C566 Master Lecture Notes
Other interesting vibrational spectroscopy papers/techniques to survey on your own time:
Look up the following reference: “Infrared spectroscopy of gas-phase C
cyclopropenyl and propargyl cations,” A.M. Ricks, G.E. Douberly, P. v.R. Schleyer, and
M. A. Duncan, J. Chem. Phys.
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
This is the technique used to measure coupling of vibrational states.
HyperRaman Spectroscopy- “almost” doubling of incident light. hv
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
Sum frequency generation: hv
) when IR light is resonant with
This is sensitive to surface layers in which inversion symmetry is broken.
Another VERY LOW signal experiment!
Selectively breaking either bond in the bimolecular reaction of HOD with hydrogen
atoms, R.B. Metz et al., J. Chem. Phys.
, 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
Please see the paper, “Vibrational spectroscopy of anions by stimulated Raman
pumping-photoelectron spectroscopy,” M.R. Furlanetto et al., Chem. Phys. Lett.
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.
the dump laser is resonant with pump – E
, 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: