T. Gerber

Imaging photoelectron photoion coincidence spectroscopy with velocity focusing electron optics

An imaging photoelectron photoion coincidence spectrometer at the vacuum ultraviolet (VUV) beamline of the Swiss Light Source is presented and a few initial measurements are reported. Monochromatic synchrotron VUV radiation ionizes the cooled or thermal gas-phase sample. Photoelectrons are velocity focused, with better than 1 meV resolution for threshold electrons, and also act as start signal for the ion time-of-flight analysis. The ions are accelerated in a relatively low, 40-80 V cm(-1) field, which enables the direct measurement of rate constants in the 10(3)-10(7) s(-1) range. All electron and ion events are recorded in a triggerless multiple-start/multiple-stop setup, which makes it possible to carry out coincidence experiments at >100 kHz event frequencies. As examples, the threshold photoelectron spectrum of the argon dimer and the breakdown diagrams for hydrogen atom loss in room temperature methane and the chlorine atom loss in cold chlorobenzene are shown and discussed.

Data acquisition schemes for continuous two-particle time-of-flight coincidence experiments

Three data acquisition schemes for two-particle coincidence experiments with a continuous source are discussed. The single-start/single-stop technique, implemented with a time-to-pulse-height converter, results in a complicated spectrum and breaks down severely at high count rates. The single-start/multiple-stop setup, based on a time-to-digital converter and the first choice in todays similar coincidence experiments, performs significantly better at high count rates, but its performance is still hampered if the time-of-flight range is large, and the false coincidence background is variable if the event frequency and the collection efficiency of the starts are both high. A straightforward, multistart/multistop setup is proposed for coincidence experiments. By collecting all detector data, it ensures the highest signal-to-noise ratio, constant background, and fast data acquisition and can now be easily constructed with commercially available time-to-digital converters. Analytical and numerically evaluated formulas are derived to characterize the performance of each setup in a variety of environments. Computer simulated spectra are presented to illustrate the analytically predicted features of the various raw time-of-flight distributions obtained with each technique.

A new double imaging velocity focusing coincidence experiment: i2PEPICO

The vacuum ultraviolet (VUV) beamline of the Swiss Light Source has been upgraded after two years of operation. A new, turntable-type monochromator was constructed at the Paul Scherrer Institut, which allows for fast yaw-alignment as well as quick grating change and exchange. In addition to the original imaging photoelectron photoion coincidence endstation (iPEPICO), a second, complementary double imaging setup (i(2)PEPICO) has been built. Volatile samples can be introduced at room temperature or in a molecular beam, a pyrolysis source allows for radical production, and non-volatile solids can be evaporated in a heated cell. Monochromatic VUV radiation ionizes the sample and both photoelectrons and photoions are velocity map imaged onto two fast position sensitive detectors and detected in delayed coincidence. High intensity synchrotron radiation leads to ionization rates above 10(5) s(-1). New data acquisition and processing approaches are discussed for recording coincidence processes at high rates. The setup is capable of resolving pulsed molecular beam profiles and the synchrotron time structure temporally. The latter is shown by photoelectron autocorrelation, which displays both the 1.04 MHz ring clock frequency as well as resolving the micro-pulses with a separation of 2 ns. Kinetic energy release analysis on the dissociative photoionization of CF(4) indicates a dissociation mechanism change in the Franck-Condon allowed energy range of the first ion state.

In situ flame chemistry tracing by imaging photoelectron photoion coincidence spectroscopy

Adaptation of a low-pressure flat flame burner with a flame-sampling interface to the imaging photoelectron photoion coincidence spectrometer (iPEPICO) of the VUV beamline at the Swiss Light Source is presented. The combination of molecular-beam mass spectrometry and iPEPICO provides a new powerful analytical tool for the detailed investigation of reaction networks in flames. First results demonstrate the applicability of the new instrument to comprehensive flame diagnostics and the potentially high impact for reaction mechanism development for conventional and alternative fuels. Isomer specific identification of stable and radical flame species is demonstrated with unrivaled precision. Radical detection and identification is achieved for the initial H-abstraction products of fuel molecules as well as for the reaction controlling H, O, and OH radicals. Furthermore, quantitative evaluation of changing species concentrations during the combustion process and the applicability of respective results for kinetic model validation are demonstrated. Utilization of mass-selected threshold photoelectron spectra is shown to ensure precise signal assignment and highly reliable spatial profiles.

Photoionization of three isomers of the C9H7 radical.

Three resonance-stabilized radicals, 1-indenyl (Ind), 1-phenylpropargyl (1PPR), and 3-phenylpropargyl (3PPR), all isomers of the composition C(9)H(7), were generated by jet flash pyrolysis. Their photoionization was examined by VUV synchrotron radiation. The mass spectra show a clean and efficient radical generation when the pyrolysis is turned on. To study the photoionization, photoion yield measurements and threshold photoionization spectroscopy techniques were applied. We determined adiabatic ionization energies (IE(ad)) of 7.53 eV for Ind, 7.20 eV for 3PPR, and 7.4 eV for 1PPR. Ab initio calculations show no major change in geometry upon ionization, in agreement with ionization from a nonbonding molecular orbital. The IEs were also computed and are in agreement with the measured ones. The difference in the IE might allow a distinction of the three isomers in flames. In the indenyl spectrum, an excited a(+) (3)B(2) state of the cation was identified at 8.10 eV, which shows a low-energy vibrational progression of 61 meV. Furthermore, we have examined the dissociative photoionization of the precursors. The indenyl precursor, 1-indenyl bromide, undergoes dissociative photoionization to Ind(+). An appearance energy (AE(0K)) of 10.2 eV was obtained from fitting the experimental breakdown diagram. A binding energy of 1.8 eV can thus be determined for the C-Br bond in 1-indenyl bromide. The phenylpropargyl precursors 1PPBr (1-phenylpropargyl bromide/3-phenyl-3-bromopropyne) and 3PPBr (3-phenylpropargyl bromide/1-phenyl-3-bromopropyne) also lose a bromine atom upon dissociative photoionization. Approximate appearance energies of 9.8 eV for 3PPBr and 9.3 eV for 1PPBr have been determined.

Determination of rotational constants in a molecule by femtosecond four-wave mixing

Femtosecond time-resolved DFWM experiments were performed on CHCl3 and SO2. The recurrences observed originate from the preparation of rotational coherences within the sample. The determination of rotational constants for a symmetric and an asymmetric top are shown. The simulation of the transients for the symmetric top allows the extraction of the main moment of inertia B and the centrifugal terms perpendicular to the molecule axis. For the asymmetric top, all three rotational constants can be derived. In addition to the transients at 1/2(B + C), two additional types of asymmetry transients at 1/4C and 1/4A arise from this experiment. The first origins from the levels at low K and the second from the levels at high K in the high-J limit. Copyright

Collision induced rotational energy transfer probed by time-resolved coherent anti- Stokes Raman scattering

We show that the technique of femtosecond time-resolved coherent anti-Stokes Raman scattering (CARS) spectroscopy provides a powerful tool for the investigation of collision-induced linewidths and the validation of rotational energy transfer (RET) models. The fs-CARS method is applied to the N2–N2 collision system, and a comparison between the commonly used exponential gap (ECS-E), power gap (ECS-P), frequency corrected (EFCS), and the recently proposed angular momentum and energy corrected (AECS) variants of the ECS model is presented. As result we show that the AECS scaling law requires only two free parameters, and is appropriate for the determination of RET rates from the measured fs-CARS signals. The AECS model is also applied to the more complex C2H2–C2H2 collision system. As vibrational energy transfer and dephasing is not negligible in this case, the model has to be modified by introducing a vibrational relaxation factor. With this modification the fs-CARS signals from acetylene can be described s...

Stimulated emission pumping of OH and NH in flames by using two-color resonant four-wave mixing

Abstract In this work we examine the analytical potential of two-color resonant four-wave mixing for the determination and characterization of trace elements in a combustion environment. Experimental results for NH and OH in flames at atmospheric pressure are presented. The selectivity of the technique is used to simplify the Q-branch region of the (0-0) A3Π−X3Σ− vibronic transition of NH. Furthermore, substantial signal-to-noise ratios in the (0-0) A2Σ+−X2Π system of OH are achieved. The high sensitivity is applied to perform stimulated emission pumping involving the weak (0–1) vibrational band. In addition, we demonstrate that the technique is sensitiive to state changing collisions.

Unimolecular Reaction Mechanism of an Imidazolin‐2‐ylidene: An iPEPICO Study on the Complex Dissociation of an Arduengo‐Type Carbene

The photoionization and dissociative photoionization of Im(iPr)2, 1,3-diisopropylimidazolin-2-ylidene, was investigated by imaging photoelectron photoion coincidence (iPEPICO) with vacuum ultraviolet (VUV) synchrotron radiation. A lone-pair electron of the carbene carbon atom is removed upon ionization and the molecular geometry changes significantly. Only 0.5 eV above the adiabatic ionization energy, IEad =7.52±0.1 eV, the carbene cation fragments, yielding propene or a methyl radical in parallel dissociation reactions with appearance energies of 8.22 and 8.17 eV, respectively. Both reaction channels appear at almost the same photon energy, suggesting a shared transition state. This is confirmed by calculations, which reveal the rate-determining step as hydrogen-atom migration from the isopropyl group to the carbene carbon center forming a resonance-stabilized imidazolium ion. Above 10.5 eV, analogous sequential dissociation channels open up. The first propene-loss fragment ion dissociates further and another methyl or propene is abstracted. Again, a resonance-stabilized imidazolium ion acts as intermediate. The aromaticity of the system is enhanced even in vertical ionization. Indeed, the coincidence technique confirms that a real imidazolium ion is produced by hydrogen transfer over a small barrier. The simple analysis of the breakdown diagram yields all the clues to disentangle the complex dissociative photoionization mechanism of this intermediate-sized molecule. Photoelectron photoion coincidence is a promising tool to unveil the fragmentation mechanism of larger molecules in mass spectrometry.

High efficiency KrF excimer flashlamp

Abstract The generation of KrF excimer molecules in a capillary discharge was investigated. Densities of excited KrF in the order of 10 15 cm -3 were measured. The emitted light arises to about 80% from the B-X band transition at 248 nm with an intrinsic efficiency up to 28%.