Broadband infrared and Raman probes of excited-state vibrational molecular dynamics: simulation protocols based on loop diagrams

KE Dorfman, BP Fingerhut, S Mukamel - Physical Chemistry Chemical …, 2013 - pubs.rsc.org
Physical Chemistry Chemical Physics, 2013pubs.rsc.org
Vibrational motions in electronically excited states can be observed either by time and
frequency resolved infrared absorption or by off resonant stimulated Raman techniques.
Multipoint correlation function expressions are derived for both signals. Three
representations which suggest different simulation protocols for the signals are developed.
These are based on the forward and the backward propagation of the wavefunction, sum
over state expansion using an effective vibrational Hamiltonian or a semiclassical treatment …
Vibrational motions in electronically excited states can be observed either by time and frequency resolved infrared absorption or by off resonant stimulated Raman techniques. Multipoint correlation function expressions are derived for both signals. Three representations which suggest different simulation protocols for the signals are developed. These are based on the forward and the backward propagation of the wavefunction, sum over state expansion using an effective vibrational Hamiltonian or a semiclassical treatment of a bath. We show that the effective temporal (Δt) and spectral (Δω) resolution of the techniques is not controlled solely by experimental knobs but also depends on the system dynamics being probed. The Fourier uncertainty ΔωΔt > 1 is never violated.
The Royal Society of Chemistry
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