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

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

Ultrafast temporal evolution of interatomic Coulombic decay in NeKr dimers

We investigate interatomic Coulombic decay in NeKr dimers after neon inner-valence photoionization [Ne+(2s-1)] using a synchrotron light source. We measure with high energy resolution the two singly charged ions of the Coulomb-exploding dimer dication and the photoelectron in coincidence. By carefully tracing the post-collision interaction between the photoelectron and the emitted ICD electron we are able to probe the temporal evolution of the state as it decays. Although the ionizing light pulses are 80 picoseconds long, we determine the lifetime of the intermediate dimer cation state and visualize the contraction of the nuclear structure on the femtosecond time scale

Hydrogen and fluorine migration in photo-double-ionization of 1,1-difluoroethylene (1,1-C2H2F2) near and above threshold

We have studied the nondissociative and dissociative photo-double-ionization of 1,1-difluoroethylene using single photons of energies ranging from 40 to 70 eV. Applying a coincident electron-ion three-dimensional momentum imaging technique, kinematically complete measurements have been achieved. We present the branching ratios of the six reaction channels identified in the experiment. Electron-ion energy maps and relative electron emission angles are used to distinguish between direct and indirect photo-double-ionization mechanisms at a few different photon energies. The influence of selection and propensity rules is discussed. Threshold energies of double ionization are extracted from the sum of the kinetic energies of the electrons, which hint to the involvement of different manifolds of states. The dissociative ionization channels with two ionic fragments are explored in detail by measuring the kinetic energy release of the fragment ions, sum of the kinetic energies, as well as the energy sharing of the two emitted electrons. We investigate the migration of hydrogen and fluorine atoms and compare the experimental results to the photo-double-ionization of centrosymmetric linear and planar hydrocarbons (C[subscript 2]H[subscript 2] and C[subscript 2]H[subscript 4]) whenever possible

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

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

Unambiguous observation of F-atom core-hole localization in CF4 through body-frame photoelectron angular distributions

Citation: McCurdy, C. W., Rescigno, T. N., Trevisan, C. S., Lucchese, R. R., Gaire, B., Menssen, A., . . . Weber, T. (2017). Unambiguous observation of F-atom core-hole localization in CF4 through body-frame photoelectron angular distributions. Physical Review A, 95(1). doi:10.1103/PhysRevA.95.011401A dramatic symmetry breaking in K-shell photoionization of the CF4 molecule in which a core-hole vacancy is created in one of four equivalent fluorine atoms is displayed in the molecular frame angular distribution of the photoelectrons. Observing the photoejected electron in coincidence with an F+ atomic ion after Auger decay is shown to select the dissociation path where the core hole was localized almost exclusively on that atom. A combination of measurements and ab initio calculations of the photoelectron angular distribution in the frame of the recoiling CF3+ and F+ atoms elucidates the underlying physics that derives from the Ne-like valence structure of the F(1s-1) core-excited atom. © 2017 American Physical Society

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