Raman Spectroscopy

Introduction

You are already aware that photons interact with molecules to induce transitions between energy states. In the discussion of Raman spectroscopy, we use language from particle theory and we say that a photon is scattered by the molecular system. Most photons are elastically scattered, a process which is called Rayleigh scattering. In Rayleigh scattering, the emitted photon has the same wavelength as the absorbing photon. Raman Spectroscopy is based on the Raman effect, which is the inelastic scattering of photons by molecules. The Raman effect comprises a very small fraction, about 1 in 107, of the incident photons. In Raman scattering, the energies of the absorbed and emitted photons are different. A simplified energy diagram that illustrates these concepts is given below. Virtual state

Stokes

Rayleigh

Anti Stokes Vibrational levels

Ground electronic state Note that energy is lost in the Stokes line and energy is produced in the anti-Stokes line. The energy gained or lost is related to the vibrational energy spacing in the molecule and therefore the wavenumber of the Stokes and anti-Stokes lines are a direct measure of the vibrational energies of the molecule. A schematic Raman spectrum may appear as:
Rayleigh Stokes Anti-Stokes

In the example spectrum, notice that the Stokes and anti-Stokes lines are equally displaced from the Rayleigh line. This occurs because in either case one vibrational quantum of energy is gained or lost. Also, note that the anti-Stokes line is much less intense than the Stokes line. In Raman

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spectroscopy, usually the more intense Stokes line is measured. Raman spectroscopy requires a high power source because of the minute Raman intensities. Raman became a common experimental technique after the development of high power lasers. In a typical setup, the laser beam irradiates the sample and the Raman scattering is observed at a 90o angle. This viewing angle minimizes interference from the laser. Infrared (IR) and Raman spectroscopy both measure the vibrational energies of molecules but these method rely only different selection rules. Recall that for a vibrational motion to be IR active, the dipole moment of the molecule must change. Therefore, the symmetric stretch in carbon dioxide is not IR active because there is not change in the dipole moment. The asymmetric stretch is IR active due to a change in dipole moment.
O C no change in dipole Not IR active O O C change in dipole IR active O

For a transition to be Raman active there must be a change in polarizability of the molecule. Polarizability is the change of the dipole moment with distance.

Molecular motion

polarizability ellipsoid

Notice that the symmetric stretch in carbon dioxide is Raman active because the polarizability of the molecule changes. You can see when you compare the ellipsoid at the equilibrium bond length to the ellipsoid for the extended and compressed symmetric motions. For a vibration to be Raman active, the polarizability of the molecule must change with the vibrational motion. Thus, Raman spectroscopy complements IR spectroscopy. Experimentally, we only observe the Stokes shift in a Raman spectrum. Recall that the Stokes lines will be at smaller wavenumbers (or higher wavelengths) than the exciting light. Since the Raman

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scattering is not very efficient, we need a high power excitation source such as a laser. We also need to have very sensitive amplification and detection equipment to monitor the weak Raman signal. In this experiment, a lock-in amplifier is used to detect the signal. A lock-in needs to have a pulsed source so the Helium-Cadmium laser beam ( = 442 nm) is passed through an optical chopper to produce a pulsed beam. The scattered light is passed through a 0.5 meter CVI monochromator and detected by a PMT. Output from the tube is passed to the lock-in and then to either a computer or strip chart recorder.
Monochromator (DK 480)

Lock-In Amplifier (SR 810) He-Cd Laser (442 nm)

Chopper Sample

Detector (PMT)

Default Instrument Parameters: DK 480 Monochromator Scan Range: typically 440 nm 510 nm Scan Speed: 20nm/min Bandpass: 1.5 nm Entrance Slit: 430 m Exit Slit: 430 m External Raman Instrument Parameters: PMT Voltage: 800 mV Chopper: 400 Hz

SR 810 Lock-In Amplifier Time Constant: 300 ms Slope: 24 dB Sensitivity: 2 mV/nA Data Storage Rate: 64 Hz

Experimental

You will investigate the vibrational properties of three molecules: methylene chloride, chloroform, and carbon tetrachloride. You will use molecular orbital theory and group theory to classify the vibrational modes and determine which modes are IR active and which are Raman active.

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Before you begin the experiment, complete these calculations: 1. Calculate the number of vibrational modes in each molecule. 2. Calculate the wavenumber for the laser line. Assuming that the highest observed vibration is at 3500 cm1, find the maximum wavenumber for the scan. Convert this wavenumber into wavelength. The Raman spectrometer is home built and will be demonstrated to you. Samples are in 5 mm NMR tubes with flat bottoms and the laser beam is oriented to pass through the bottom of the NMR tube. Good spectra depend on careful alignment of the laser beam and the optics. You will obtain the IR and Raman spectra of each sample. For the Raman spectra, start the scan at 447. Safety Note: These substances are potential carcinogens. Use gloves and minimize exposure.
Molecular Orbital Calculations

Each molecule will also be modeled on Spartan at the 3-21*G level. Optimize the geometry, and then calculate the vibrational frequencies using the 3-21*G basis. Animate each vibration to determine which atoms contribute to the motion.
Calculations

1. Classify each molecule into its point group and then use the character table for that point group to determine, from your Spartan calculations, which modes are IR active and which are Raman active. 2. Predict the number of peaks for the IR and Raman spectra. 3. Convert the experimental peak positions from wavelength to wavenumbers. The Raman shift is the difference between the wavenumber of the laser line and the wavenumber of the observed peak (Since these are Stokes lines, the Raman shift is always >0). 4. It has been well documented that HF calculations always overestimate vibrational frequencies.1 A correction or scaling factor is used to bring the calculated values in agreement with experimental data. The scaling factor is 0.9085 for the 3-21*G basis. After scaling your results, compare the calculated wavenumbers with the experimental values. What are the percent errors in the calculated results? 5. At what wavenumber would the Raman peak appear for CDCl3?

L. Radom & A. Scott, J. Phys. Chem. 1996, 100, 16502.

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Mutual exclusion principle

In a molecule with a center of symmetry it is seen that vibrations that are Raman active are IR inactive and vice-versa, this is called the Principle of mutual exclusion (eg, as in CO2 see details in the end). In molecules with different elements of symmetry, certain bands may be active in IR, Raman, both or neither. For a complex molecule that has no symmetry except identity element, all of the normal modes are active in both IR and Raman. This does not; however mean that they can be observed. In both types the neighbouring strong bands may obscure weak bands, while others may be intrinsically too weak to be observed even if they are theoretically allowed.

In general the strong bands in the IR spectrum of a compound corresponds to weak bands in the Raman and vice versa. This complimentary nature is due to the electrical characteristic of the vibration. If a bond is strongly polarised, a small change in its length such as that occurs during a vibration, will have only a small additional effect on polarisation. Vibrations involving polar bonds ( C-O , N-O , O-H ) are therefore, comparatively weak Raman scatterers. Such polarised bonds, however, carry their charges during the vibrational motion, ( unless neutralised by symmetry factors), which results in a large net dipole moment change and produce strong IR absorption band. Conversely, relatively neutral bonds ( C-C , C-H , C=C ,) suffer large changes in polarisability during a vibration, though this is less easy to visualise. But the dipole moment is not similarly affected and vibrations that predominantly involve this type of bond are strong Raman scatterers but weak in the IR.

Mutual exclusion principle as seen in CO2

In molecules having inversion center, none of the normal modes of vibrations will be both Raman and IR active. This is known as mutual exclusion principle. A simple molecule which obeys this principle is CO2. Carbondioxide has an inversion center or center of symmetry. The following are its normal modes of vibrations. The IR and Raman active modes are indicated below each type of vibration.

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Differences between IR and Raman methods

Raman
1 It is due to the scattering of light by the vibrating molecules. The vibration is Raman active if it causes a change in polarisability. The molecule need not possess a permanent dipole moment. Water can be used as a solvent. Sample preparation is not very elaborate sample can be almost in any state.

IR
It is the result of absorption of light by vibrating molecules. The vibration is IR active if there is a change in dipole moment during the vibration. The vibration concerned should have a change in dipole moment due to that vibration. Water cannot be used due to its intense absorption. Sample preparation is elaborate Gaseous samples can rarely be used.

6 7

Gives an indication of covalent character in the molecule. Gives an indication of ionic character in the molecule. Cost of instrumentation is very high Comparatively inexpensive.

References:

1. Physical methods of Chemistry : Drago 2. Instrumental methods of analysis : Willard 3. IR and Raman spectra of Inorganic and coordination compounds : Nakamoto 4. Instrumental analysis for Science and Technology : W. Ferren

What is Raman Spectroscopy?

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Raman spectroscopy provides information about molecular vibrations that can be used for sample identification and quantitation. The technique involves shining a monochromatic light source (i.e. laser) on a sample and detecting the scattered light. The majority of the scattered light is of the same frequency as the excitation source; this is known as Rayleigh or elastic scattering. A very small amount of the scattered light (ca. 10-5% of the incident light intensity) is shifted in energy from the laser frequency due to interactions between the incident electromagnetic waves and the vibrational energy levels of the molecules in the sample. Plotting the intensity of this "shifted" light versus frequency results in a Raman spectrum of the sample. Generally, Raman spectra are plotted with respect to the laser frequency such that the Rayleigh band lies at 0 cm-1. On this scale, the band positions will lie at frequencies that correspond to the energy levels of different functional group vibrations. The Raman spectrum can thus be interpreted similar to the infrared absorption spectrum.

Why and Where Should I Use Raman?

Raman scattering is a spectroscopic technique that is complementary to infrared absorption spectroscopy. Raman offers several advantages over mid-IR and near-IR spectroscopy, including: Little or no sample preparation is required Water is a weak scatterer - no special accessories are needed for measuring aqueous solutions Water and CO2 vapors are very weak scatterers - purging is unnecessary Inexpensive glass sample holders are ideal in most cases Fiber optics (up to 100's of meters in length) can be used for remote analyses Since fundamental modes are measured, Raman bands can be easily related to chemical structure Raman spectra are "cleaner" than mid-IR spectra - Raman bands are narrower, and overtone and combination bands are generally weak The standard spectral range reaches well below 400 cm-1, making the technique ideal for both organic and inorganic species Raman spectroscopy can be used to measure bands of symmetric linkages which are weak in an infrared spectrum (e.g. -S-S-, -C-S-, -C=C-)

Raman spectroscopy can be used for both qualitative and quantitative applications. The spectra are very specific, and chemical identifications can be performed by using search algorithms against digital databases. As in infrared spectroscopy, band areas are proportional to concentration, making Raman amenable to quantitative analysis. In fact, because Raman bands are inherently sharper than their infrared counterparts, isolated bands are often present in the spectrum for more straightforward quantitative analysis. Infrared absorption and Raman scattering are governed by completely different selection rules. Infrared bands arise from an interaction between light and the oscillating dipole moment of a vibrating molecule. Raman bands arise from an oscillating induced dipole caused by light waves interacting with the polarizability ellipsoid of a vibrating molecule. (It is common to describe the polarizability ellipsoid as the shape of the electron cloud around the molecule). Thus, symmetric stretches, vibrations involving multiple bonds, and vibrations of heavier atoms typically give rise to strong bands in the Raman spectrum. Asymmetric molecules will have bands at similar frequencies in both the infrared and Raman spectra, but

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their relative intensities will be very different. In most cases, a chemical species will have strong, indicative bands in both its Raman and IR spectra but they may not coincide. Which technique is superior depends upon the molecule of interest, the concentration level, the matrix or solution, other interfering species present, and the desired sampling method. For many applications, Raman may be the better answer to your spectroscopic identification or monitoring needs. Please continue browsing our website to learn about Raman products from InPhotonics and chemical applications we have developed. Download a printable version of this page Technical Note #11: An Introduction to Raman for the Infrared Spectroscopist (requires Adobe Acrobat Reader)

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