Excited-state energy surfaces in molecules revealed by impulsive stimulated Raman excitation profiles

Abstract

Photophysical and photochemical processes are ruled by the interplay between transient vibrational and electronic degrees of freedom, which are ultimately determined by the multidimensional potential energy surfaces (PESs). Differences between ground and excited PESs are encoded in the relative intensities of resonant Raman bands, but they are experimentally challenging to access requiring measurements at multiple wavelengths under identical conditions. Here we perform a two-color impulsive vibrational scattering experiment to launch nuclear wavepacket motions by an impulsive pump and record their coupling with a targeted excited-state potential by resonant Raman processes with a delayed probe, generating in a single-measurement background-free vibrational spectra across the entire sample absorption. Building on the interference between the multiple pathways resonant with the excited-state manifold that generate the Raman signal, we show how to experimentally tune their relative phase by varying the probe chirp, decoding nuclear displacements along different normal modes and revealing the multidimensional PESs. Our results are validated against time-dependent density functional theory.

References in corpus (5)

• Probing Femtosecond Lattice Displacement upon Photo-carrier generation in Lead Halide Perovskite
• Coherent anti-Stokes Raman Spectroscopy of single and multi-layer graphene
• Time-resolved broadband Raman spectroscopies; A unified six-wave-mixing representation
• Accessing Excited State Molecular Vibrations by Femtosecond Stimulated Raman Spectroscopy
• Broadband Impulsive Stimulated Raman Scattering based on a Chirped Detection

Cited by in corpus (2)

• Stimulated Raman lineshapes in the large light-matter interaction limit
• Retrieving genuine nonlinear Raman responses in ultrafast spectroscopy via deep learning