Sub-7-femtosecond conical-intersection dynamics probed at the carbon K-edge

Zinchenko, Kristina; Ardana-Lamas, Fernando; Seidu, Issaka; Neville, Simon P.; Veen, Joscelyn van der; Lanfaloni, Valentina Utrio; Schuurman, Michael S.; Wörner, Hans Jakob

doi:10.1364/cleo_qels.2021.ftu4j.2

Cited by 3 publications

(2 citation statements)

References 51 publications

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“…The detection of chemical dynamics with electronic-state and vibrationalmode specificity is especially important for understanding nonadiabatic conical intersection dynamics in which the interplay of electronic and nuclear degrees of freedom is key in determining the course of a chemical reaction. [1][2][3][4][5][6][7] Attosecond transient absorption spectroscopy (ATAS) is a powerful, recently developed experimental tool for investigating chemical dynamics. 8 In ATAS, dynamics are tracked through the measurement of element-specific core-tovalence absorption transitions using isolated attosecond pulses in the extreme-ultraviolet (XUV).…”

Section: Introductionmentioning

confidence: 99%

Conical intersection and coherent vibrational dynamics in alkyl iodides captured by attosecond transient absorption spectroscopy

Chang

Wang

Poullain

et al. 2022

The Journal of Chemical Physics

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The photodissociation dynamics of alkyl iodides along the C–I bond are captured by attosecond extreme-ultraviolet (XUV) transient absorption spectroscopy employing resonant ∼20 fs UV pump pulses. The methodology of previous experiments on CH3I [Chang et al., J. Chem. Phys. 154, 234301 (2021)] is extended to the investigation of a C–I bond-breaking reaction in the dissociative A-band of C2H5I, i-C3H7I, and t-C4H9I. Probing iodine 4 d core-to-valence transitions in the XUV enables one to map wave packet bifurcation at a conical intersection in the A-band as well as coherent vibrations in the ground state of the parent molecules. Analysis of spectroscopic bifurcation signatures yields conical intersection crossing times of 15 ± 4 fs for CH3I, 14 ± 5 fs for C2H5I, and 24 ± 4 fs for i-C3H7I and t-C4H9I, respectively. Observations of coherent vibrations, resulting from a projection of A-band structural dynamics onto the ground state by resonant impulsive stimulated Raman scattering, indirectly reveal multimode C–I stretch and CCI bend vibrations in the A-bands of C2H5I, i-C3H7I, and t-C4H9I.

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Section: Introductionmentioning

confidence: 99%

Conical intersection and coherent vibrational dynamics in alkyl iodides captured by attosecond transient absorption spectroscopy

Chang

Wang

Poullain

et al. 2022

The Journal of Chemical Physics

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“…Femtosecond x-ray absorption spectroscopy on furfural 49 identified the chemical shift and population of PES, but it could not resolve electronic coherences or vibrational excitations upon diabatic passage. Thus far, despite encouraging progress 49,50 , identifying the ultrafast pathways with their expected electronic and vibrational coherences has been obscured by the challenge of temporally resolving and directly spectrally identifying them 19,51 . Even more so, the evolution of the coupling of electronic and vibrational dynamics in real-time has been largely elusive.…”

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confidence: 99%

Attosecond Core-Level Absorption Spectroscopy Reveals the Electronic and Nuclear Dynamics of Molecular Ring-Opening

Biegert,

Severino,

Reduzzi

et al. 2023

Preprint

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We show that attosecond core-level spectroscopy is a powerful tool for investigating molecular dynamics due to its combined attosecond temporal resolution and the broad coherent spectrum that allows deciphering the signatures of nuclear and electronic motion through their different energetic signatures. The method reveals the correlated real-time electronic and nuclear wave packet dynamics nonadiabatic transitions across conical intersections, identifies electronic and nuclear coherences, and registers symmetry changes directly in the x-ray absorption spectrum. We demonstrate the method's efficacy to unveil the entire time history of the ring-opening dynamics of furan. The investigation establishes attosecond core level spectroscopy as a potent method to investigate the real-time dynamics of photochemical reaction pathways in molecular systems.

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Sub-7-femtosecond conical-intersection dynamics probed at the carbon K-edge

Zinchenko

Ardana-Lamas

Seidu

et al. 2021

Science

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125

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Conical intersections allow electronically excited molecules to return to their electronic ground state. Here, we observe the fastest electronic relaxation dynamics measured to date by extending attosecond transient-absorption spectroscopy (ATAS) to the carbon K-edge. We selectively launch wave packets in the two lowest electronic states (D0 and D1) of C2H4+. The electronic D1 → D0 relaxation takes place with a short time constant of 6.8 ± 0.2 femtoseconds. The electronic-state switching is directly visualized in ATAS owing to a spectral separation of the D1 and D0 bands caused by electron correlation. Multidimensional structural dynamics of the molecule are simultaneously observed. Our results demonstrate the capability to resolve the fastest electronic and structural dynamics in the broad class of organic molecules. They show that electronic relaxation in the prototypical organic chromophore can take place within less than a single vibrational period.

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Sub-7-femtosecond conical-intersection dynamics probed at the carbon K-edge

Cited by 3 publications

References 51 publications

Conical intersection and coherent vibrational dynamics in alkyl iodides captured by attosecond transient absorption spectroscopy

Conical intersection and coherent vibrational dynamics in alkyl iodides captured by attosecond transient absorption spectroscopy

Attosecond Core-Level Absorption Spectroscopy Reveals the Electronic and Nuclear Dynamics of Molecular Ring-Opening

Sub-7-femtosecond conical-intersection dynamics probed at the carbon K-edge

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