Waveform control of molecular dynamics close to a conical intersection

Schüppel, Franziska; Schnappinger, Thomas; Bäuml, Lena; Vivie‐Riedle, Regina de

doi:10.1063/5.0031398

Cited by 15 publications

(21 citation statements)

References 50 publications

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“…The interaction of the IR pulse with the system is non-trivial, and uncoupling different effects is complicated. In their simulations the controllability of nuclear and electron dynamics using the CEP of the IR pulse was demonstrated: by projecting out different observables two mechanisms of CEP control were observed as seen in their earlier paper, 46 with periodicities of π and 2π. The nuclear asymmetry relating to the derivative coupling vector (see Figure 2)…”

Section: Graphical Toc Entrymentioning

confidence: 82%

Attochemistry: Is Controlling Electrons the Future of Photochemistry?

Merritt

Jacquemin

Vacher

2021

J. Phys. Chem. Lett.

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Controlling matter with light has always been a great challenge, leading to the ever-expanding field of photochemistry. In addition, since the first generation of light pulses of attosecond (1 as = 10 −18 s) duration, a great deal of efforts has been devoted to observing and controlling electrons on their intrinsic timescale. Because of their short duration, attosecond pulses have a large spectral bandwidth populating several electronically excited states in a coherent manner, i.e., an electronic wavepacket. Due to interference, such a wavepacket has a new electronic distribution implying a potentially different and totally new reactivity as compared to traditional photochemistry, and leading to the novel concept of "attochemistry". This nascent field requires the support of theory right from the start. In this Perspective, we discuss the opportunities offered by attochemistry, the related challenges, as well as the current and future state-of-art developments in theoretical chemistry needed to model it accurately.

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Section: Graphical Toc Entrymentioning

confidence: 82%

Attochemistry: Is Controlling Electrons the Future of Photochemistry?

Merritt

Jacquemin

Vacher

2021

J. Phys. Chem. Lett.

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“…In comparison with the pulse parameters used by Richter et al 57,59 all values are quite similar. Only our intensity is lower to stay in the range where the influence of the CEP pulse is mainly determined by the interplay of the non-adiabatic transition and the light induced electronic coherence 76 . By this we also ensure to stay below or at the threshold of ionization.…”

Section: B Dynamics In the Presence Of A Few-cycle Ir Pulsementioning

confidence: 94%

“…In the last part we investigate the controllability of the nuclear and electron dynamics by the variation of the CEP φ of a few-cycle IR laser pulse. As shown in the literature 68,[70][71][72][74][75][76] the CEP control scheme offers the possibility to steer electrons and nuclei in the ionization process but also during the passage through a CoIn. The few-cycle IR pulse builds up a coherent electronic and nuclear wavepacket with a well-defined phase-relationship controllable by the CEP.…”

Section: Waveform Control Of Molecular Dynamicsmentioning

confidence: 99%

“…Beside the free relaxation of NO 2 we also studied the influence on the coupled electron dynamics when applying a few-cycle IR laser pulse in the vicinity of the CoIn. The variation of the carrier envelope phase φ (CEP) of such a few-cycle pulse offers the possibility to steer electrons and nuclei 56,57,59,64,[68][69][70][71][72][73][74][75][76] . Similar to previous studies 56,57,59,64 we apply this CEP-control-scheme to NO 2 and evaluate the CEP-dependence of the resulting coupled nuclear and electron dynamics.…”

Section: Introductionmentioning

confidence: 99%

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Coupled nuclear and electron dynamics in the vicinity of a conical intersection

Schnappinger,

de Vivie-Riedle

2021

Preprint

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Ultrafast optical techniques allow to study ultrafast molecular dynamics involving both nuclear and electronic motion. To support interpretation, theoretical approaches are needed that can describe both the nuclear and electron dynamics. Hence, we revisit and expand our ansatz for the coupled description of the nuclear and electron dynamics in molecular systems (NEMol). In this purely quantum mechanical ansatz the quantum-dynamical description of the nuclear motion is combined with the calculation of the electron dynamics in the eigenfunction basis. The NEMol ansatz is applied to simulate the coupled dynamics of the molecule NO 2 in the vicinity of a conical intersection (CoIn) with a special focus on the coherent electron dynamics induced by the non-adiabatic coupling. Furthermore, we aim to control the dynamics of the system when passing the CoIn. The control scheme relies on the carrier envelope phase (CEP) of a few-cycle IR pulse. The laser pulse influences both the movement of the nuclei and the electrons during the population transfer through the CoIn.

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“…As shown in previous studies [47,48], the photo-excitation and the initial steps of the subsequent relaxation can be well-described on two-dimensional PES. We adopt these adiabatic PES, which were first reported by Keefer et al [47] and later modified [52,59]. The underlying two-dimensional coordinate space spanned by the vectors q 1 and q 2 includes all relevant structures, the FC point, the S 2 minimum, the optimized The potential surface exhibits a double-well structure with a small barrier separating the S 2 minimum on the top left from the CoIn seam on the bottom right (black).…”

Section: Photo-induced Dynamics Of Uracilmentioning

confidence: 99%

Photo-Induced Coupled Nuclear and Electron Dynamics in the Nucleobase Uracil

et al. 2021

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Photo-initiated processes in molecules often involve complex situations where the induced dynamics is characterized by the interplay of nuclear and electronic degrees of freedom. The interaction of the molecule with an ultrashort laser pulse or the coupling at a conical intersection (CoIn) induces coherent electron dynamics which is subsequently modified by the nuclear motion. The nuclear dynamics typically leads to a fast electronic decoherence but also, depending on the system, enables the reappearance of the coherent electron dynamics. We study this situation for the photo-induced nuclear and electron dynamics in the nucleobase uracil. The simulations are performed with our ansatz for the coupled description of the nuclear and electron dynamics in molecular systems (NEMol). After photo-excitation uracil exhibits an ultrafast relaxation mechanism mediated by CoIn's. Both processes, the excitation by a laser pulse and the non-adiabatic relaxation, are explicitly simulated and the coherent electron dynamics is monitored using our quantum mechanical NEMol approach. The electronic coherence induced by the CoIn is observable for a long time scale due to the delocalized nature of the nuclear wavepacket.

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Waveform control of molecular dynamics close to a conical intersection

Cited by 15 publications

References 50 publications

Attochemistry: Is Controlling Electrons the Future of Photochemistry?

Attochemistry: Is Controlling Electrons the Future of Photochemistry?

Coupled nuclear and electron dynamics in the vicinity of a conical intersection

Photo-Induced Coupled Nuclear and Electron Dynamics in the Nucleobase Uracil

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