arXiv subjects

Jochen Küpper

Publications and source records attributed to Jochen Küpper.

At least 109 records · Page 6Linked to original sources

arXiv2017

Characterizing and optimizing a laser-desorption molecular beam source

The design and characterization of a new laser-desorption molecular beam source, tailored for use in x-ray-free-electron-laser and ultrashort-pulse-laser imaging experiments, is presented. It consists of a single mechanical unit containing all source components, including the molecular-beam valve, the sample, and the fiber-coupled desorption laser, which is movable in five axes, as required for experiments at central facilities. Utilizing strong-field ionization, we characterize the produced molecular beam and evaluate the influence of desorption laser pulse energy, relative timing of valve opening and desorption laser, sample bar height, and which part of the molecular packet is probed on the sample properties. Strong-field ionization acts as a universal probe and allows to detect all species present in the molecular beam, and hence enables us to analyze the purity of the produced molecular beam, including molecular fragments. We present optimized experimental parameters for the production of the purest molecular beam, containing the highest yield of intact parent ions, which we find to be very sensitive to the placement of the desorbed-molecules plume within the supersonic expansion.

physics.chem-ph↗

arXiv2017

General variational approach to nuclear-quadrupole coupling in rovibrational spectra of polyatomic molecules

A general algorithm for computing the quadrupole-hyperfine effects in the rovibrational spectra of polyatomic molecules is presented for the case of ammonia (NH$_3$). The method extends the general variational approach TROVE by adding the extra term in the Hamiltonian that describes the nuclear quadrupole coupling, with no inherent limitation on the number of quadrupolar nuclei in a molecule. We applied the new approach to compute the nitrogen-nuclear-quadrupole hyperfine structure in the rovibrational spectrum of NH$_3$. These results agree very well with recent experimental spectroscopic data for the pure rotational transitions in the ground vibrational and $ν_2$ states, and the rovibrational transitions in the $ν_1$, $ν_3$, $2ν_4$, and $ν_1+ν_3$ bands. The computed hyperfine-resolved rovibrational spectrum of ammonia will be beneficial for the assignment of experimental rovibrational spectra, further detection of ammonia in interstellar space, and studies of the proton-to-electron mass variation.

physics.chem-ph↗

arXiv2017

Velocity-map imaging for emittance characterization of multiphoton-emitted electrons from a gold surface

A velocity-map-imaging spectrometer is demonstrated to characterize the normalized transverse emittance of photoemitted electron bunches. The two-dimensional (2D) projected velocity distribution images of photoemitted electrons are recorded by the detection system and analyzed to obtain the normalized transverse emittance. With the presented distribution function of the electron photoemission angles a mathematical method is implemented to reconstruct the three-dimensional (3D) velocity distribution curve. As a first example, multiphoton emission from a planar Au surface is studied via irradiation at a glancing angle by intense 45 fs laser pulses at a central wavelength of 800 nm. The reconstructed energy distribution agrees very well with the Berglund-Spicer theory of photoemission. The normalized transverse emittance of the intrinsic electron bunch is characterized to be 0.52 and 0.05 $π\cdot mm \cdot mrad$ in $X$- and $Y$-directions, respectively.

physics.app-ph↗

arXiv2017

Improved spatial separation of neutral molecules

We have developed and experimentally demonstrated an improved electrostatic deflector for the spatial separation of molecules according to their dipole-moment-to-mass ratio. The device features a very open structure that allows for significantly stronger electric fields as well as for stronger deflection without molecules crashing into the device itself. We have demonstrated its performance using the prototypical OCS molecule and we discuss opportunities regarding improved quantum-state-selectivity for complex molecules and the deflection of unpolar molecules.

physics.chem-ph↗

arXiv2017

Time-dependent analysis of the mixed-field orientation of molecules without rotational symmetry

We present a theoretical study of the mixed-field orientation of molecules without rotational symmetry. The time-dependent one-dimensional and three-dimensional orientation of a thermal ensemble of 6-chloropyridazine-3-carbonitrile molecules in combined linearly or elliptically polarized laser fields and tilted dc electric fields is computed. The results are in good agreement with recent experimental results of one-dimensional orientation for weak dc electric fields [J. Chem. Phys. 139, 234313 (2013)]. Moreover, they predict that using elliptically polarized laser fields or strong dc fields three-dimensional orientation is obtained. The field-dressed dynamics of excited rotational states is characterized by highly non-adiabatic effects. We analyze the sources of these non-adiabatic effects and investigate their impact on the mixed-field orientation for different field configurations in mixed-field-orientation experiments.

physics.chem-ph↗

arXiv2017

Alignment, Orientation, and Coulomb Explosion of Difluoroiodobenzene Studied with the Pixel Imaging Mass Spectrometry (PImMS) Camera

Laser-induced adiabatic alignment and mixed-field orientation of 2,6-difluoroiodobenzene (C6H3F2I) molecules are probed by Coulomb explosion imaging following either near-infrared strong-field ionization or extreme-ultraviolet multi-photon inner-shell ionization using free-electron laser pulses. The resulting photoelectrons and fragment ions are captured by a double-sided velocity map imaging spectrometer and projected onto two position-sensitive detectors. The ion side of the spectrometer is equipped with the Pixel Imaging Mass Spectrometry (PImMS) camera, a time-stamping pixelated detector that can record the hit positions and arrival times of up to four ions per pixel per acquisition cycle. Thus, the time-of-flight trace and ion momentum distributions for all fragments can be recorded simultaneously. We show that we can obtain a high degree of one- and three-dimensional alignment and mixed- field orientation, and compare the Coulomb explosion process induced at both wavelengths.

physics.chem-ph↗

arXiv2017

Characterizing gas flow from aerosol particle injectors

A novel methodology for measuring gas flow from small orifices or nozzles into vacuum is presented. It utilizes a high-intensity femtosecond laser pulse to create a plasma within the gas plume produced by the nozzle, which is imaged by a microscope. Calibration of the imaging system allows for the extraction of absolute number densities. We show detection down to helium densities of $4\times10^{16}$~cm$^{-3}$ with a spatial resolution of a few micrometer. The technique is used to characterize the gas flow from a convergent-nozzle aerosol injector [Struct.\ Dyn.~2, 041717 (2015)] as used in single-particle diffractive imaging experiments at free-electron laser sources. Based on the measured gas-density profile we estimate the scattering background signal under typical operating conditions of single-particle imaging experiments and estimate that fewer than 50 photons per shot can be expected on the detector.

physics.ins-det↗

arXiv2016

Adiabatic mixed-field orientation of ground-state-selected carbonyl sulfide molecules

We experimentally demonstrated strong adiabatic mixed-field orientation of carbonyl sulfide molecules (OCS) in their absolute ground state of $\text{N}_{\text{up}}/\text{N}_{\text{tot}}=0.882$. OCS was oriented in combined non-resonant laser and static electric fields inside a two-plate velocity map imaging spectrometer. The transition from non-adiabatic to adiabatic orientation for the rotational ground state was studied by varying the applied laser and static electric field. Above static electric field strengths of 10 kV/cm and laser intensities of $10^{11} \text{W/cm}^2$ the observed degree of orientation reached a plateau. These results are in good agreement with computational solutions of the time-dependent Schrödinger equation.

physics.chem-ph↗

arXiv2016

Imaging electron dynamics with time- and angle-resolved photoelectron spectroscopy

We theoretically study how time- and angle-resolved photoemission spectroscopy can be applied for imaging coherent electron dynamics in molecules. We consider a process in which a pump pulse triggers coherent electronic dynamics in a molecule by creating a valence electron hole. An ultrashort extreme ultraviolet (XUV) probe pulse creates a second electron hole in the molecule. Information about the electron dynamics is accessed by analyzing angular distributions of photoemission probabilities at a fixed photoelectron energy. We demonstrate that a rigorous theoretical analysis, which takes into account the indistinguishability of transitions induced by the ultrashort, broadband probe pulse and electron hole correlation effects, is necessary for the interpretation of time- and angle-resolved photoelectron spectra. We show how a Fourier analysis of time- and angle-resolved photoelectron spectra from a molecule can be applied to follow its electron dynamics by considering photoelectron distributions from an indole molecular cation with coherent electron dynamics.

physics.optics↗

arXiv2016

High-repetition-rate and high-photon-flux 70 eV high-harmonic source for coincidence ion imaging of gas-phase molecules

Unraveling and controlling chemical dynamics requires techniques to image structural changes of molecules with femtosecond temporal and picometer spatial resolution. Ultrashort-pulse x-ray free-electron lasers have significantly advanced the field by enabling advanced pump-probe schemes. There is an increasing interest in using table-top photon sources enabled by high-harmonic generation of ultrashort-pulse lasers for such studies. We present a novel high-harmonic source driven by a 100 kHz fiber laser system, which delivers 10$^{11}$ photons/s in a single 1.3 eV bandwidth harmonic at 68.6 eV. The combination of record-high photon flux and high repetition rate paves the way for time-resolved studies of the dissociation dynamics of inner-shell ionized molecules in a coincidence detection scheme. First coincidence measurements on CH$_3$I are shown and it is outlined how the anticipated advancement of fiber laser technology and improved sample delivery will, in the next step, allow pump-probe studies of ultrafast molecular dynamics with table-top XUV-photon sources. These table-top sources can provide significantly higher repetition rates than the currently operating free-electron lasers and they offer very high temporal resolution due to the intrinsically small timing jitter between pump and probe pulses.

physics.atom-ph↗

arXiv2015

Visualizing aerosol-particle injection for diffractive-imaging experiments

Delivering sub-micrometer particles to an intense x-ray focus is a crucial aspect of single-particle diffractive-imaging experiments at x-ray free-electron lasers. Enabling direct visualization of sub-micrometer aerosol particle streams without interfering with the operation of the particle injector can greatly improve the overall efficiency of single-particle imaging experiments by reducing the amount of time and sample consumed during measurements. We have developed in-situ non-destructive imaging diagnostics to aid real-time particle injector optimization and x-ray/particle-beam alignment, based on laser illumination schemes and fast imaging detectors. Our diagnostics are constructed to provide a non-invasive rapid feedback on injector performance during measurements, and have been demonstrated during diffraction measurements at the FLASH free-electron laser.

physics.optics↗

arXiv2015

High-intracavity-power thin-disk laser for the alignment of molecules

We propose a novel approach for strong alignment of gas-phase molecules for experiments at arbitrary repetition rates. A high-intracavity-power continuous-wave laser will provide the necessary ac electric field of $\!10^{10}$- $10^{11}~\text{W}/\text{cm}^2$. We demonstrate thin-disk lasers based on Yb:YAG and Yb:Lu$_2$O$_3$ in a linear high-finesse resonator providing intracavity power levels in excess of 100~kW at pump power levels on the order of 50~W. The multi-longitudinal-mode operation of this laser avoids spatial-hole burning even in a linear standing-wave resonator. The system will be scaled up as in-vacuum system to allow for the generation of fields of $10^{11}~\text{W}/\text{cm}^2$. This system will be directly applicable for experiments at modern X-ray light sources, such as synchrotrons or free-electron lasers, which operate at various very high repetition rates. This would allow to record molecular movies through temporally resolved diffractive imaging of fixed-in-space molecules, as well as the spectroscopic investigation of combined X-ray-NIR strong-field effects of atomic and molecular systems.

physics.optics↗

arXiv2015

Strongly aligned gas-phase molecules at Free-Electron Lasers

We demonstrate a novel experimental implementation to strongly align molecules at full repetition rates of free-electron lasers. We utilized the available in-house laser system at the coherent x-ray imaging beamline at the Linac Coherent Light Source. Chirped laser pulses, i. e., the direct output from the regenerative amplifier of the Ti:Sa chirped pulse amplification laser system, were used to strongly align 2,5-diiodothiophene molecules in a molecular beam. The alignment laser pulses had pulse energies of a few mJ and a pulse duration of 94 ps. A degree of alignment of $\left<\cos^2\!θ_{2D}\right>$ = 0.85 was measured, limited by the intrinsic temperature of the molecular beam rather than by the available laser system. With the general availability of synchronized chirped-pulse-amplified near-infrared laser systems at short-wavelength laser facilities, our approach allows for the universal preparation of molecules tightly fixed in space for experiments with x-ray pulses.

physics.atm-clus↗

arXiv2015

Electron gun for diffraction experiments off controlled molecules

A dc electron gun, generating picosecond pulses with up to $8\times10^{6}$ electrons per pulse, was developed. Its applicability for future time-resolved-diffraction experiments on state- and conformer-selected laser-aligned or oriented gaseous samples was characterized. The focusing electrodes were arranged in a velocity-map imaging spectrometer configuration. This allowed to directly measure the spatial and velocity distributions of the electron pulses emitted from the cathode. The coherence length and pulse duration of the electron beam were characterized by these measurements combined with electron trajectory simulations. Electron diffraction data off a thin aluminum foil illustrated the coherence and resolution of the electron-gun setup.

physics.chem-ph↗

arXiv2015

Spatially-controlled complex molecules and their applications

The understanding of molecular structure and function is at the very heart of the chemical and molecular sciences. Experiments that allow for the creation of structurally pure samples and the investigation of their molecular dynamics and chemical function have developed tremendously over the last few decades, although "there's plenty of room at the bottom" for better control as well as further applications. Here, we describe the use of inhomogeneous electric fields for the manipulation of neutral molecules in the gas-phase, \ie, for the separation of complex molecules according to size, structural isomer, and quantum state. For these complex molecules, all quantum states are strong-field seeking, requiring dynamic fields for their confinement. Current applications of these controlled samples are summarised and interesting future applications discussed.

physics.chem-ph↗

arXiv2015

Two-state wave packet for strong field-free molecular orientation

We demonstrate strong laser-field-free orientation of absolute-ground-state carbonyl sulfide molecules. The molecules are oriented by the combination of a 485-ps-long non-resonant laser pulse and a weak static electric field. The edges of the laser pulse create a coherent superposition of two rotational states resulting in revivals of strong transient molecular orientation after the laser pulse. The experimentally attained degree of orientation of 0.6 corresponds to the theoretical maximum for mixing of the two states. Switching off the dc field would provide the same orientation completely field-free.

physics.chem-ph↗

arXiv2014

Toward atomic resolution diffractive imaging of isolated molecules with x-ray free-electron lasers

We give a detailed account of the theoretical analysis and the experimental results of an x-ray-diffraction experiment on quantum-state selected and strongly laser-aligned gas-phase ensembles of the prototypical large asymmetric rotor molecule 2,5-diiodobenzonitrile, performed at the Linac Coherent Light Source [Phys. Rev. Lett. 112, 083002 (2014)]. This experiment is the first step toward coherent diffractive imaging of structures and structural dynamics of isolated molecules at atomic resolution, i. e., picometers and femtoseconds, using x-ray free-electron lasers.

physics.atom-ph↗

arXiv2014

X-ray diffraction from isolated and strongly aligned gas-phase molecules with a free-electron laser

We report experimental results on x-ray diffraction of quantum-state-selected and strongly aligned ensembles of the prototypical asymmetric rotor molecule 2,5-diiodobenzonitrile using the Linac Coherent Light Source. The experiments demonstrate first steps toward a new approach to diffractive imaging of distinct structures of individual, isolated gas-phase molecules. We confirm several key ingredients of single molecule diffraction experiments: the abilities to detect and count individual scattered x-ray photons in single shot diffraction data, to deliver state-selected, e. g., structural-isomer-selected, ensembles of molecules to the x-ray interaction volume, and to strongly align the scattering molecules. Our approach, using ultrashort x-ray pulses, is suitable to study ultrafast dynamics of isolated molecules.

physics.atom-ph↗