C566lecture14_000 - C566 Master Lecture Notes Lecture 14...

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C566 Master Lecture Notes Lecture 14 Other interesting vibrational spectroscopy papers/techniques to survey on your own time: 1. Look up the following reference: “Infrared spectroscopy of gas-phase C 3 H 3 + ions: The cyclopropenyl and propargyl cations,” A.M. Ricks, G.E. Douberly, P. v.R. Schleyer, and M. A. Duncan, J. Chem. Phys. 132, Art. 051101 (2010). Another strategy for measuring IR spectra of low-number density ions involves tagging the species with rare-gas atoms, which do little to perturb the bonding in the molecule of interest. But what about symmetry???? 2. 2DIR—Martin Zanni at U-Wisconsin, Andrei Tokmakoff at MIT, Michael Fayer at Stanford. This is the technique used to measure coupling of vibrational states. 3. HyperRaman Spectroscopy- “almost” doubling of incident light. hv out = 2(hv in ) E vib 4. Surface Enhanced Raman Spectroscopy- Huge polarizability introduced via proximity to a metal surface. Extreme Raman signal enhancements are encountered when chromophore is in the crevice between two nanoparticles [Please see the paper, “Designing, Fabricating, and Imaging Raman Hot Spots,” L. Qin et al., PNAS 103 , 13300 (2006)] 5. Sum frequency generation: hv vis + hv IR h(v vis + v IR ) when IR light is resonant with vibration. This is sensitive to surface layers in which inversion symmetry is broken. Another VERY LOW signal experiment! 6. Selectively breaking either bond in the bimolecular reaction of HOD with hydrogen atoms, R.B. Metz et al., J. Chem. Phys. 99 , 1744 (1993). In this paper, the two unique HOD molecular bonds are independently excited, resulting in controlled O H or O D bond breaking in the reaction with H 2 . 7. Please see the paper, “Vibrational spectroscopy of anions by stimulated Raman pumping-photoelectron spectroscopy,” M.R. Furlanetto et al., Chem. Phys. Lett. 326 , 439 (2000). In this technique, low number density ions are pumped to a virtual state, with a “dump” laser tuned to stimulate Raman excitation of vibrational modes. When the dump laser is resonant with pump – E vib , electron signal is produced from a third laser set just below the detachment continuum. 8. A combination of experimental and computational tools is highlighted in:
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“Raman spectra of size-selected silicon clusters and comparison with calculated structures,” E.C. Honea et al., Nature 366 , 42 (1993). In this paper, cationic silicon clusters are mass selected then gently deposited in a
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This note was uploaded on 01/18/2012 for the course C 566 taught by Professor Carolinechickjarroll during the Spring '11 term at Indiana.

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C566lecture14_000 - C566 Master Lecture Notes Lecture 14...

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