Frontiers in Spectroscopy
Chemical Physics 880.01 and 880.02
|Instructor: Terry A. Miller||Phone: 292-2569|
|Office: 18 Celeste Lab||email: firstname.lastname@example.org|
Course Description: This course will provide students with an overview of topics on the frontier of spectroscopic research. It will exploit internationally renowned lecturers, as well as outstanding OSU faculty, to cover topics ranging from very fundamental to quite applied. General areas to be covered will include fundamental characteristics of molecular quantum structure, electromagnetics, new experimental techniques, remote sensing, ultra-high sensitivity analytical techniques, astrophysical applications, etc. It is planned that the course will be offered multiple times, with topics and speakers varying with each offering. The lecturers for the upcoming Winter quarter are listed below.A new feature of ChemPhys 880 this year is a one hour "pre-lecture" discussion period led by an OSU faculty member. It is designed to help orient students to the readings, which they are expected to have read prior to the pre-lecture. Unless otherwise indicated, the pre-lecture will be held in 2015 McPherson at 5pm on the Tuesdays of the weeks with lectures.
Each topic will be covered by lectures on Wednesday and Friday mornings, 9:00-10:18AM, in MP2015.
Thursdays discussions (for students only) will begin at 9:00-10:18AM on Thursdays in MP2015.
Prerequisites: a previous spectroscopy course at OSU in Chemistry or Physics or prior permission of the instructor
Required Text: None; suggested articles for reading will be supplied prior to the lecture on a given topic.
All readings and lecture notes will be kept current on Carmen. If you were enrolled for Frontiers this quarter, you have your normal student login and password. If you are an advisor or post-doc and would like access to the readings and notes, email Becky Gregory, email@example.com, and she will arrange for a login and password for this site.
List of speakers and dates scheduled:
January 5 - 5pm-6pm in 2015 McPherson Lab - Pre-Lecture discussion by Anne McCoy
January 6-8 John Tully, Yale University
January 26 - 5pm-6pm in 2015 McPherson Lab - Pre-Lecture discussion by Brenda Winnewisser
January 27-29 Brooks Pate, University of Virginia
This lecture will provide an introduction to molecular rotational spectroscopy. The presentation will provide brief background on the assignment of rotational spectra by fitting to molecular Hamiltonians. This part of the talk will focus on "rigid" molecules but some of the effects from small and large amplitude vibrational motion will be included. Applications of molecular rotational spectroscopy in physical chemistry and analytical chemistry will be presented. The content of this lecture will be shaped by the 1968 review article by E. Bright Wilson, Jr. in Science titled "Microwave Spectroscopy in Chemistry."
E.B. Wilson, Jr., "Microwave Spectroscopy in Chemistry", Science 162, 59-66 (1968).
Other Recommended Material
D.M. Rank, C.H. Townes, and W.J. Welch, "Interstellar Molecules and Dense Clouds", Science 174, 1083-1101 (1971).
The second lecture will present results from a recent development in the field of molecular rotational spectroscopy. For highly vibrationally excited molecules there is a breakdown of the small-amplitude vibrational motion model that is the basis of the normal-mode approximation. In these cases, there is energy exchange between the vibrational modes, a process often called "intramolecular vibrational energy redistribution (IVR)." This physical process is required to move energy into the reaction coordinate during chemical reactions. Rapid IVR (on the time scale of the chemical reaction) is required for the validity of statistical theories of chemical reaction rates such as the widely used RRKM theory. Rotational spectroscopy offers unique advantages for monitoring vibrational energy flow in the low-frequency vibrational motions connected to reactions. The basic theory of molecular rotational spectroscopy in the presence of IVR will be presented.
J. Keske, D.A. McWhorter, and B.H. Pate, "Molecular rotation in the presence of intramolecular vibrational energy redistribution", Int. Rev. Phys. Chem. 19, 363-407 (2000).
Other Recommended Material
D.J. Nesbitt and R.W. Field, "Vibrational Energy Flow in Highly Excited Molecules: Role of Intramolecular Vibrational Redistribution", J. Phys. Chem. 100, 12735-12756 (1996).
U. Lourderaj and W.L. Hase, "Theoretical and Computational Studies of Non-RRKM Unimolecular Dynamics", J. Phys. Chem. A 113, 2236-2253 (2009).
Kevin O. Douglass, Brian C. Dian, Gordon G. Brown, James E. Johns, Pradeep M. Nair, and Brooks H. Pate, "Motional Narrowing of the Rotational Spectrum of Trifluoropropyne at 6550 cm-1 by Intramolecular Vibrational Energy Redistribution", J. Chem. Phys. 121, 6845-6854 (2004).
Brian C. Dian, Gordon G. Brown, Kevin O. Douglass, and Brooks H. Pate, "Measuring Picosecond Isomerization Dynamics via Ultra-broadband Fourier Transform Microwave Spectroscopy", Science 320, 924-928 (2008.
The field of molecular rotational spectroscopy is being transformed by technology advances in high-speed digital electronics. These advances will force changes in the way spectroscopists approach data analysis in both laboratory and in radio astronomy. The spectrometers and radio telescopes designed around high-speed digital technology will make rotational spectroscopy the first area of molecular spectroscopy to enter the realm of TB/day data rates. At the simplest level, these advances translate to faster measurement time. In both laboratory spectroscopy and radio astronomy this technology will reduce measurement times by factors of about 1000; what took years to do in the past will now take days. However, the challenge to spectroscopists is to develop ways to exploit these advances to solve new problems in chemistry. Issues and opportunities associated with the combination of high-throughput rotational spectroscopy and high-performance computing will be presented.
Gordon G. Brown, Brian C. Dian, Kevin O. Douglass, Scott M. Geyer, and Brooks H. Pate, "A Broadband Fourier Transform Microwave Spectrometer Based on Chirped Pulse Excitation" Rev. Sci. Instrum. 79, 053103 (2008).
Other Recommended Material
S. Albert, D.T. Petkie, R.P.A. Bettens, S.P. Belov, and F.C. DeLucia, "A New Gas-Phase Analytical Tool", Analytical Chemistry 70, 719A-727A (1998).
Z. Kisiel, O. Dorosh. M. Winnewisser, M. Behnke, I.R. Medvedev, and F.C. DeLucia, "Comprehensive analysis of the FASSST rotational spectrum of S(CN)2", J. Mol. Spectrosc. 246, 39-56 (2007).
"Ensuring the Integrity, Accessibility, and Stewardship of Research Data in the Digital Age (Executive Summary)", National Academy of Sciences, Published by the National Academy Press (www.nap.edu).
J. Markoff, "A Deluge of Data Shapes a New Era in Computing", New York Times, December 14, 2009.
A. Vance, "Training to Climb an Everest of Digital Data", New York Times, October 11, 2009.
Additional Background in Radio Astronomy:
Textbooks for Molecular Rotational Spectroscopy:
C.H. Townes and A.L. Schawlow, Microwave Spectroscopy, (Dover, 1955).
J.E. Wollrab, Rotational Spectra and Molecular Structure, (Academic Press, 1967).
H.W. Kroto, Molecular Rotation Spectra, (John-Wiley, 1975).
W. Gordy and R.L. Cook, Microwave Molecular Spectra, 3rd Edition, (Wiley Interscience, 1984).
The Gordy and Cook text is available on-line: http://www.knovel.com/web/portal/browse/display?_EXT_KNOVEL_DISPLAY_bookid=1303
Preliminary lecture topics:
Roaming Atoms and Radicals: A New Mechanism in Molecular Dissociation by Arthur G. Suits, Accounts of Chemical Research 2008.
The Roaming Atom: Straying from the Reaction Path in Formaldehyde Decomposition by Bowman et al, Science 2004.
Photodissociation of acetaldehyde as a second example of the roaming mechanism by P. L. Houston and S. H. Kable, 2006.
Roaming is the dominant mechanism for molecular products in acetaldehyde photodissociation by Bowman et al, PNAS 2008.
Other Suggested Readings
Two-Dimensional Fluorescence (Excitation/Emission) Spectroscopy as a Probe of Complex Chemical Environments by Scott Kable et al, J. Phys. Chem. A Letters, 2006.
Laser-induces fluorescence and dispersed fluorescence spectroscopy of jet-cooled 1-phenylpropargyl radical by Kable et al, J. Chem. Phys. 2009.
Spectroscopic Identification of the Resonance-Stabilized cis- and trans-1-Vinylpropargyl Radicals by Timothy Schmidt et al, JACS, 2009.
March 2 - 5pm-6pm in 2015 McPherson Lab - Pre-Lecture discussion by Frank DeLucia
March 3-5 Tom Wilson, ALMA, Santiago Chile
Relevant websites: Stars and Habitable Planets and The Outer Planets: A Star is Born
Grading: Satisfactory/Unsatisfactory options: Class attendance and participation
Letter grade option: Class attendance and participation plus term paper
(Grades will be assigned solely by OSU faculty.)
(3 hours) Call number 5920 for ChemPhys 880.01 (S/U option)(3 hours) Call number 28805 for ChemPhys 880.02 (graded option)