40 research outputs found
Field-induced diastereomers for chiral separation
A novel approach for the state-specific enantiomeric enrichment and the
spatial separation of enantiomers is presented. Our scheme utilizes techniques
from strong-field laser physics, specifically an optical centrifuge in
conjunction with a static electric field, to create a chiral field with defined
handedness. Molecular enantiomers experience unique rotational excitation
dynamics and this can be exploited to spatially separate the enantiomers using
electrostatic deflection. Notably, the rotational-state-specific enantiomeric
enhancement and its handedness is fully controllable. To explain these effects,
we introduce the conceptual framework of
of a chiral molecule and perform robust quantum mechanical simulations on the
prototypical chiral molecule propylene oxide (CHO), for which ensembles
with an enantiomeric excess of up to were obtained
Ultrafast light-induced dynamics in solvated biomolecules: The indole chromophore with water
Interactions between proteins and their solvent environment can be studied in
a bottom-up approach using hydrogen-bonded chromophore-solvent clusters. The
ultrafast dynamics following UV-light-induced electronic excitation of the
chromophores, potential radiation-damage, and their dependence on solvation are
important open questions. The microsolvation effect is challenging to study due
to the inherent mix of the produced gas-phase aggregates. We used the deflector
to spatially separate different molecular species in combination with
pump-probe velocity-map-imaging experiments. We demonstrated that this powerful
experimental approach reveals intimate details of the UV-induced dynamics in
the near-UV-absorbing prototypical biomolecular indole-water system. We
determined the time-dependent appearance of the different reaction products and
disentangled the occurring ultrafast processes. This novel approach ensures
that the reactants are well-known and that detailed characteristics of the
specific reaction products are accessible -- paving the way for the complete
chemical-reactivity experiment
Strong-field ionization of complex molecules
Strong-field photoelectron momentum imaging of the prototypical biomolecule
indole was disentangled in a combined experimental and computational approach.
Experimentally, strong control over the molecules enabled the acquisition of
photoelectron momentum distributions in the molecular frame for a well-defined,
narrow range of incident intensities. A novel, highly efficient semiclassical
simulation setup based on the adiabatic tunneling theory quantitatively
reproduced these results. Jointly, experiment and computations revealed
holographic structures in the asymptotic momentum distributions, which were
found to sensitively depend on the alignment of the molecular frame. We
identified the essential molecular properties that shape the photoelectron
wavepacket in the first step of the ionization process and employ a
quantum-chemically exact description of the cation during the subsequent
continuum dynamics. The detailed modeling of the molecular ion, which accounts
for its polarization by the laser-electric field, enables the simulation of
laser-induced electron diffraction off large and complex molecules and provides
full insight into the photoelectron's dynamics in terms of semiclassical
trajectories. This provides the computational means to unravel strong-field
diffractive imaging of biomolecular systems on femtosecond time scales
Spatial separation of pyrrole and pyrrole-water clusters
We demonstrate the spatial separation of pyrrole and pyrrole(HO) clusters
from the other atomic and molecular species in a supersonically-expanded beam
of pyrrole and traces of water seeded in high-pressure helium gas. The
experimental results are quantitatively supported by simulations. The obtained
pyrrole(HO) cluster beam has a purity of ~100 %. The extracted rotational
temperature of pyrrole and pyrrole(HO) from the original supersonic
expansion is K, whereas the temperature of the
deflected, pure-pyrrole(HO) part of the molecular beam corresponds to
K
Knife edge skimming for improved separation of molecular species by the deflector
A knife edge for shaping a molecular beam is described to improve the spatial
separation of the species in a molecular beam by the electrostatic deflector.
The spatial separation of different molecular species from each other as well
as from atomic seed gas is improved. The column density of the selected
molecular-beam part in the interaction zone, which corresponds to higher signal
rates, was enhanced by a factor of 1.5, limited by the virtual source size of
the molecular beam.Comment: 3 pages, 2 figure
Setting the photoelectron clock through molecular alignment
The interaction of strong laser fields with matter intrinsically provides
powerful tools to image transient dynamics with an extremely high
spatiotemporal resolution. Here, we study strong-field ionisation of
laser-aligned molecules and show a full real-time picture of the photoelectron
dynamics in the combined action of the laser field and the molecular
interaction. We demonstrate that the molecule has a dramatic impact on the
overall strong-field dynamics: it sets the clock for the emission of electrons
with a given rescattering kinetic energy. This result represents a benchmark
for the seminal statements of molecular-frame strong-field physics and has
strong impact on the interpretation of self-diffraction experiments.
Furthermore, the resulting encoding of the time-energy relation in
molecular-frame photoelectron momentum distributions shows the way of probing
the molecular potential in real-time and accessing a deeper understanding of
electron transport during strong-field interactions.Comment: Final version. Added appendixes and supplementary display item