44 research outputs found
Photodynamics and Ground State Librational States of ClF Molecule in solid Ar. Comparison of experiment and theory
Photodynamics calculations of a ClF molecule in solid Ar are compared to experimental results and a new interpretation is given for the observed femtosecond-pump-probe signal modulation. We analyze the round-trip and depolarization times for the excited state wave-packet motion and discuss the incorporation of lattice cage motions that partially explain the time dependence of the measured signal. Librational eigenstates and -energies are calculated by solving the rotational Schrödinger equation in the previously computed [T. Kiljunen, M. Bargheer, M. Gühr, and N. Schwentner, Phys. Chem. Chem. Phys. 6 (9), 2185-2197 (2004)] octahedral potentials that hinder free molecular rotation in the solids. The obtained level structure is compared to infrared-spectroscopic results. We comment on the correspondence between temperature effects in the classical dynamics of the nuclei and the quantum mechanical probability distributions. We find the combinative treatment of different simulation temperatures congruous for interpreting the experimental results at cryogenic conditions
Influence of Phase Matching on the Cooper Minimum in Ar High Harmonic Spectra
We study the influence of phase matching on interference minima in high
harmonic spectra. We concentrate on structures in atoms due to interference of
different angular momentum channels during recombination. We use the Cooper
minimum (CM) in argon at 47 eV as a marker in the harmonic spectrum. We measure
2d harmonic spectra in argon as a function of wavelength and angular
divergence. While we identify a clear CM in the spectrum when the target gas
jet is placed after the laser focus, we find that the appearance of the CM
varies with angular divergence and can even be completely washed out when the
gas jet is placed closer to the focus. We also show that the argon CM appears
at different wavelengths in harmonic and photo-absorption spectra measured
under conditions independent of any wavelength calibration. We model the
experiment with a simulation based on coupled solutions of the time-dependent
Schr\"odinger equation and the Maxwell wave equation, including both the single
atom response and macroscopic effects of propagation. The single atom
calculations confirm that the ground state of argon can be represented by its
field free symmetry, despite the strong laser field used in high harmonic
generation. Because of this, the CM structure in the harmonic spectrum can be
described as the interference of continuum and channels, whose relative
phase jumps by at the CM energy, resulting in a minimum shifted from the
photoionization result. We also show that the full calculations reproduce the
dependence of the CM on the macroscopic conditions. We calculate simple phase
matching factors as a function of harmonic order and explain our experimental
and theoretical observation in terms of the effect of phase matching on the
shape of the harmonic spectrum. Phase matching must be taken into account to
fully understand spectral features related to HHG spectroscopy
Strongly dispersive transient Bragg grating for high harmonics
We create a transient Bragg grating in a high-harmonic generation medium using two counterpropagating pulses. The Bragg grating disperses the harmonics in angle and can diffract a large bandwidth with temporal resolution limited only by the source size. © 2010 Optical Society of America
Conformer-specific photochemistry imaged in real space and time
Conformational isomers (conformers) of molecules play a decisive role in biology and organic chemistry. However, experimental methods for investigating chemical reaction dynamics are typically not conformersensitive. We report on a gas-phase megaelectronvolt ultrafast electron diffraction investigation of a-phellandrene undergoing an electrocyclic ring-opening reaction. We directly imaged the evolution of a specific set of a-phellandrene conformers into the product isomer predicted by the Woodward-Hoffmann rules in real space and time. Our experimental results are in quantitative agreement with nonadiabatic quantum molecular dynamics simulations, which provide considerable detail of how conformation influences the time scale and quantum efficiency of photoinduced ring-opening reactions.
Supplemental files attached
Ultraintense X-Ray Induced Ionization, Dissociation, and Frustrated Absorption in Molecular Nitrogen
Sequential multiple photoionization of the prototypical molecule N_2 is studied with femtosecond time resolution using the Linac Coherent Light Source (LCLS). A detailed picture of intense x-ray induced ionization and dissociation dynamics is revealed, including a molecular mechanism of frustrated absorption that suppresses the formation of high charge states at short pulse durations. The inverse scaling of the average target charge state with x-ray peak brightness has possible implications for single-pulse imaging applications
The photochemical ring-opening of 1,3-cyclohexadiene imaged by ultrafast electron diffraction
The ultrafast photoinduced ring-opening of 1,3-cyclohexadiene constitutes a
textbook example of electrocyclic reactions in organic chemistry and a model
for photobiological reactions in vitamin D synthesis. Here, we present direct
and unambiguous observation of the ring-opening reaction path on the
femtosecond timescale and sub-{\AA}ngstr\"om length scale by megaelectronvolt
ultrafast electron diffraction. We follow the carbon-carbon bond dissociation
and the structural opening of the 1,3-cyclohexadiene ring by direct measurement
of time-dependent changes in the distribution of interatomic distances. We
observe a substantial acceleration of the ring-opening motion after internal
conversion to the ground state due to steepening of the electronic potential
gradient towards the product minima. The ring-opening motion transforms into
rotation of the terminal ethylene groups in the photoproduct 1,3,5-hexatriene
on the sub-picosecond timescale. Our work demonstrates the potential of
megaelectronvolt ultrafast electron diffraction to elucidate photochemical
reaction paths in organic chemistry
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Probing nucleobase photoprotection with soft x-rays
Nucleobases absorb strongly in the ultraviolet region, leading to molecular excitation into reactive states. The molecules avoid the photoreactions by funnelling the electronic energy into less reactive states on an ultrafast timescale via non-Born-Oppenheimer dynamics. Current theory on the nucleobase thymine discusses two conflicting pathways for the photoprotective dynamics. We present our first results of our free electron laser based UV-pump soft x-ray-probe study of the photoprotection mechanism of thymine. We use the high spatial sensitivity of the Auger electrons emitted after the soft x-ray pulse induced core ionization. Our transient spetra show two timescales on the order of 200 fs and 5 ps, in agreement with previous (all UV) ultrafast experiments. The timescales appear at different Auger kinetic energies which will help us to decipher the molecular dynamics
Coherent ultrafast lattice-directed reaction dynamics of triiodide anion photodissociation
Solid-state reactions are influenced by the spatial arrangement of the reactants and the electrostatic environment of the lattice, which may enable lattice-directed chemical dynamics. Unlike the caging imposed by an inert matrix, an active lattice participates in the reaction, however, little evidence of such lattice participation has been gathered on ultrafast timescales due to the irreversibility of solid-state chemical systems. Here, by lowering the temperature to 80 K, we have been able to study the dissociative photochemistry of the triiodide anion (I<sub>3</sub>−) in single-crystal tetra-n-butylammonium triiodide using broadband transient absorption spectroscopy. We identified the coherently formed tetraiodide radical anion (I<sub>4</sub>•−) as a reaction intermediate. Its delayed appearance after that of the primary photoproduct, diiodide radical I<sub>2</sub>•−, indicates that I<sub>4</sub>•− was formed via a secondary reaction between a dissociated iodine radical (I<sup>•</sup>) and an adjacent I<sub>3</sub>−. This chemistry occurs as a result of the intermolecular interaction determined by the crystalline arrangement and is in stark contrast with previous solution studies