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

TL;DR

This study introduces a novel two-color impulsive vibrational scattering technique that captures excited-state potential energy surfaces in molecules by analyzing resonant Raman profiles, validated through theoretical calculations.

Contribution

It presents a new experimental method to directly access and decode multidimensional excited-state PESs using phase-tuned resonant Raman spectroscopy.

Findings

Successful mapping of excited-state PESs in molecules.

Validation of experimental results with density functional theory.

Demonstration of phase tuning to decode nuclear displacements.

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.