Enabling liquid vapor analysis using synchrotron VUV single photon ionization mass spectrometry with a microfluidic interface.

Vacuum ultraviolet (VUV) single photon ionization mass spectrometry (SPI-MS) is a vacuum-based technique typically used for the analysis of gas phase and solid samples, but not for liquids due to the challenge in introducing volatile liquids in a vacuum. Here we present the first demonstration of in situ liquid analysis by integrating the System for Analysis at the Liquid Vacuum Interface (SALVI) microfluidic reactor into VUV SPI-MS. Four representative volatile organic compound (VOC) solutions were used to illustrate the feasibility of liquid analysis. Our results show the accurate mass identification of the VOC molecules and the reliable determination of appearance energy that is consistent with ionization energy for gaseous species in the literature as reported. This work validates that the vacuum-compatible SALVI microfluidic interface can be utilized at the synchrotron beamline and enable the in situ study of gas-phase molecules evaporating off the surface of a liquid, which holds importance in the study of condensed matter chemistry.

Native Frames: Disentangling Sequential from Concerted Three-Body Fragmentation.

A key question concerning the three-body fragmentation of polyatomic molecules is the distinction of sequential and concerted mechanisms, i.e., the stepwise or simultaneous cleavage of bonds. Using laser-driven fragmentation of OCS into O^{+}+C^{+}+S^{+} and employing coincidence momentum imaging, we demonstrate a novel method that enables the clear separation of sequential and concerted breakup. The separation is accomplished by analyzing the three-body fragmentation in the native frame associated with each step and taking advantage of the rotation of the intermediate molecular fragment, CO^{2+} or CS^{2+}, before its unimolecular dissociation. This native-frame method works for any projectile (electrons, ions, or photons), provides details on each step of the sequential breakup, and enables the retrieval of the relevant spectra for sequential and concerted breakup separately. Specifically, this allows the determination of the branching ratio of all these processes in OCS^{3+} breakup. Moreover, we find that the first step of sequential breakup is tightly aligned along the laser polarization and identify the likely electronic states of the intermediate dication that undergo unimolecular dissociation in the second step. Finally, the separated concerted breakup spectra show clearly that the central carbon atom is preferentially ejected perpendicular to the laser field.

Note: Determining the detection efficiency of excited neutral atoms by a microchannel plate detector.

We present a method for determining the detection efficiency of neutral atoms relative to keV ions. Excited D* atoms are produced by D2 fragmentation in a strong laser field. The fragments are detected by a micro-channel plate detector either directly as neutrals or as keV ions following field ionization and acceleration by a static electric field. Moreover, we propose a new mechanism by which neutrals are detected. We show that the ratio of the yield of neutrals and ions can be related to the relative detection efficiency of these species.

Note: Position dependence of time signals picked off a microchannel plate detector.

Using an ultrafast laser and a precision mask, we demonstrate that time signals picked off directly from a microchannel plate detector depend on the position of the hit. This causes a time spread of about 280 ps, which can affect the quality of imaging measurements using large detectors.

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→C2H2(2+)→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.

Carrier-envelope phase control over pathway interference in strong-field dissociation of H2+.

The dissociation of an H2+ molecular-ion beam by linearly polarized, carrier-envelope-phase-tagged 5 fs pulses at 4×10(14) W/cm2 with a central wavelength of 730 nm was studied using a coincidence 3D momentum imaging technique. Carrier-envelope-phase-dependent asymmetries in the emission direction of H+ fragments relative to the laser polarization were observed. These asymmetries are caused by interference of odd and even photon number pathways, where net zero-photon and one-photon interference predominantly contributes at H+ + H kinetic energy releases of 0.2-0.45 eV, and net two-photon and one-photon interference contributes at 1.65-1.9 eV. These measurements of the benchmark H2+ molecule offer the distinct advantage that they can be quantitatively compared with ab initio theory to confirm our understanding of strong-field coherent control via the carrier-envelope phase.