Ultrafast strong-field dissociation of vinyl bromide: An attosecond transient absorption spectroscopy and non-adiabatic molecular dynamics study
| Autor: | Regina de Vivie-Riedle, Stephen R. Leone, Thomas Schnappinger, Henry Timmers, Florian Rott, Yuki Kobayashi, Daniel M. Neumark, Kristina F. Chang, Maurizio Reduzzi |
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| Rok vydání: | 2021 |
| Předmět: |
Materials science
Attosecond Population Ab initio 02 engineering and technology 01 natural sciences Molecular physics Spectral line Theory and Modelling Molecular dynamics ARTICLES 0103 physical sciences Ultrafast laser spectroscopy Physics::Atomic and Molecular Clusters Molecule 010306 general physics Spectroscopy education Instrumentation education.field_of_study Radiation Crystallography 021001 nanoscience & nanotechnology Condensed Matter Physics QD901-999 0210 nano-technology |
| Zdroj: | Structural dynamics (Melville, N.Y.), vol 8, iss 3 Structural Dynamics Structural Dynamics, Vol 8, Iss 3, Pp 034104-034104-12 (2021) |
| Popis: | Attosecond extreme ultraviolet (XUV) and soft x-ray sources provide powerful new tools for studying ultrafast molecular dynamics with atomic, state, and charge specificity. In this report, we employ attosecond transient absorption spectroscopy (ATAS) to follow strong-field-initiated dynamics in vinyl bromide. Probing the Br M edge allows one to assess the competing processes in neutral and ionized molecular species. Using ab initio non-adiabatic molecular dynamics, we simulate the neutral and cationic dynamics resulting from the interaction of the molecule with the strong field. Based on the dynamics results, the corresponding time-dependent XUV transient absorption spectra are calculated by applying high-level multi-reference methods. The state-resolved analysis obtained through the simulated dynamics and related spectral contributions enables a detailed and quantitative comparison with the experimental data. The main outcome of the interaction with the strong field is unambiguously the population of the first three cationic states, D 1, D 2, and D 3. The first two show exclusively vibrational dynamics while the D 3 state is characterized by an ultrafast dissociation of the molecule via C-Br bond rupture within 100 fs in 50% of the analyzed trajectories. The combination of the three simulated ionic transient absorption spectra is in excellent agreement with the experimental results. This work establishes ATAS in combination with high-level multi-reference simulations as a spectroscopic technique capable of resolving coupled non-adiabatic electronic-nuclear dynamics in photoexcited molecules with sub-femtosecond resolution. |
| Databáze: | OpenAIRE |
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