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Updated: May 10, 2026

Ultrafast Time-resolved Near-IR Stimulated Raman Measurements of Functional π-conjugate Systems
Published on: February 10, 2020
Broadband infrared and Raman probes of excited-state vibrational molecular dynamics: simulation protocols based on
Konstantin E Dorfman1, Benjamin P Fingerhut, Shaul Mukamel
1Department of Chemistry, University of California, Irvine, California 92697-2025, USA. kdorfman@uci.edu
Abstract:
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.
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