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Abstract The primary and secondary fragmentation dynamics of iodobenzene following its ionization at 120 eV were determined using three-dimensional velocity map imaging and covariance analysis. Site-selective iodine 4d ionization was used to populate a range of excited polycationic parent states, which primarily broke apart at the carbon-iodine bond to produce I⁺with phenyl or phenyl-like cations (C_nH ${{}_x}^{+}$or C_nH ${{}_x}^{2+}$, withn  =  1 – 6 andx  =  1 – 5). The molecular products were produced with varying degrees of internal excitation and dehydrogenation, leading to stable and unstable outcomes. This further allowed the secondary dynamics of ${\mathrm{C}}_6{\mathrm{H}}_x{}^{2+}$intermediates to be distinguished using native-frame covariance analysis, which isolated these processes in their own centre-of-mass reference frames. The mass resolution of the imaging mass spectrometer used for these measurements enabled the primary and secondary reaction channels to be specified at the level of individual hydrogen atoms, demonstrating the ability of covariance analysis to comprehensively measure the competing fragmentation channels of aryl cations, including those involving intermediate steps. 

Abstract Filming atomic motion within molecules is an active pursuit of molecular physics and quantum chemistry. A promising method is laser-induced Coulomb Explosion Imaging (CEI) where a laser pulse rapidly ionizes many electrons from a molecule, causing the remaining ions to undergo Coulomb repulsion. The ion momenta are used to reconstruct the molecular geometry which is tracked over time (i.e., filmed) by ionizing at an adjustable delay with respect to the start of interatomic motion. Results are distorted, however, by ultrafast motion during the ionizing pulse. We studied this effect in water and filmed the rapid “slingshot” motion that enhances ionization and distorts CEI results. Our investigation uncovered both the geometry and mechanism of the enhancement which may inform CEI experiments in many other polyatomic molecules. 

Abstract Structural imaging of transient excited-state species is a key goal of molecular physics, promising to unveil rich information about the dynamics underpinning photochemical transformations. However, separating the electronic and nuclear contributions to the spectroscopic observables is challenging, and typically requires the application of high-level theory. Here, we employ site-selective ionisation via ultrashort soft X-ray pulses and time-resolved Coulomb explosion imaging to interrogate structural dynamics of the ultraviolet photochemistry of carbon disulfide. This prototypical system exhibits the complex motifs of polyatomic photochemistry, including strong non-adiabatic couplings, vibrational mode couplings, and intersystem crossing. Immediately following photoexcitation, we observe Coulomb explosion signatures of highly bent and stretched excited-state geometries involved in the photodissociation. Aided by a model to interpret such changes, we build a comprehensive picture of the photoinduced nuclear dynamics that follows initial bending and stretching motions, as the reaction proceeds towards photodissociation. 

It has recently been shown that strong field multiple ionization of water depends on the duration and intensity of the laser pulse. While the polarizability of neutral water is isotropic, the polarizability of the molecular ions can be significant and evolve in time. If the molecular ions spend enough time in the field, dynamic alignment can reorient them and modify the yield of dissociating fragments as a function of angle relative to the polarization of the laser. Unbending motion is one way that the polarizability of the molecular ions increases. Here, we study strong field ionization of water in the long pulse regime where dynamic alignment and unbending are known to contribute at 800 nm, and we tune the laser wavelength to modify coupling between the states of the monocation. A resonance between the X and A states at 660 nm should excite the monocation and initiate unbending motion, but our results cannot be explained without considering the dynamics and structure of the dication and trication. To conduct these measurements, we utilize laser pulses with a duration of 40 fs and central wavelengths of 660 nm, 800 nm, and 1330 nm to multiply-ionize an effusive molecular beam of water. The resulting charged fragments are detected using a velocity map imaging apparatus. Our results provide additional clues about the strong field ionization of water. *M.B., G.A.M., A.J.H., N.P., and P.H.B. were supported by the National Science Foundation. A.J.H. was additionally supported under a Stanford Graduate Fellowship as the 2019 Albion Walter Hewlett Fellow. N.P. was additionally supported by the Hertz Foundation. R.F. was supported by the Department of Energy office of Basic Energy Science, Facilities Division. 

We present results from an experimental ion imaging study into the fragmentation dynamics of 1-iodopropane and 2-iodopropane following interaction with extreme ultraviolet intense femtosecond laser pulses with a photon energy of 95 eV. Using covariance imaging analysis, a range of observed fragmentation pathways of the resulting polycations can be isolated and interrogated in detail at relatively high ion count rates (∼12 ions shot −1 ). By incorporating the recently developed native frames analysis approach into the three-dimensional covariance imaging procedure, contributions from three-body concerted and sequential fragmentation mechanisms can be isolated. The angular distribution of the fragment ions is much more complex than in previously reported studies for triatomic polycations, and differs substantially between the two isomeric species. With support of simple simulations of the dissociation channels of interest, detailed physical insights into the fragmentation dynamics are obtained, including how the initial dissociation step in a sequential mechanism influences rovibrational dynamics in the metastable intermediate ion and how signatures of this nuclear motion manifest in the measured signals.