Two-Dimensional Impulsively Stimulated Resonant Raman Spectroscopy of Molecular Excited States

Giuseppe Fumero,Tullio Scopigno,Giovanni Bassolino,Matz Liebel,Torsten Wende,Carino Ferrante,Philipp Kukura,Shaul Mukamel,Giovanni Batignani,Christoph Schnedermann

doi:10.1103/physrevx.10.011051

Abstract

C. S. acknowledges financial support by the Royal Commission for the Exhibition of 1851. G. Bat. acknowledges the “Avvio Alla Ricerca 2018” grant by Sapienza Universita di Roma. T. W. acknowledges the Marie Curie Intra-European Fellowship (PIEF-GA-2013-623651) within the 7th European Community Framework Programme. S. M. gratefully acknowledges the support of the National Science Foundation Grant No. CHE-1663822.

Highlights

The investigation of light-induced processes is essential to the understanding of a variety of complex phenomena at the interface between physics, chemistry, and biology, in which excited-state dynamics cause the transient reconfiguration of atomic positions and electronic phases
After a second variable time delay T2, a broadband white-light continuum (WLC) probe pulse records the temporal evolution of the vibrational coherences through spectrally-resolved transient absorption
We introduced a resonant 2D-impulsive stimulated Raman scattering (ISRS) technique for multidimensional Raman spectroscopy

Summary

Introduction

The investigation of light-induced processes is essential to the understanding of a variety of complex phenomena at the interface between physics, chemistry, and biology, in which excited-state dynamics cause the transient reconfiguration of atomic positions and electronic phases. Ultrafast spectroscopy exploits tailored sequences of laser pulses to photoexcite and subsequently probe these channels, with the aim of unveiling the dynamics and the underlying vibronic structure. This goal requires the correct identification of the excited-state PESs involved in the photoinduced process as well as the mapping of their relative orientations and displacements. A number of different pulse schemes and strategies have been developed to meet these tasks, but the unambiguous identification of vibronic properties, such as quasiparticle couplings, mode-mixing and nonadiabatic effects, remains challenging [5,6]—in particular, on electronically excited states after the system has left the Franck-Condon (FC) region— due to overlapping signal contributions arising from

Results

Discussion

Conclusion