorption spectrometer Among the important parts of the spectrometer are: 1) Source ² the types of sources will depend on the types of interaction desired (refer to handouts). This part of the spectrometer is usually called a monochromator (below). Used in conjunction with a slit (see handout). 3) Dispersing element or a grating ² used to disperse EMW into its constituent frequencies.mtholyoke.Diagram 1.edu/~mpeterso/classes/phys301/laboratories/balmer . Unfortunately.
. 91-93) ² See brochure of Lambda series of spectrometers.au/people/mcintyre/applets/optics/grating. chart recorders. we need the signal to be at least 3 or 4 times larger than noise. The noise can come from the electronic cricuitry in the spectrometer or from the detector. We should also consider the two types of operation in a spectrometer ² single beam and double beam operation ² this is done in order to compensate for the background which may affect the spectrum due to the presence of water vapour and carbon dioxide absorption.3 Signal to Noise Ratio (pg. This is especially true for IR spectroscopy (pg.html Diagram1.uq. KBR. 2.5 : Monochromator (action of a grating) 4) Sample holder ² to hold sample ² quartz and glass (UV/Vis). Noise is usually described in termso fluctuation.edu.physics. 15) Modern electronic instruments can·t escape from noise. NaCl salt slabs (IR) ² depending on the EMW region 5) Detector ² types of which are determined by the different EMW sources ² see handout 6) Display ² displays the spectrum ² computers. To differentiate between signal and noise.http://www.
26). the SNR is 20 times the base-10 logarithm of the amplitude ratio.4 Spectral resolution (pg. Use appropriate illustrations. 16) Often used as a mesure of the performance of a spectrometer. 2. Q10: Explain how the size of the output slits can affect the resolving power of a spectrometer. . SNRs are often expressed in terms of the logarithmic decibel scale. In decibels.Signal-to-noise ratio is an engineering term for the power ratio between a signal (meaningful information) and the background noise: Because many signals have a very wide dynamic range. or 10 times the logarithm of the power ratio: where P is average power and A is RMS amplitude There are various techniques to increase S/N ratio such as filtering and computer averaging (pg.
first look at beat frequency. Visit: http://www.(pg. Say.pingry. 93-96) Conventionally a spectrum is taken by sweeping over the whole range of frequencies within the spectral domain.htm http://physics.5 Fourier Transformation in Spectroscopy (pg. To understand FT.com/explrsci/dswmedia/tonebeat. the whole spectrum can be taken simultaneously within the required region.2. 20-26). Very inefficient. The frequency is swept smoothly from 1000 to 4000cm-1 (by rotating the grating in the monochromator). This takes a long time. With FT technology. a spectrum from 1000cm-1 to 4000cm-1 is to be recorded.org/Explorations/Acoustics/Beats/ .ithacasciencezone.
they cancel out (pg. The oscillation is due to the beat pattern set up by all the superimposed. in fact imagine interfering hundreds of frequencies together. «. all waves in the package are in step but as time goes by they start to be out of phase that on average.for audio demonstration of beat frequency.. Conceptually. . 300Hz + about 300Hz (say 301 Hz) gives«. but slightly different sine waves emitted.22-23) Good applets to demonstrate time domain to frequency domain using FT.a beat frequency..which is an interference pattern. This pattern is in time domain (serial domain). You can·t tell what the different frequencies are«we have to convert this interference pattern into a frequency domain spectrum where interfering frequencies can be identified ² FT!! Note that an interferogram shows an oscillating signal decaying smoothly to zero. The decay can be imagined by considering that initially. Imagine interfering more than 2 frequencies. . a combination of many different frequencies will result in a particular interference pattern.
edu/oldsep/hale/FftLab. Read about the interferogram and understand how it works.si/CoLoS/applets/fft/ftd. How does it work? Diagram 1.uni-mb. A typical arrangement of an FTIR is depicted below (diagram 1. 105.6 : FTIR Demonstration of Michelson interferometer.4GHz into wavenumber (cm-1).ht ml Tutorial: 1) Convert 99.http://storm. 103.html http://sepwww.6).3MHz.uq. we can take the spectrum instantaneously and by using FT. What happened to it? .edu.html By using an interferometer. 2) Which region of the EMW causes molecular rotation? What are the selection rules required in order to observe rotational spectrum? 3) A molecule X absorbs EMW at 3500cm-1.9MHz dan 2. the interferogram is transformed into a frequency domain spectrum.3MHz.au/people/mcintyre/applets/michelson/michel.stanford. http://www.physics.
12) Explain why the natural linewidth in a rotational spectrum is smaller that the natural linewidth of a UV spectrum? 13) What is S/N ratio? 14) What is Rmn? .4) Electron redistribution in a molecule or atom occurs in the EMW region of«. 8) Write down the energies of a molecule based on the Born Oppenheimer approximation. 9) List down the factors that influence the intensity of a spectral line 10) Discuss the three types of spectral line broadening 11) Discuss how an FTIR spectrometer works. 5) Draw the diagram of a simple absorption spectrometer and explain the workings of this apparatus 6) What is the function of the first dispersion element of an emission spectrometer (in the monochromator before EMW enters the sample? 7) Give example of the source of EMW for each identifiable region of the spectrum.
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