Broadband impulsive stimulated Raman spectroscopy reveals electronic state-specific vibronic coupling and vibrational coherence transfer through nonadiabatic electronic coupling

TL;DR

This study introduces a broadband impulsive stimulated Raman spectroscopy method to analyze vibronic couplings and vibrational coherence transfer in iodine, revealing state-specific dynamics and nonadiabatic electronic interactions.

Contribution

It develops a new chirp correction technique and a benchmark method for calculating state-specific Raman cross-sections directly from pump-probe data.

Findings

Distinct dispersion characteristics of vibrational modes in ground and excited states.

Time-dependent spectral shifts correlate with pre-dissociation and solvent effects.

Evidence of vibrational coherence transfer mediated by nonadiabatic electronic coupling.

Abstract

Vibrational wavepacket dynamics in the ground (X) and excited (B) electronic states of iodine under impulsive-pump/broadband-probe excitation are revisited. A method for accurate chirp correction, necessary to determine the zero time for each component of spectrally dispersed data and thereby separate coherent vibrational dynamics from coherent artifacts and population kinetics, is introduced. While from these processed time-domain data the absolute Raman cross-section in the ground electronic state can be calculated using steady-state absorption, we show that the same can be done using the pump-probe data itself, and further extend this method as a benchmark to calculate the same for the excited electronic state; these cross-sections report on vibronic couplings specific to these states. Further, since the Fourier transform of the processed data yields information on vibrational modes averaged over the dephasing time, a wavelet analysis is performed to yield a joint time-frequency distribution of the vibrational modes, demonstrating how the time evolution of their frequencies can be extracted. The vibrational modes of the ground and excited electronic states are shown to exhibit distinct dispersion characteristics. Since overlapping spectral features appear at different time windows, such an analysis can disentangle spectral congestion, even from a simple one-dimensional measurement. Most interestingly, a rapid time-dependent spectral shift and decay of the B state mode, followed by the appearance and growth of the A-state mode, directly correlates with the pre-dissociation, followed by solvent caging-induced recombination. Thus, the present work reveals transfer of vibrational coherence from one electronic state (B) to another (A), mediated via nonadiabatic coupling to the intermediate dissociative state (a), underscoring the importance of electronic coherence.