Observing the Structural Evolution in the Photodissociation of Diiodomethane with Femtosecond Solution X-Ray Scattering

Panman, Matthijs R.; Biasin, Elisa; Berntsson, Oskar; Hermann, Markus; Niebling, Stephan; Hughes, Ashley J.; Kübel, Joachim; Atkovska, Kalina; Gustavsson, Emil; Nimmrich, Amke; Dohn, Asmus Ougaard; Laursen, Mads G.; Zederkof, Diana Bregenholt; Honarfar, Alireza; Tono, Kensuke; Katayama, Tetsuo; Owada, Shigeki; Driel, Tim B. van; Kjær, Kasper Skov; Nielsen, Martin Meedom; Davidsson, Jan; Uhlig, Jens; Haldrup, Kristoffer; Hub, Jochen S.; Westenhoff, Sebastian

doi:10.1103/physrevlett.125.226001

Cited by 28 publications

(34 citation statements)

References 65 publications

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“…This initial escaping speed of I is compatible with the result obtained from the time-resolved electron diffraction method aided by MD simulations, by which the dissociation speed of 5.8 Å/ps was determined 42 . In a recent study of the photodynamics of CH 2 I 2 studied by TRXL 44 , similar to I 3 − , the rapid dissociation upon photoexcitation of I radicals was observed. The reported escape speed of the dissociated I radical is 2.1 Å/ps, which is slower than 5.6 Å/ps in I 3 − .…”

Section: Resultsmentioning

confidence: 96%

Determining the charge distribution and the direction of bond cleavage with femtosecond anisotropic x-ray liquidography

et al. 2022

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Energy, structure, and charge are fundamental quantities characterizing a molecule. Whereas the energy flow and structure change in chemical reactions are experimentally characterized, determining the atomic charges of a molecule in solution has been elusive, even for a triatomic molecule such as triiodide ion, I3−. Moreover, it remains to be answered how the charge distribution is coupled to the molecular geometry; which I-I bond, if two I-I bonds are unequal, dissociates depending on the electronic state. Here, femtosecond anisotropic x-ray solution scattering allows us to provide the following answers in addition to the overall rich structural dynamics. The analysis unravels that the negative charge of I3− is highly localized on the terminal iodine atom forming the longer bond with the central iodine atom, and the shorter I-I bond dissociates in the excited state, whereas the longer one in the ground state. We anticipate that this work may open a new avenue for studying the atomic charge distribution of molecules in solution and taking advantage of orientational information in anisotropic scattering data for solution-phase structural dynamics.

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Section: Resultsmentioning

confidence: 96%

Determining the charge distribution and the direction of bond cleavage with femtosecond anisotropic x-ray liquidography

et al. 2022

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“…Femtosecond TRXSS (fs-TRXSS) at X-ray free-electron lasers (XFELs) is one of the promising experimental methods to study the initial structural response of HbI in the solution phase. Indeed, fs-TRXSS has been used to disclose the ultrafast structural dynamics of small molecules 19 – 25 and proteins 26 , 27 . In spite of its strong potential, however, fs-TRXSS has been applied to a limited number of model protein systems such as myoglobin (Mb) and photosynthetic reaction center unlike time-resolved serial femtosecond X-ray crystallography (TR-SFX), which has been used for various protein systems 28 – 34 .…”

Section: Introductionmentioning

confidence: 99%

Ultrafast coherent motion and helix rearrangement of homodimeric hemoglobin visualized with femtosecond X-ray solution scattering

et al. 2021

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Ultrafast motion of molecules, particularly the coherent motion, has been intensively investigated as a key factor guiding the reaction pathways. Recently, X-ray free-electron lasers (XFELs) have been utilized to elucidate the ultrafast motion of molecules. However, the studies on proteins using XFELs have been typically limited to the crystalline phase, and proteins in solution have rarely been investigated. Here we applied femtosecond time-resolved X-ray solution scattering (fs-TRXSS) and a structure refinement method to visualize the ultrafast motion of a protein. We succeeded in revealing detailed ultrafast structural changes of homodimeric hemoglobin involving the coherent motion. In addition to the motion of the protein itself, the time-dependent change of electron density of the hydration shell was tracked. Besides, the analysis on the fs-TRXSS data of myoglobin allows for observing the effect of the oligomeric state on the ultrafast coherent motion.

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“…Although Boltzmann‐TDDFT can solve the hot‐carrier cooling problem, it is a mean‐field approximation for the nuclear motion, so the nuclear path is deterministic 34 . In reality, in many problems, like chemical reactions, there could be several possible reaction outcomes 17,67 . These outcomes have certain probabilities, and the whole process is stochastic.…”

Section: Introductionmentioning

confidence: 99%

Algorithm advances and applications of time‐dependent first‐principles simulations for ultrafast dynamics

Liu

Wang

Chen

et al. 2021

WIREs Comput Mol Sci

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Far from equilibrium phenomenon is a central theme of contemporary material research. Such phenomenon can exhibit itself in atomic structure and dynamics, but very often it also happens as non-equilibrium phenomenon in the electronic structure. In ab initio material simulation, density functional theory (DFT) has played an essential role in studying electronic ground state problems. For excited states, besides many-body perturbation theory, another powerful tool is the time dependent DFT (TDDFT) method. In particular, the real-time TDDFT (rt-TDDFT) method can be used to simulate many non-equilibrium phenomena directly. Here we introduce our works on some algorithm advances based on our recently rt-TDDFT method. This method uses the plane-wave basis set, and significantly accelerates its efficiency by increasing the time step from 0.1-1 as in traditional methods to 0.2-0.5 fs. The noncollinear magnetic moments and spin-orbit coupling have also been included in our rt-TDDFT method. Furthermore, a Boltzmann-TDDFT algorithm has been developed to solve the hot carrier overheating problem in Ehrenfest dynamics, and a natural orbital branching algorithm has been developed to overcome the mean-field approximation in Ehrenfest dynamics nuclear trajectory, thus allows stochastic multiple paths in chemical reactions. Utilizing these methods, we have studied the photoinduced ultrafast demagnetization, ultrafast phase transition, energy transfer between plasmon and hot carriers, as well as the high-energy ion implantation and low-energy atomic diffusion in semiconductors.We believe the tools as the ones introduced here can enable us to study a wide range of phenomena which are of great interest in modern day material research.

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Observing the Structural Evolution in the Photodissociation of Diiodomethane with Femtosecond Solution X-Ray Scattering

Cited by 28 publications

References 65 publications

Determining the charge distribution and the direction of bond cleavage with femtosecond anisotropic x-ray liquidography

Determining the charge distribution and the direction of bond cleavage with femtosecond anisotropic x-ray liquidography

Ultrafast coherent motion and helix rearrangement of homodimeric hemoglobin visualized with femtosecond X-ray solution scattering

Algorithm advances and applications of time‐dependent first‐principles simulations for ultrafast dynamics

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