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Resonance IR: A Coherent Multidimensional Analogue of Resonance Raman
journal contribution
posted on 2015-12-17, 01:54 authored by Erin S. Boyle, Nathan A. Neff-Mallon, Jonathan D. Handali, John C. WrightThis
work demonstrates the use of triply resonant sum frequency
(TRSF) spectroscopy as a “resonance IR” analogue to
resonance Raman spectroscopy. TRSF is a four-wave-mixing process where
three lasers with independent frequencies interact coherently with
a sample to generate an output at their triple summation frequency.
The first two lasers are in the infrared and result in two vibrational
excitations, while the third laser is visible and induces a two-quantum
anti-Stokes resonance Raman transition. The signal intensity grows
when the laser frequencies are all in resonance with coupled vibrational
and electronic states. The method therefore provides electronic enhancement
of IR-active vibrational modes. These modes may be buried beneath
solvent in the IR spectrum and also be Raman-inactive and therefore
inaccessible by other techniques. The method is presented on the centrosymmetric
complex copper phthalocyanine tetrasulfonate. In this study, the two
vibrational frequencies were scanned across ring-breathing modes,
while the visible frequency was left in resonance with the copper
phthalocyanine tetrasulfonate Q band, resulting in a two-dimensional
infrared plot that also reveals coupling between vibrational states.
TRSF has the potential to be a very useful probe of structurally similar
biological motifs such as hemes, as well as synthetic transition-metal
complexes.
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TRSFsignal intensityvibrational frequenciessum frequencycopper phthalocyanine tetrasulfonateResonance IRResonance RamanThis workvibrational excitationsCoherent Multidimensional AnalogueIR spectrumlaser frequenciesvibrational statesresonance Raman spectroscopycopper phthalocyanine tetrasulfonate Q bandsummation frequencymode
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