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. Herein, 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.

Excited-State Energy Surfaces in Molecules Revealed by Impulsive Stimulated Raman Excitation Profiles / Batignani, Giovanni; Sansone, Carlotta; Ferrante, Carino; Fumero, Giuseppe; Mukamel, Shaul; Scopigno, Tullio. - In: THE JOURNAL OF PHYSICAL CHEMISTRY LETTERS. - ISSN 1948-7185. - 12:(2021), pp. 9239-9247.

Excited-State Energy Surfaces in Molecules Revealed by Impulsive Stimulated Raman Excitation Profiles

Giovanni Batignani
Primo
;
Carlotta Sansone;Carino Ferrante;Giuseppe Fumero;Tullio Scopigno
Ultimo
2021

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. Herein, 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.
Raman Spectroscopy
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Excited-State Energy Surfaces in Molecules Revealed by Impulsive Stimulated Raman Excitation Profiles / Batignani, Giovanni; Sansone, Carlotta; Ferrante, Carino; Fumero, Giuseppe; Mukamel, Shaul; Scopigno, Tullio. - In: THE JOURNAL OF PHYSICAL CHEMISTRY LETTERS. - ISSN 1948-7185. - 12:(2021), pp. 9239-9247.
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Utilizza questo identificativo per citare o creare un link a questo documento: https://hdl.handle.net/11573/1569143
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