A new route for enantio-sensitive structure determination by photoelectron scattering on molecules in the gas phase.

X-Ray as well as electron diffraction are powerful tools for structure determination of molecules. Studies on randomly oriented molecules in the gas phase address cases in which molecular crystals cannot be generated or the interaction-free molecular structure is to be addressed. Such studies usually yield partial geometrical information, such as interatomic distances. Here, we present a complementary approach, which allows obtaining insight into the structure, handedness, and even detailed geometrical features of molecules in the gas phase. Our approach combines Coulomb explosion imaging, the information that is encoded in the molecular-frame diffraction pattern of core-shell photoelectrons and ab initio computations. Using a loop-like analysis scheme, we are able to deduce specific molecular coordinates with sensitivity even to the handedness of chiral molecules and the positions of individual atoms, e.g., protons.

Influence of the emission site on the photoelectron circular dichroism in trifluoromethyloxirane.

We report a joint experimental and theoretical study of the differential photoelectron circular dichroism (PECD) in inner-shell photoionization of uniaxially oriented trifluoromethyloxirane. By adjusting the photon energy of the circularly polarized synchrotron radiation, we address 1s-photoionization of the oxygen, different carbon, and all fluorine atoms. The photon energies were chosen such that in all cases electrons with a similar kinetic energy of about 11 eV are emitted. Employing coincident detection of electrons and fragment ions, we concentrate on identical molecular fragmentation channels for all of the electron-emitter scenarios. Thereby, we systematically examine the influence of the emission site of the photoelectron wave on the differential PECD. We observe large differences in the PECD signals. The present experimental results are supported by corresponding relaxed-core Hartree-Fock calculations.

Measuring the photoelectron emission delay in the molecular frame.

How long does it take to emit an electron from an atom? This question has intrigued scientists for decades. As such emission times are in the attosecond regime, the advent of attosecond metrology using ultrashort and intense lasers has re-triggered strong interest on the topic from an experimental standpoint. Here, we present an approach to measure such emission delays, which does not require attosecond light pulses, and works without the presence of superimposed infrared laser fields. We instead extract the emission delay from the interference pattern generated as the emitted photoelectron is diffracted by the parent ion's potential. Targeting core electrons in CO, we measured a 2d map of photoelectron emission delays in the molecular frame over a wide range of electron energies. The emission times depend drastically on the photoelectrons' emission directions in the molecular frame and exhibit characteristic changes along the shape resonance of the molecule.

Photoelectron circular dichroism of O 1s-photoelectrons of uniaxially oriented trifluoromethyloxirane: energy dependence and sensitivity to molecular configuration.

The photoelectron circular dichroism (PECD) of the O 1s-photoelectrons of trifluoromethyloxirane (TFMOx) is studied experimentally and theoretically for different photoelectron kinetic energies. The experiments were performed employing circularly polarized synchrotron radiation and coincident electron and fragment ion detection using cold target recoil ion momentum spectroscopy. The corresponding calculations were performed by means of the single center method within the relaxed-core Hartree-Fock approximation. We concentrate on the energy dependence of the differential PECD of uniaxially oriented TFMOx molecules, which is accessible through the employed coincident detection. We also compare the results for the differential PECD of TFMOx to those obtained for the equivalent fragmentation channel and similar photoelectron kinetic energy of methyloxirane (MOx), studied in our previous work. Thereby, we investigate the influence of the substitution of the methyl group by the trifluoromethyl group at the chiral center on the molecular chiral response. Finally, the presently obtained angular distribution parameters are compared to those available in the literature.

Phase-contrast acceleration mapping with synchronized encoding.

PURPOSE: To develop a phase-contrast (PC) -based method for direct and unbiased quantification of the acceleration vector field by synchronization of the spatial and acceleration encoding time points. The proposed method explicitly aims at in-vitro applications, requiring high measurement accuracy, as well as the validation of clinically relevant acceleration-encoded sequences. METHODS: A velocity-encoded sequence with synchronized encoding (SYNC SPI) was modified to allow direct acceleration mapping by replacing the bipolar encoding gradients with tripolar gradient waveforms. The proposed method was validated in two in-vitro flow cases: a rotation and a stenosis phantom. The thereby obtained velocity and acceleration vector fields were quantitatively compared to those acquired with conventional PC methods, as well as to theoretical data. RESULTS: The rotation phantom study revealed a systematic bias of the conventional PC acceleration mapping method that resulted in an average pixel-wise relative angle between the measured and theoretical vector field of (7.8 ± 3.2)°, which was reduced to (-0.4 ± 2.7)° for the proposed SYNC SPI method. Furthermore, flow features in the stenosis phantom were displaced by up to 10 mm in the conventional PC data compared with the acceleration-encoded SYNC SPI data. CONCLUSIONS: This work successfully demonstrates a highly accurate method for direct acceleration mapping. It thus complements the existing velocity-encoded SYNC SPI method to enable the direct and unbiased quantification of both the velocity and acceleration vector field for in vitro studies. Hence, this method can be used for the validation of conventional acceleration-encoded PC methods applicable in-vivo.

Equivalent Scalar Stress Formulation Taking into Account Non-Resolved Turbulent Scales.

PURPOSE: Cardiovascular engineering includes flows with fluid-dynamical stresses as a parameter of interest. Mechanical stresses are high-risk factors for blood damage and can be assessed by computational fluid dynamics. By now, it is not described how to calculate an adequate scalar stress out of turbulent flow regimes when the whole share of turbulence is not resolved by the simulation method and how this impacts the stress calculation. METHODS: We conducted direct numerical simulations (DNS) of test cases (a turbulent channel flow and the FDA nozzle) in order to access all scales of flow movement. After validation of both DNS with literature und experimental data using magnetic resonance imaging, the mechanical stress is calculated as a baseline. Afterwards, same flows are calculated using state-of-the-art turbulence models. The stresses are computed for every result using our definition of an equivalent scalar stress, which includes the influence from respective turbulence model, by using the parameter dissipation. Afterwards, the results are compared with the baseline data. RESULTS: The results show a good agreement regarding the computed stress. Even when no turbulence is resolved by the simulation method, the results agree well with DNS data. When the influence of non-resolved motion is neglected in the stress calculation, it is underpredicted in all cases. CONCLUSION: With the used scalar stress formulation, it is possible to include information about the turbulence of the flow into the mechanical stress calculation even when the used simulation method does not resolve any turbulence.

Multi-channel photodissociation and XUV-induced charge transfer dynamics in strong-field-ionized methyl iodide studied with time-resolved recoil-frame covariance imaging.

The photodissociation dynamics of strong-field ionized methyl iodide (CH3I) were probed using intense extreme ultraviolet (XUV) radiation produced by the SPring-8 Angstrom Compact free electron LAser (SACLA). Strong-field ionization and subsequent fragmentation of CH3I was initiated by an intense femtosecond infrared (IR) pulse. The ensuing fragmentation and charge transfer processes following multiple ionization by the XUV pulse at a range of pump-probe delays were followed in a multi-mass ion velocity-map imaging (VMI) experiment. Simultaneous imaging of a wide range of resultant ions allowed for additional insight into the complex dynamics by elucidating correlations between the momenta of different fragment ions using time-resolved recoil-frame covariance imaging analysis. The comprehensive picture of the photodynamics that can be extracted provides promising evidence that the techniques described here could be applied to study ultrafast photochemistry in a range of molecular systems at high count rates using state-of-the-art advanced light sources.

CFD validation using in-vitro MRI velocity data - Methods for data matching and CFD error quantification.

Predicting blood flow velocities in patient-specific geometries with Computational Fluid Dynamics (CFD) can provide additional data for diagnosis and treatment planning but the solution can be inaccurate. Therefore, it is crucial to understand the simulation errors and calibrate the numerical model. In-vitro velocity-encoded MRI is a versatile tool to validate CFD. The comparison between CFD and in-vitro MRI velocity data, and the analysis of the simulation error are the objectives of this study. A three-step routine is presented to validate medical CFD data. First, a properly scaled model of the patient-specific geometry is fabricated to achieve high relative resolution in the MRI experiment. Second, the measured flow geometry is matched with the CFD data using one of two algorithms, Coherent Point Drift and Iterative Closest Point. The aligned data sets are then interpolated onto a common grid to enable a point-to-point comparison. Third, the global and local deviations between CFD and MRI velocity data are calculated using different algorithms to reliably estimate the simulation error. The routine is successfully tested with a patient-specific model of a cerebral aneurysm. In conclusion, the methods presented here provide a framework for CFD validation using in-vitro MRI velocity data.

An unbiased method for PRF-shift temperature measurements in convective heat transfer systems with functional parts made of metal.

The purpose of this study is to provide a PRF-shift method for fluid temperature measurements in convective heat transfer systems, which contain functional parts made of metal. Such measurements are extremely useful to examine and design convective cooling systems for industrial devices. Metals like copper seem inevitable for such applications because no commonly available non-metallic material reaches the same level of thermal conductivity as for example copper. In MRI, electrically conductive parts embedded in the measured sample are known to produce various kinds of errors including errors in the image phase caused by eddy currents. Two methods are compared that can be used to remove the eddy currents induced phase: via the phase difference of two readouts at different echo times and via the sum of the phase of two acquisitions with reverse gradient polarity and same echo time. The latter method, termed Rot-Echo, provides a better measurement efficiency because of higher temperature sensitivity. Also, this technique is able to directly measure the eddy currents induced phase map. After verification in a stationary water experiment, the Rot-Echo method was applied to time-averaged temperature measurements in a Pin Fin heat exchanger, comprised of water flow that is heated by an array of copper pins. The temperature fields acquired in the Pin Fin heat exchanger under stable thermal-hydraulic conditions agreed well with data from temperature sensors. No eddy currents effects were visible in any of the data sets in the vicinity of the copper rods. In conclusion, this study shows that unbiased PRF-shift temperature measurements are feasible in complex flow systems even if metallic material is used for the functional parts.

Double Core-Hole Generation in O_{2} Molecules Using an X-Ray Free-Electron Laser: Molecular-Frame Photoelectron Angular Distributions.

We report on a multiparticle coincidence experiment performed at the European X-ray Free-Electron Laser at the Small Quantum Systems instrument using a COLTRIMS reaction microscope. By measuring two ions and two electrons in coincidence, we investigate double core-hole generation in O_{2} molecules in the gas phase. Single-site and two-site double core holes have been identified and their molecular-frame electron angular distributions have been obtained for a breakup of the oxygen molecule into two doubly charged ions. The measured distributions are compared to results of calculations performed within the frozen- and relaxed-core Hartree-Fock approximations.

Zeptosecond birth time delay in molecular photoionization.

Photoionization is one of the fundamental light-matter interaction processes in which the absorption of a photon launches the escape of an electron. The time scale of this process poses many open questions. Experiments have found time delays in the attosecond (10-18 seconds) domain between electron ejection from different orbitals, from different electronic bands, or in different directions. Here, we demonstrate that, across a molecular orbital, the electron is not launched at the same time. Rather, the birth time depends on the travel time of the photon across the molecule, which is 247 zeptoseconds (1 zeptosecond = 10-21 seconds) for the average bond length of molecular hydrogen. Using an electron interferometric technique, we resolve this birth time delay between electron emission from the two centers of the hydrogen molecule.

Observation of Photoion Backward Emission in Photoionization of He and N_{2}.

We experimentally investigate the effects of the linear photon momentum on the momentum distributions of photoions and photoelectrons generated in one-photon ionization in an energy range of 300 eV≤E_{γ}≤40 keV. Our results show that for each ionization event the photon momentum is imparted onto the photoion, which is essentially the system's center of mass. Nevertheless, the mean value of the ion momentum distribution along the light propagation direction is backward-directed by -3/5 times the photon momentum. These results experimentally confirm a 90-year-old prediction.

Electron spectroscopic study of nanoplasma formation triggered by intense soft x-ray pulses.

Using electron spectroscopy, we investigated the nanoplasma formation process generated in xenon clusters by intense soft x-ray free electron laser (FEL) pulses. We found clear FEL intensity dependence of electron spectra. Multistep ionization and subsequent ionization frustration features are evident for the low FEL-intensity region, and the thermal electron emission emerges at the high FEL intensity. The present FEL intensity dependence of the electron spectra is well addressed by the frustration parameter introduced by Arbeiter and Fennel [New J. Phys. 13, 053022 (2011)].

Phase-contrast single-point imaging with synchronized encoding: a more reliable technique for in vitro flow quantification.

PURPOSE: The purpose of this study is to provide a standard method for flow velocity measurements with phase-contrast (PC) MRI. This method can be used for in vitro studies that place high demands on measurement accuracy. Clinically relevant PC MRI techniques can be validated using this method before being applied in vivo. METHODS: Many motion-related errors in PC MRI, particularly flow misregistration, depend on the timing of the encoding gradients in the pulse sequence. By synchronizing all encoding gradients and shortening the overall encoding interval, these errors can be significantly reduced. Based on this concept, a single-point PC MRI method is proposed. RESULTS: Flow experiments were conducted in vitro. No considerable errors were found in the velocity data of the proposed method. For comparison, a conventional PC MRI technique showed up to 100% local velocity deviation and up to 35% flow rate deviation in the same experiments. CONCLUSIONS: With the proposed method, the overall measurement accuracy is significantly increased compared to conventional PC MRI techniques. Due to long acquisition times and high specific absorption rates, this method can only be applied in vitro.

Acquisition of 3D temperature distributions in fluid flow using proton resonance frequency thermometry.

PURPOSE: Proton resonance frequency thermometry is well established for monitoring small temperature changes in tissue. Application of the technique to the measurement of complex temperature distributions within fluid flow is of great interest to the engineering community and could also have medical applications. This work presents an experimental approach to reliably measure three-dimensional (3D) temperature fields in fluid flow using proton resonance frequency thermometry. METHODS: A velocity-compensated three-dimensional gradient echo sequence was used. A flexible pumping system was attached to an MR compatible double pipe heat exchanger. The temperature of two separate flow circuits could be adjusted to produce various three-dimensional spatial temperature distributions within the fluid flow. Validation was performed using MR compatible temperature probes in a uniformly heated flow. A comparative study was conducted with thermocouples in the presence of a spatially varying temperature distribution. RESULTS: In uniformly heated flow, temperature changes were accurately measured to within 0.5 K using proton resonance frequency thermometry, while spatially varying temperature changes measured with MR showed good qualitative agreement with pointwise measurements using thermocouples. CONCLUSION: Proton resonance frequency thermometry can be used in a variety of complex flow situations to address medical as well as engineering questions. This work makes it possible to gain new insights into fundamental heat transfer phenomena. Magn Reson Med 76:145-155, 2016. © 2015 Wiley Periodicals, Inc.

Dental therapy before and after radiotherapy--an evaluation on patients with head and neck malignancies.

The present investigation evaluates the dental care situation of patients with head and neck cancer before and after radiotherapy. The situations of these patients in 1993 and 2005 were compared to detect similarities, differences and developments. In the years 1993 and 2005, 37 and 36 patients, respectively, with head and neck cancer treated by the local departments of otorhinolaryngology and of radiotherapy were examined consecutively according to their aftercare appointments. Time points of radiotherapy treatment of the patients evaluated in 1993 varied from 1984 to 1993. The patients evaluated in 2005 had received radiotherapy between 1998 and 2005. Therefore the applied radiotherapeutic regimen differed not only between the two groups of patients, but also within each group. The information for these investigations was provided anonymously. It was evaluated with descriptive statistics. The evaluation of the data shows distinct differences with respect to preventive and therapeutic dental care measures. In 2005, 35 out of 36 patients (97.2%) had a dental consultation before radiotherapy (1993, 65%). All 27 dentate patients (100%) obtained a splint for fluoride application (1993, none). 29% fewer edentulous patients were seen than in 1993. The number of teeth destroyed decreased from 19.2% (1993) to 7.8% in 2005. Mycoses due to Candida spp. and chronic failures in wound healing were rare (5.5%). In the course of the 12 years, prophylactic measures, such as the application of splints for fluoride treatment, were intensified. However, concepts for the dental care of patients undergoing radiotherapy, especially following the radiation, should be widened to avoid ruined teeth and long delayed wound healings.