Stimulated Raman signals at conical intersections: <i>Ab initio</i> surface hopping simulation protocol with direct propagation of the nuclear wave function

Kowalewski, Markus; Mukamel, Shaul

doi:10.1063/1.4927475

Cited by 20 publications

(20 citation statements)

References 28 publications

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“…These experiments successfully demonstrated the capabilities of this spectroscopic technique and provided further evidence for the importance of low‐frequency motions in controlling excited‐state reactive dynamics. In addition, a tremendous amount of theoretical work has been devoted to several aspects of 2D‐FSRS, including the energy flow between spectral components, the resolution limit of fifth‐order signals with overlapping pulses and the applicability to the study of conical intersections …”

Section: Methodsmentioning

confidence: 99%

Femtosecond Stimulated Raman Spectroscopy

2016

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Femtosecond stimulated Raman spectroscopy (FSRS) is an ultrafast nonlinear optical technique that provides vibrational structural information with high temporal (sub-50 fs) precision and high spectral (10 cm(-1) ) resolution. Since the first full demonstration of its capabilities ≈15 years ago, FSRS has evolved into a mature technique, giving deep insights into chemical and biochemical reaction dynamics that would be inaccessible with any other technique. It is now being routinely applied to virtually all possible photochemical reactions and systems spanning from single molecules in solution to thin films, bulk crystals and macromolecular proteins. This review starts with an historic overview and discusses the theoretical and experimental concepts behind this technology. Emphasis is put on the current state-of-the-art experimental realization and several variations of FSRS that have been developed. The unique capabilities of FSRS are illustrated through a comprehensive presentation of experiments to date followed by prospects.

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Section: Methodsmentioning

confidence: 99%

Femtosecond Stimulated Raman Spectroscopy

2016

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“…The correlation functions in Eqs. 8, 14, and 15 have been calculated by a direct propagation simulation protocol [76]. The wave packet dynamics have been calculated with our in-house software QDng.…”

Section: Truecarsmentioning

confidence: 99%

Capturing Fingerprints of Conical Intersection: Complementary Information of Non-Adiabatic Dynamics from Linear X-ray Probes

Jadoun,

Gudem,

Kowalewski

2021

Preprint

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Many recent experimental ultrafast spectroscopy studies have hinted at non-adiabatic dynamics indicating the existence of conical intersections, but their direct observation remains a challenge. The rapid change of the energy gap between the electronic states complicated their observation by requiring bandwidths of several electron volts. In this manuscript, we propose to use the combined information of different X-ray pump-probe techniques to identify the conical intersection. We theoretically study the conical intersection in pyrrole using transient X-ray absorption, time-resolved X-ray spontaneous emission, and linear off-resonant Raman spectroscopy to gather evidence of the curve crossing.

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“…We propose a novel, background-free technique that can directly and unambiguously monitor the passage through a CoIn by using recently-developed attosecond broadband X-ray sources. Available optical techniques monitor state populations [3,11] or look for signatures in transient vibrational spectra to identify CoIns [8,10,12,13]. The technique proposed in this paper looks directly at electronic Raman resonances created by the electronic coherence generated as the system passes through the CoIn and is not sensitive to electronic populations.…”

Section: Introductionmentioning

confidence: 99%

Catching Conical Intersections in the Act: Monitoring Transient Electronic Coherences by Attosecond Stimulated X-Ray Raman Signals

et al. 2015

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Conical intersections (CoIn) dominate the pathways and outcomes of virtually all photophysical and photochemical molecular processes. Despite extensive experimental and theoretical effort, CoIns have not been directly observed yet and the experimental evidence is being inferred from fast reaction rates and some vibrational signatures. We show that short X-ray (rather than optical) pulses can directly detect the passage through a CoIn with the adequate temporal and spectral sensitivity. The technique is based on a coherent Raman process that employs a composite femtosecond/attosecond X-ray pulse to detect the electronic coherences (rather than populations) that are generated as the system passes through the CoIn.

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Stimulated Raman signals at conical intersections: Ab initio surface hopping simulation protocol with direct propagation of the nuclear wave function

Cited by 20 publications

References 28 publications

Femtosecond Stimulated Raman Spectroscopy

Femtosecond Stimulated Raman Spectroscopy

Capturing Fingerprints of Conical Intersection: Complementary Information of Non-Adiabatic Dynamics from Linear X-ray Probes

Catching Conical Intersections in the Act: Monitoring Transient Electronic Coherences by Attosecond Stimulated X-Ray Raman Signals

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