Raman Spectroscopy

Joe A. Granados Summer Bridge Program July 17, 2003

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Raman Spectroscopy Introduction: Rubies! Emeralds! Diamonds! Tables upon tables of these precious stones are collected from all over the world at the Gem and Mineral Show. Crowds of people gather to buy, sell, and trade their little rarities. What if amidst all of these items were a few eye catching gems that could only be found on another planet? How much would people pay to have a ring with a Martian mineral imbedded on its surface? In the year 2008 another rover is going to make a six to eight month trip to Mars. Onboard the rover, will be a probe attached to a device that can identify minerals with more efficiency than any other Mars bound instrument. This device is called a Raman Spectrometer. It is governed by the theory of Raman scattering which was discovered in 1928 (Skoog). Now, with the advent of modern technologies, Raman spectroscopy is a valuable tool for analyzing molecules. Objective: Before this upcoming rover mission can begin, a Raman instrument specific to the Mars bound machine needs to be constructed as well as a database and a program for operating the instrument and interfacing with the database. The purpose of this project was to assist in the creation of the mineral portion of the database. For this, a basic understanding of Raman spectroscopy was required in order to use a Raman spectrometer in a lab setting for the purpose of collecting data for the database. Knowledge of the instruments devices and the program that links the operator to the instrument is also vital in creating a library of Raman spectra. Theory: Raman spectroscopy is the creation and investigation of Raman scattering for the purpose of identifying molecules (C. & G.). Raman scattering is created by irradiating a sample with a light source at one specific wavelength or color. Today, this monochromatic light source is usually in the form of a laser. In order for this to work, the laser has to be at a wavelength so as not to be absorbed by the molecule (Skoog). Absorption occurs when the source has enough energy to bring the molecule into an exited electronic state. The resulting observed light radiating from the sample will be in the form of luminescence. This can be florescence which is radiation emitted as the molecule transitions from an excited state to a lower one of the phosphorescence which is radiation emitted as the

Granados molecule transitions from an excited state to a lower one of a different multiplicity (Karplus). To prevent this type of absorption the light source needs to have energy lower than the energy required to bring a molecule from the ground state to the lowest electronic state. E = h * = h * (c / ) where the energy is equal to planks constant multiplied by the frequency of the light which is nothing but the velocity of light divided by its wavelength. This suggests that a light source with the longest possible wavelength would be ideal. However, there is another form of absorption that is used for infrared spectroscopy. IR absorption spectra of substances can be acquired by irradiating molecules with infrared radiation of varying frequencies to achieve a resonance that matches the vibration of the molecule. IR is light at wavelengths greater than 700 nm. Also, the detector that picks up the light spectra has a detection limit that begins to drop off at 1050 nm and terminates at 1100 nm. Since the Raman Shift is measured in wave numbers away from the light source, not all of the Raman scattering may be observed by the detector. For example a light source at 900 nm would be restricted to Raman scattering less than 1587 cm-1 or wave numbers from converting the laser wavelength and the detector drop off wavelength to wave numbers by: cm-1 = (107 nm) / ( nm cm). The company that is constructing the instrument for the a Mars rover would like to view Raman shifts up to 4000 cm-1. Furthermore, the intensity of the scattering looks like the following: ~ (ex)ex4Eonie-Ei/kT where ex is the frequency of the excitation energy and Eo is the power of the laser (Ingle). With frequency inversely proportioned to the wavelength = c / , a longer wavelength will yield a smaller frequency even though more power can be used without compromising the sample. This is because of the excitation energy raised to a power of four. The term (ex) is Raman cross section which is dependent on the sample, ni is the number density of state i, and e-Ei/kT is the Boltzmann factor for state i (Ingle). Raman and Rayleigh scattering can now occur with the right light source generally closer to a wavelength near IR allowing for a smaller excitation energy. This can be an energy that brings the molecule to some virtual state between the ground state and the lowest

Granados electronic state. Most of the time the molecule will jump back down to where it originated from emitting Rayleigh scattering. This scattering is the same wavelength as the light source because there is no change in excitation energy which is a function of h. where is the frequency of the scattered light and h is Plancks constant. When the molecule leaves the virtual state and finishes on the first vibrational level of the ground state, then E is subtracted from the initial Energy of the light source equaling E E. Since the energy is smaller, the wavelength is longer. This is know as Stokes emissions. if the molecule starts off in the first vibrational level in the ground state when it is irradiated, and the molecule travels back down to the lowest ground state a change in energy is also observed. This is an increase in energy equaling E + E which indicates an emission of a shorter wavelength. In general Rayleigh scattering is 103 times more intense than the stokes and antistokes lines. Stokes lines are usually more intense than anti-Stokes lines, but the ration of anti-stokes to stokes increases with temperature as molecules appear in the first vibrational level of the ground state more often. Though anti-

Granados Stokes lines are not affected by florescence as Stokes lines are. Raman scattering is also about 10-5 of the power of the initial light source. The laser has an electric field that is described by: E = Eocos(2ext) where E0 is the amplitude of the wave (Skoog). There an induced dipole moment (m) when the electric field of the laser interacts with the molecule. m = E = Eocos(2ext) and is defined as a constant called the polarizability of the molecular bond. This constant measure the molecules ability to move in response to a passing electric field. If the polarizability varies as a function of the distance between nuclei of the atoms in the bond, then the molecule is said to be Raman active. This function of the polarizability will look like the following: = o + (r - req)(/r) where o is the polarizability of the bond at the equilibrium internuclear distance req and r is the internuclear separation at any instant. The change in internuclear separation varies with the frequency of the vibration v as given by: r req = rmcos(2vt) where rm is the maximum internuclear separation relative to the equilibrium position. I then have the equation: = o + rmcos(2vt)(/r). The expression for the induced dipole moment is no m = Eocos(2ext) + Eo * rmcos(2vt)(/r) * cos(2ext). Then using the trigonometric identity of cos x cos y = (cos (x+y) + cos (x-y)) / 2, I get m = Eocos(2ext) + (Eo/2)rm(/r)cos(2(ex - v)t) + (Eo/2)rm(/r)cos(2(ex + v)t). The first term in the equation represents Rayleigh scattering which is at the same frequency as the light source. The second term in the equation represents the stokes as well as the third term represents the anti-stokes emissions. This shows that the magnitude of the Raman Shift is independent of the frequency of the laser (Skoog). With this theory in place, All that is needed is an instrument. Procedure: On the first day of working in the Laboratory, I was to report to a scientist by the name of John Algeo. I was also partnered with another REU student by the name of Niki Farnsworth. John gave Niki and I a thorough tour of the lab that we were to be working in. The tour covered the operations and functions of the Raman instrument. He also told me what I would be doing in the lab. I would be first identifying the chemical formula of new minerals delivered to the lab. Then, I was to use a digital camera and take pictures of the individual minerals like the picture of gearksutite that is below.

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I then needed to transfer the picture files from the camera to the computers hard drive. I then was to save the pictures under there specific name and UAMM number which was the University of Arizona Mineral Museums method of classification. After preparing the minerals, I was then ready to run the Raman spectrometer and obtain spectra or separated light scattered from the mineral.

Gearksutite spectra with intensity as a function of Raman shift:

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After optimizing the Raman spectra by obtaining as high of an intensity as possible, I then had to format the spectra under two different file types. The first was a datalogue file that contained the parameters of the instrument, spectra, and mineral information. The second file was a file that could be read by a program called Omnic, which allows for the comparison against other spectrum. With these instructions John was ready to set us off on the tasks. Raman spectroscopy is the creation and investigation of Raman scattering for the purpose of identifying molecules. This is done with an instrument called a Raman spectrometer. This works by having a monochromatic light source which is light at one specific wavelength. The light then travels through some focusing optics before hitting the sample. The sample then radiates scattered light. Collecting optics grab some of the scattered light and direct it into some filtering optics that take any unwanted light. This light is then separated out by its wavelengths before entering the detector.

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The Raman spectrometer that I have been working with uses a diode laser that operates at 785 nm. This is a measurement of nana-meters which is a measurement of the wavelength of the light. Therefore the light has a long wavelength with a small amount of energy. The laser then travels through a transmission grating which spreads out the outlying light of slightly differing wavelengths while reflecting the light ninety degrees. Next the laser light passes through the collimating lens which straightens the light and concentrates the light into a point. From there, the light passed through an iris that only allows the central light that is at 785 nm through. The outlying light is absorbed by the iris. The laser then irradiates the sample which is placed on a movable stage. Below is a cross section of the laser as it passes through each device before hitting the sample.

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The stage is adjustable so that maximum scattering can be collected by the off axis paraboloid. The scattered light is then reflected ninety degrees and directed through the holographic notch filters. These filters are designed to take out a small range of light. In this case the range is at wavelengths of 785 nm give or take a few nana-meters. The notch filters are used to block the Rayleigh scattering which is of the same wavelengths as the diode laser. After the filters comes the focusing lens that focuses the light into an entrance slit. This slit is the point were the scattered light begins its journey through the spectrograph. This device bounce the light around reflecting out any remaining Rayleigh scattering and converts the Raman scattering into a detectable spectra of light wavelengths. A charged couple device then converts the light signal into electric signal, amplifies the signal and sends the signal to a card on the computer for processing. A computer program is used to interpret the signal from the card in the computer and create a set of data points to graph. The computer language used to create the program is called Labview. This programming language is a good platform for running and collecting data from scientific instruments. For the Raman spectrometer, the main important experimental data is saved as a datalogue file. Below is an image of the program that operates and accepts data from the Raman instrument.

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The only problem with this format is that when the programming language that reads these kinds of files is updated, the files become difficult to deal with. In this case the program that runs the Raman spectrometer in the Denton group uses labview version five programming. All the other computers in the laboratories contain labview version six. In the past the only way to view the datalogue files was in the Raman lab. Therefore in addition to building a mineral database, John Algeo gave Niki and I the task of creating a program using labview version six. Before I began working with the Denton group, I interviewed with Dr. Denton. I told him that I would be interested in learning the labview programming language. I believe that is why he had John Algeo start me off by going through a tutorial of the program. I did this for one day and realized that I wasnt going to gain very much by continuing. I had learned about the basic functions of the program, but I was having a hard time looking at example programs and learning from them. Luckily the next day John revealed the conversion problem. I received a formally typed description of a program that he wanted to create. This program was called Mineral Library Format Conversion. What it needed to do was be able to read old datalogue files in labview version six without reformatting the files. John then wanted to be able to save more experimental information to the files and be able to view them again with the same MinLibFmtCon program. As a plus, the files would still hopefully be viewable on the program that runs the Raman instrument. On the next page is image of the Mineral Library Format Conversion program. This shows the added features such as a link to a picture and many other text boxes and drop down menu options.

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For the first two to three weeks of working in the Gould Simpson Building at the U of A, I was building a mineral database using Raman spectroscopy for mineral identification and creating a program that reads the mineral database files and allow for files modification. After the general completion of the program, a post doctorate by the first name of Kevin Toerne asked me if I would help him out with the programming that operates his mass spectrometer. He wanted to be able to zoom in on his graphs of the data points while the program was operational. He also wanted to be able to create graphs that contained fifteen to thirty-two thousand data points with out having to reformat the graph with each file, because the program that he has creates fifty files with fifteen to thirty-two thousand data points roughly every half minute that the instrument is operational. During an experiment with several solutions, that have several minutes in which ionization occurs, many data files can be created. In affect, I spent another week or two learning about his program that runs the mass spectrometer and the functions of the instrument itself, while getting his labview program to run better, and creating a program that uses an entirely different programming language called Visual Basics to operate Microsoft Excel and create standardized graphs for his large data files. The rest of my time in the program was spent in meetings on average of twice a week and with discussions with Dr. Denton, John Algeo, and the other scientists in the Denton group. There was also much collaboration with Niki Farnsworth in regards to running the Raman instrument, creating the mineral database, and working on the Mineral Library Format Conversion program. I have conducted much research through books from the library, books from the Denton group, and articles published from the Denton group in Raman spectroscopy. This was for the purpose of creating an educational power point presentation for my peers as well as for a formalized report containing the details of my experience in the Summer Bridge Program.

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Acknoledgements: I would like to give thanks to Dr. Bonner Denton for taking me in and spending the time to teach me of the many aspects of analytical chemistry. I also give thanks to John Algeo, John Yamasaki, and everyone else in the Denton group who has guided me. I want to also give thanks to Niki Farnsworth who I worked on the project in the program with. The mentors James Little, John Lawver, Erwin Sucipto also played a huge roll in keeping everything on track.

Granados Bibliography

Bilhorn, R. B., J. V. Sweedler, P.M. Epperson, and M. B. Denton. Charge Transfer Device Detectors for Analytical Optical SpectroscopyOperation and Characteristics. Applied Spectroscopy. 41(7), 1114 (1987). C. & G. Merriam Co. Websters Revised Unabridged Dictionary. Dictionary.com (1988): 18 July 2003 <http://dictionary.reference.com/>. Ferraro, John R., and Kazuo Nakamoto. Introductory Raman Spectroscopy. San Diego: Academic, 1994. Ingle, James D. Jr., and Stanley R. Crouch. Petrochemical Analysis. Upper Saddle River: Prentice-Hall, 1988. Karplus, Martin, and Richard N. Porter. Atoms & Molecules. Menlo Park: Benjamin, 1970. Miessler, Gary L., and Donald A. Tarr. Inorganic Chemistry. Englewood Cliffs: PrenticeHall, 1991. Skoog, Douglas A., F. James Holler, and Timothy A. Nieman. Principles of Instrumental Analysis. Philadelphia: Harcourt, 1998. Sweedler, Jonathan V., Robert B. Bilhorn, Patrik M. Epperson, Gary R. Sims, and M. Bonner Denton. High-Performance Charge Transfer Device Detectors. Analytical Chemistry. 60(5), 282A (1988). Venkataraman, G. Journey Into Light. Sadashivanagar Bangalor: Indian Academy, 1988. Weissbluth, Mitchel. Atoms and Molecules. New York: Academic, 1978.