Bond-rearrangement and ionization mechanisms in the photo-double-ionization of simple hydrocarbons (C2H4, C2H3F, and 1,1-C2H2F2) near and above threshold

Citation: Gaire, B., Gatton, A., Wiegandt, F., Neff, J., Janke, C., Zeller, S., . . . Weber, T. (2016). Bond-rearrangement and ionization mechanisms in the photo-double-ionization of simple hydrocarbons (C2H4, C2H3F, and 1,1-C2H2F2) near and above threshold. Physical Review A, 94(3), 8. doi:10.1103/PhysRevA.94.033412We investigate bond-rearrangement driven by photo-double-ionization (PDI) near and above the double-ionization threshold in a sequence of carbon-carbon double-bonded hydrocarbon molecules: ethylene, fluoroethylene, and 1,1-difluoroethylene. We employ the kinematically complete cold target recoil ion momentum spectroscopy method to resolve all photo-double-ionization events leading to two-ion fragments. We observe changes in the branching ratios of different dissociative ionization channels depending on the presence of no, one, or two fluorine atoms. The role of the fluorine atom in the bond-rearrangement channels is intriguing, as evident by the reordering of the threshold energies of the PDI in the fluorinated molecules. These effects offer a compelling argument that the electronegativity of the fluorine (or the polarity of the molecule) strongly influences the potential energy surfaces of the molecules and drives bond rearrangement during the dissociation process. The energy sharing and the relative angle between the three-dimensional momentum vectors of the two electrons enable us to distinguish between knockout and other ionization mechanisms of the PDI processes

Fragmentation of CD+ induced by intense ultrashort laser pulses

Citation: Graham, L., Zohrabi, M., Gaire, B., Ablikim, U., Jochim, B., Berry, B., . . . Ben-Itzhak, I. (2015). Fragmentation of CD+ induced by intense ultrashort laser pulses. Physical Review A, 91(2), 11. doi:10.1103/PhysRevA.91.023414The fragmentation of CD[superscript +] in intense ultrashort laser pulses was investigated using a coincidence three-dimensional momentum imaging technique improved by employing both transverse and longitudinal electric fields. This allowed clear separation of all fragmentation channels and the determination of the kinetic energy release down to nearly zero, for a molecule with significant mass asymmetry. The most probable dissociation pathways for the two lowest dissociation limits, C[superscript +]+D and C+D[superscript +], were identified for both 22-fs, 798-nm and 50-fs, 392-nm pulses. Curiously, the charge asymmetric dissociation of CD[superscript 2+] was not observed for 392-nm photons, even though it was clearly visible for the fundamental 798 nm at the same peak intensity

Auger decay and subsequent fragmentation pathways of ethylene following K-shell ionization

Citation: Gaire, B., Haxton, D. J., Sturm, F. P., Williams, J., Gatton, A., Bocharova, I., . . . Weber, T. (2015). Auger decay and subsequent fragmentation pathways of ethylene following K-shell ionization. Physical Review A, 92(1), 13. doi:10.1103/PhysRevA.92.013408The fragmentation pathways and dynamics of ethylene molecules after core ionization are explored using coincident measurements of the Auger electron and fragment ions by employing the cold target recoil-ion momentum spectroscopy method. The influence of several factors on the dynamics and kinematics of the dissociation is studied. These include propensity rules, ionization mechanisms, symmetry of the orbitals from which the Auger electrons originate, multiple scattering, conical intersections, interference, and possible core-hole localization for the double ionization of this polyatomic molecule. Energy correlation maps allow probing the multidimensional potential energy surfaces and, in combination with our multiconfiguration self-consistent field calculations, identifying the populated electronic states of the dissociating dication. The measured angular distributions of the Auger electrons in the molecular frame further support and augment these assignments. The deprotonation and molecular hydrogen ion elimination channels show a nearly isotropic Auger electron angular distribution with a small elongation along the direction perpendicular to the molecular axis. For the symmetric breakup the angular distributions show a clear influence of multiple scattering on the outgoing electrons. The lowest kinetic energy release feature of the symmetric breakup channel displays a fingerprint of entangled Auger and photoelectron motion in the angular emission pattern identifying this transition as an excellent candidate to probe core-hole localization at a conical intersection of a polyatomic molecule.Additional Authors: Landers, A. L.;Belkacem, A.;Dorner, R.;Weber, T

Adaptive strong-field control of chemical dynamics guided by three-dimensional momentum imaging.

Shaping ultrafast laser pulses using adaptive feedback can manipulate dynamics in molecular systems, but extracting information from the optimized pulse remains difficult. Experimental time constraints often limit feedback to a single observable, complicating efforts to decipher the underlying mechanisms and parameterize the search process. Here we show, using two strong-field examples, that by rapidly inverting velocity map images of ions to recover the three-dimensional photofragment momentum distribution and incorporating that feedback into the control loop, the specificity of the control objective is markedly increased. First, the complex angular distribution of fragment ions from the nω+C2D4→C2D3++D interaction is manipulated. Second, isomerization of acetylene (nω+C2H2→C2H22+→CH2++C+) is controlled via a barrier-suppression mechanism, a result that is validated by model calculations. Collectively, these experiments comprise a significant advance towards the fundamental goal of actively guiding population to a specified quantum state of a molecule

Incorporating real time velocity map image reconstruction into closed-loop coherent control

We report techniques developed to utilize three-dimensional momentum information as feedback in adaptive femtosecond control of molecular dynamics. Velocity map imaging is used to obtain the three-dimensional momentum map of the dissociating ions following interaction with a shaped intense ultrafast laser pulse. In order to recover robust feedback information, however, the two-dimensional momentum projection from the detector must be inverted to reconstruct the full three-dimensional momentum of the photofragments. These methods are typically slow or require manual inputs and are therefore accomplished offline after the images have been obtained. Using an algorithm based upon an “onion-peeling” (also known as “back projection”) method, we are able to invert 1040 × 1054 pixel images in under 1 s. This rapid inversion allows the full photofragment momentum to be used as feedback in a closed-loop adaptive control scheme, in which a genetic algorithm tailors an ultrafast laser pulse to optimize a specific outcome. Examples of three-dimensional velocity map image based control applied to strong-field dissociation of CO and O2 are presented

Strong-field dissociation dynamics of molecular dications

Citation: Jochim, B., Severt, T., Zohrabi, M., Ablikim, U., Berry, B., Gaire, B., . . . Ben-Itzhak, I. (2015). Strong-field dissociation dynamics of molecular dications. 635(11). doi:10.1088/1742-6596/635/11/112044We focus on the dissociation of metastable molecular dications induced by intense, ultrafast laser pulses. In particular, we demonstrate the dominant role of commonly-neglected permanent-dipole transitions and drive dissociation via a pump-dump-like mechanism within a single laser pulse. © Published under licence by IOP Publishing Ltd

Nuclear β-catenin expression is closely related to ulcerative growth of colorectal carcinoma

Although most colorectal cancer develops based on the adenoma–adenocarcinoma sequence, morphologically, colorectal cancer is not a homogeneous disease entity. Generally, there are two distinct morphological types: polypoid and ulcerative colorectal tumours. Previous studies have demonstrated that K-ras codon 12 mutations are preferentially associated with polypoid growth of colorectal cancer; however, little is known about the molecular mechanism that determines ulcerative growth of colorectal cancer. β-catenin complex plays a critical role both in tumorigenesis and morphogenesis. We examined the differential expression of β-catenin and its related factors among different types of colorectal cancer in order to determine any relationship with gross tumour morphology. Immunohistochemical staining of β-catenin, E-cadherin and MMP-7 was performed on 51 tumours, including 26 polypoid tumours and 25 ulcerative tumours. Protein truncation tests and single-strand conformational polymorphism for mutation of the adenomatous polyposis coli tumour suppressor gene, as well as single-strand conformational polymorphism for the mutation of β-catenin exon 3 were also done. Nuclear expression of β-catenin was observed in 18 out of 25 (72%) cases of ulcerative colorectal cancer and seven out of 26 (26.9%) cases of polypoid colorectal cancer. A significant relationship of nuclear β-catenin expression with ulcerative colorectal cancer was found (P<0.001). However, this finding was independent of adenomatous polyposis coli tumour suppressor gene mutation and E-cadherin expression. Together with previous data, we propose that different combinations of genetic alterations may underlie different morphological types of colorectal cancer. These findings should be taken into consideration whenever developing a new genetic diagnosis or therapy for colorectal cancer

Application of a risk-management framework for integration of stromal tumor-infiltrating lymphocytes in clinical trials

Stromal tumor-infiltrating lymphocytes (sTILs) are a potential predictive biomarker for immunotherapy response in metastatic triple-negative breast cancer (TNBC). To incorporate sTILs into clinical trials and diagnostics, reliable assessment is essential. In this review, we propose a new concept, namely the implementation of a risk-management framework that enables the use of sTILs as a stratification factor in clinical trials. We present the design of a biomarker risk-mitigation workflow that can be applied to any biomarker incorporation in clinical trials. We demonstrate the implementation of this concept using sTILs as an integral biomarker in a single-center phase II immunotherapy trial for metastatic TNBC (TONIC trial, NCT02499367), using this workflow to mitigate risks of suboptimal inclusion of sTILs in this specific trial. In this review, we demonstrate that a web-based scoring platform can mitigate potential risk factors when including sTILs in clinical trials, and we argue that this framework can be applied for any future biomarker-driven clinical trial setting

Why is the Winner the Best?

International benchmarking competitions have become fundamental for the comparative performance assessment of image analysis methods. However, little attention has been given to investigating what can be learnt from these competitions. Do they really generate scientific progress? What are common and successful participation strategies? What makes a solution superior to a competing method? To address this gap in the literature, we performed a multicenter study with all 80 competitions that were conducted in the scope of IEEE ISBI 2021 and MICCAI 2021. Statistical analyses performed based on comprehensive descriptions of the submitted algorithms linked to their rank as well as the underlying participation strategies revealed common characteristics of winning solutions. These typically include the use of multi-task learning (63%) and/or multi-stage pipelines (61%), and a focus on augmentation (100%), image preprocessing (97%), data curation (79%), and post-processing (66%). The “typical” lead of a winning team is a computer scientist with a doctoral degree, five years of experience in biomedical image analysis, and four years of experience in deep learning. Two core general development strategies stood out for highly-ranked teams: the reflection of the metrics in the method design and the focus on analyzing and handling failure cases. According to the organizers, 43% of the winning algorithms exceeded the state of the art but only 11% completely solved the respective domain problem. The insights of our study could help researchers (1) improve algorithm development strategies when approaching new problems, and (2) focus on open research questions revealed by this work