10.1021/jp404713x.s001
Erin S. Boyle
Erin S.
Boyle
Andrei V. Pakoulev
Andrei V.
Pakoulev
John C. Wright
John C.
Wright
Fully Coherent Triple Sum Frequency Spectroscopy of
a Benzene Fermi Resonance
American Chemical Society
2013
output beam
Benzene Fermi ResonanceIn
vibrational resonances
technique
probe states
Triple Sum Frequency
Raman transition
ω2 pulses
τ31 delay times
coherence pathway
τ21
ω1
Coherent Triple Sum Frequency Spectroscopy
ω2 axes
parity selection rules
time orderings
frequency excitation pulses
ω3 pulse
model system
TSF CMDS
excitation pulses
2013-07-11 00:00:00
Journal contribution
https://acs.figshare.com/articles/journal_contribution/Fully_Coherent_Triple_Sum_Frequency_Spectroscopy_of_a_Benzene_Fermi_Resonance/2396857
In this paper we present a new multiresonant
coherent multidimensional
spectroscopy (CMDS) technique employing a pathway that is both fully
coherent and necessarily unique. This technique is based on a Triple
Sum Frequency (TSF) coherence pathway with three excitation pulses
having frequencies ω<sub>1</sub>, ω<sub>2</sub>, and ω<sub>3</sub> and the phase matching condition <i>k⃗</i><sub>1</sub> + <i>k⃗</i><sub>2</sub> + <i>k⃗</i><sub>3</sub>. Two-dimensional spectra are created by independently
tuning the ω<sub>1</sub> and ω<sub>2</sub> pulses across
vibrational resonances while monitoring the intensity of a visible
output beam created by a Raman transition induced by the ω<sub>3</sub> pulse. Two-dimensional plots of the coherent dynamics are
created by independently scanning the τ<sub>21</sub> and τ<sub>31</sub> delay times between the different frequency excitation pulses
over all time orderings. TSF CMDS separates fundamental and overtone/combination
band states uniquely onto the ω<sub>1</sub> and ω<sub>2</sub> axes when τ<sub>21</sub> ≠ 0. TSF is valuable
in its ability to probe states of complementary parity to those seen
in Doubly Vibrationally Enhanced Four-Wave Mixing (DOVE-FWM), the
other fully coherent mixed electronic/vibrational CMDS method. This
capability is demonstrated through the use of neat benzene as a model
system, where the center of inversion imposes strict parity selection
rules.