Attosecond molecular dynamics: fact or fiction?

Lépine, F.; Ivanov, Misha; Vrakking, Marc J. J.

doi:10.1038/nphoton.2014.25

Cited by 400 publications

(353 citation statements)

References 130 publications

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“…In molecules [8][9][10], electronic excitation is accompanied by redistribution of charge and the subsequent rearrangement-rotation, torsion, bond elongation-of the nuclei, on a time scale of femtoseconds to picoseconds, which can ultimately lead to the breaking of chemical bonds. Recent advances in the generation of attosecond light pulses [11] and time-resolved spectroscopic techniques [12] have opened the possibility of attosecond photochemistry [13,14], wherein the initial electronic excitation can steer a chemical reaction along a particular trajectory.…”

Section: Introductionmentioning

confidence: 99%

Reconstruction of an excited-state molecular wave packet with attosecond transient absorption spectroscopy

et al. 2016

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Attosecond science promises to allow new forms of quantum control in which a broadband isolated attosecond pulse excites a molecular wave packet consisting of a coherent superposition of multiple excited electronic states. This electronic excitation triggers nuclear motion on the molecular manifold of potential energy surfaces and can result in permanent rearrangement of the constituent atoms. Here, we demonstrate attosecond transient absorption spectroscopy (ATAS) as a viable probe of the electronic and nuclear dynamics initiated in excited states of a neutral molecule by a broadband vacuum ultraviolet pulse. Owing to the high spectral and temporal resolution of ATAS, we are able to reconstruct the time evolution of a vibrational wave packet within the excited B 1 u + electronic state of H 2 via the laser-perturbed transient absorption spectrum.

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Section: Introductionmentioning

confidence: 99%

Reconstruction of an excited-state molecular wave packet with attosecond transient absorption spectroscopy

et al. 2016

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“…[3][4][5][6][7] Molecular experiments to investigate such dynamics are particularly difficult to interpret as changes in nuclear geometry are also expected while electron dynamics is occurring. The computational cost of a full quantum mechanical treatment of both electron and nuclear dynamics is high.…”

Section: Introductionmentioning

confidence: 99%

Electron dynamics upon ionization: Control of the timescale through chemical substitution and effect of nuclear motion

Vacher

Mendive-Tapia

Bearpark

et al. 2015

The Journal of Chemical Physics

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Articles you may be interested inPhotoelectron spectroscopic study of the E⊗e Jahn-Teller effect in the presence of a tunable spin-orbit interaction. I. Photoionization dynamics of methyl iodide and rotational fine structure of CH3I+ and CD3I+ J. Chem. Phys. 134, 054308 (2011) Photoionization can generate a non-stationary electronic state, which leads to coupled electronnuclear dynamics in molecules. In this article, we choose benzene cation as a prototype because vertical ionization of the neutral species leads to a Jahn-Teller degeneracy between ground and first excited states of the cation. Starting with equal populations of ground and first excited states, there is no electron dynamics in this case. However, if we add methyl substituents that break symmetry but do not radically alter the electronic structure, we see charge migration: oscillations in the spin density that we can correlate with particular localized electronic structures, with a period depending on the gap between the states initially populated. We have also investigated the effect of nuclear motion on electron dynamics using a complete active space self-consistent field (CASSCF) implementation of the Ehrenfest method, most previous theoretical studies of electron dynamics having been carried out with fixed nuclei. In toluene cation for instance, simulations where the nuclei are allowed to move show significant differences in the electron dynamics after 3 fs, compared to simulations with fixed nuclei. C 2015 AIP Publishing LLC. [http://dx

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“…The technique is especially sensitive as the current density of a recolliding electron wavepacket exceeds that of conventional electron sources by several orders of magnitude [7]. Furthermore, the inherently subcycle and phase-locked nature of the recollision process gives access to electron dynamics on the attosecond scale, via information embedded in the photoelectron spectrum [8,9].One of the open questions in strong-field science concerns the importance of electron rescattering for negative ions. Significant progress has been made in understanding and controlling the equivalent process in neutral atoms and positive ions [10], but above-threshold detachment (ATD) presents a different challenge.…”

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confidence: 99%

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Electron rescattering in strong-field photodetachment ofF−

et al. 2015

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We present ab initio studies of photoelectron spectra for above threshold detachment (ATD) of F − anions in short, 1300 nm and 1800 nm laser pulses. We identify and assess the importance of electron rescattering in strong-field photodetachment of a negative ion through comparison with an analytic, Keldysh-type approach, demonstrating the capability of ab-initio computation in the challenging near-IR regime. We further assess the influence of the strong electron correlation on the photodetachment.PACS numbers: 32.80.Gc 31.15.VElectron rescattering is one of the fundamental processes occuring in the interaction between matter and intense light fields [1]. The mechanism is a critical part of the well known three-step or recollision model for high harmonic generation (HHG) or strong field double ionisation. According to the model an electron is first ionised, then driven by a strong laser field, before recolliding with the parent ion, either recombining, leading to HHG [2,3], or rescattering, leading to high-energy electron emission [4,5], or non-sequential double ionisation [6].Electron rescattering also encodes structural information about the residual ion into the wavepacket of the ejected electron and can thus be exploited as an experimental probe of the structure of the parent ion [1]. The technique is especially sensitive as the current density of a recolliding electron wavepacket exceeds that of conventional electron sources by several orders of magnitude [7]. Furthermore, the inherently subcycle and phase-locked nature of the recollision process gives access to electron dynamics on the attosecond scale, via information embedded in the photoelectron spectrum [8,9].One of the open questions in strong-field science concerns the importance of electron rescattering for negative ions. Significant progress has been made in understanding and controlling the equivalent process in neutral atoms and positive ions [10], but above-threshold detachment (ATD) presents a different challenge. The small binding energy allows detachment at low intensities. Hence to reach significant recollision energies, nearinfrared (NIR) laser fields are required. In addition, the absence of the Coulomb potential makes it easier for the electron wavepacket to spread out, reducing the effect of rescattering [4,5]. While evidence for rescattering from negative ions has been found experimentally [11], no verification has yet been provided from ab initio theory. A theoretical approach, based on first order correction to the strong field approximation, was able to reproduce experimental results from Br − and F − , [12] but a more recent study, using a numerical solution of the time-dependent Schrödinger equation (TDSE), found "no qualitative evidence of rescattering" for H − [13]. In this report we demonstrate that ab-initio theory can be used to investigate rescattering in the NIR regime.An additional complication in the description of negative ions is the much larger influence of dielectronicrepulsion. Several approximate methods have been empl...

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Attosecond molecular dynamics: fact or fiction?

Cited by 400 publications

References 130 publications

Reconstruction of an excited-state molecular wave packet with attosecond transient absorption spectroscopy

Reconstruction of an excited-state molecular wave packet with attosecond transient absorption spectroscopy

Electron dynamics upon ionization: Control of the timescale through chemical substitution and effect of nuclear motion

Electron rescattering in strong-field photodetachment ofF−

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