Broadband infrared and Raman probes of excited-state vibrational molecular dynamics; Simulation protocols based on loop diagram

Abstract

Vibrational motions in electronically excited states can be observed by either time and frequency resolved infrared absorption or by off resonant stimulated Raman techniques. Multipoint correlation function expressions are derived for both signals. Three representations for the signal which suggest different simulation protocols are developed. These are based on the forward and the backward propagation of the wavefunction, sum over state expansion using an effective vibration Hamiltonian and a semiclassical treatment of a bath. We show that the effective temporal ($\Delta t$) and spectral ($\Delta \omega$) resolution of the techniques is not controlled solely by experimental knobs but also depends on the system dynamics being probed. The Fourier uncertainty $\Delta \omega \Delta t>1$ is never violated.

References in corpus (3)

• Nonlinear optical spectroscopy of single, few, and many molecules; nonequilibrium Green's function QED approach
• Partially-Time-Ordered Schwinger-Keldysh Loop Expansion of Coherent Nonlinear Optical Susceptibilities
• Multidimensional measures of impulsively driven stochastic systems based on the Kullback-Leibler distance

Cited by in corpus (5)

• Nonlinear optical signals and spectroscopy with quantum light
• Time-resolved broadband Raman spectroscopies; A unified six-wave-mixing representation
• Stochastic Liouville Equations for Femtosecond Stimulated Raman Spectroscopy
• Retrieving genuine nonlinear Raman responses in ultrafast spectroscopy via deep learning
• Stimulated Raman Spectroscopy with Entangled Light; Enhanced Resolution and Pathway Selection