Diss. (sammanfattning) Stockholm : Karol. inst., 2004. / Härtill 5 uppsatser.

Doctor of Philosophy / Department of Physics / Charles L. Cocke / An underlying goal of studying atomic or molecular dynamics with short laser pulses is to reach a time scale short enough to study the evolution of the system in the time domain. In this thesis, the strong field ionization of atoms and molecules has been investigated with the highly resolved technique known as cold target recoil momentum spectroscopy (COLTRIMS). The thesis can be divided into two parts: single and double ionization. In the first part, we studied the momentum vectors of low energy electrons generated by short laser pulses of wavelengths varying from 400 to 800 nm with atomic and molecular targets with intensities in the tunneling region. Most of the structures observed in the momentum spectra of atomic and molecular targets can be explained as due to above-threshold ionization, and Freeman resonances. The most significant structure in our observed spectra is the angular structure in the lowest part of the momentum image, and this is attributed to the diffraction pattern evolved by tunneling electrons. Surprisingly, we observed that the structure produced by the electrons from high Rydberg states is independent of the internal structure of the target atom and molecules. The same work is extended to aligned molecules. The basic idea of this part of the work is to see whether the angular distribution of electrons from aligned molecules resembles the orbital structures of the molecules. The rotational revival structure was used to align the molecules. We observed pronounced energy and angular structures of the momentum images which show a dependence on the alignment of the molecule. The last part of this work mainly focuses on double ionization, i.e. the removal of two electrons from the target atoms sequentially by a short laser pulse. Measuring the complete momentum vector of Ar2+ and Ne2+, we demonstrate that these can be used to extract the angular correlation between two electrons sequentially released in the circularly polarized pulse. We demonstrate how the measurement of full momentum vectors of the doubly ionized argon and neon ions can be used to extract the time gap of the two emissions.

Doctor of Philosophy / Department of Physics / Carlos A. Trallero / Ultra-fast spectroscopy has become a common tool for understanding the structure and dynamics of atoms and molecules, as evidenced by the award of the 1999 Nobel Prize in Chemistry to Ahmed H. Zewail for his pioneering work in femtochemistry. The use of shorter and more energetic laser pulses have given rise to high intensity table-top light sources in the visible and infrared which have pushed spectroscopic measurements of atomic and molecular systems into the strong-field limit. Within this limit, there are unique phenomena that are still not well understood. Many of such phenomena involve a photoionization step. For three decades, there has been a steady investigation of the single ionization of atomic systems in the strong-field regime both experimentally and theoretically. The investigation of the ionization of more complex molecular systems is of great interest presently and will help with the understanding of ultra-fast spectroscopy as a whole. In this thesis, we explore the single ionization of molecules in the presence of a strong electric field. In particular, we study molecular isomer pairs, molecules that are the same elementally, but different structurally. The main goal of this work is to compare the ionization yields of these similar molecular pairs as a function of intensity and gain some insight into what differences caused by their structure contribute to how they ionize in the strong-field limit. Through our studies we explore a wavelength dependence of the photoionization yield in order to move from the multi-photon regime of ionization to the tunneling regime with increasing wavelength. Also, in contrast to our strong-field studies, we investigate isomeric molecules in the weak-field limit through single photon absorption by measuring the total ionization yield as a function of photon energy. Our findings shed light on the complexities of photoionization in both the strong- and weak-field limits and will serve as examples for the continued understanding of single ionization both experimentally and theoretically.

Indiana University-Purdue University Indianapolis (IUPUI) / Paper spray mass spectrometry (PS-MS) is an ambient ionization technique that has been proven useful in many types of investigative analyses. However, the use of this technique with regards to environmental samples has been largely unexplored since the technique’s development. In this work, paper spray mass spectrometry was utilized to detect and quantify compounds for environmental, forensic and chemical defense applications. Due to the sensitive nature of some projects, the work was split into two volumes. Volume 1 focuses on the detection of pharmaceuticals in soil using paper spray (Chapter 2) and the detection of chemical warfare agent (CWA) simulants and CWA hydrolysis products (Chapter 3). Volume 2 focuses on the detection and quantitation of fentanyl analogs in environmental matrices. Chapter 5 focuses on the rapid analysis of fentanyl analogs in soil matrices. The following chapter evaluates the ability of PS-MS to detect low concentrations of fentanyl analogs in water (Chapter 6). Throughout this work, paper spray has proven to be an effective, rapid alternative to chromatography for the analysis of environmental samples.

Laser-Ionization Time-of-Flight Mass Spectrometry (LI-TOF-MS) is a sophisticated tool for the molecular-weight determination and structural characterization of a variety of molecules. Advances in instrumentation and ionization methods have recently expanded its role in the analysis of high-mass analytes. Large multimetallic complexes, which are efficient solar-energy converters, rely heavily on their chemical structure for optimum operation. Molecular mass determinations of these multimetallic complexes have been problematic due to their lability and high molecular weights. This thesis describes the characterization of a LI-TOF-MS instrument and confirmation of theoretical time-of-flight mass-separation principles. Several test cases demonstrate the instrument's proper operation and calibration for a wide mass range of analytes. Mass spectral results of three organometallic compounds: i. [Ir(dpp)₂Cl₂](PF₆), ii. {[(bpy)₂Ru(dpp)]₂IrCl₂}(PF₆)₅, and iii. {[(bpy)₂Ru(dpp)]₂RuCl₂}(PF₆)₅ under a variety of laser ionization and sample preparation conditions are compared. A complete structural characterization of the monometallic complex, [Ir(dpp)₂Cl₂](PF₆), is presented. The two trimetallic analytes fragmented easily, but significant components of the molecules are successfully identified. After optimizing the ionization and analytical procedure, LI-TOF-MS proved useful in the analysis of high molecular mass metal complexes. / Master of Science

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Doctor of Philosophy / Department of Physics / Vinod Kumarappan / In general, molecules in the gas phase are free to rotate, and measurements made on such samples are averaged over a randomly oriented distribution of molecules. Any orientation dependent information is lost in such measurements. The goal of the work presented here is to a) mitigate or completely do away with orientational averaging, and b) make fully resolved orientation dependent measurements. In pursuance of similar goals, over the past 50 years chemists and physicists have developed techniques to align molecules, or to measure their orientation and tag other quantities of interest with the orientation. We focus on laser induced alignment of asymmetric top molecules. The first major contribution of our work is the development of an effective method to align all molecular axes under field-free conditions. The method employs a sequence of nonresonant, impulsive laser pulses with varied ellipticities. The efficacy of the method is first demonstrated by solution of the time dependent Schr\"{o}dinger equation for iodobenzene, and then experimentally implemented to three dimensionally align 3,5 difluoroiodobenzene. Measurement from molecules aligned in this manner greatly reduces orientational averaging. The technique was developed via a thorough understanding and extensive computations of the dynamics of rotationally excited asymmetric top molecules. The second, and perhaps more important, contribution of our work is the development of a new measurement technique to extract the complete orientation dependence of a variety of molecular processes initiated by ultrashort laser pulses. The technique involves pump-probe measurements of the process of interest from a rotational wavepacket generated by impulsive excitation of asymmetric top molecules. We apply it to make the first measurement of the single ionization probability of an asymmetric top molecule in a strong field as a function of all relevant alignment angles. The measurement and associated calculations help identify the orbital from which the electron is ionized. We expect that this technique will be widely applicable to ultrafast-laser driven processes in molecules and provide unique insight into molecular physics and chemistry.

Call number: LD2668 .T4 1983 J66 / Master of Science

The Muon Ionization Cooling Experiment (MICE) is the first technical demonstration of muon ionization cooling, using a prototype section of a Neutrino Factory cooling channel. MICE is currently under construction at the Rutherford-Appleton Laboratory in the UK and will make the first cooling measurements in 2015, in Step IV of the experimental programme. Cooling predictions in Monte Carlo simulations of Step IV were found to disagree with the predictions of the 'cooling formula', a widely-used approximation, by up to 30% in liquid hydrogen (LH2). This disagreement was shown to originate, largely, from the multiple scattering expression used in the cooling formula. It was necessary to go back to the fundamental physics of scattering to derive a more accurate expression that includes scattering from atomic electrons. A modified form of the cooling formula was derived using this expression and gave better agreement with the Monte Carlo in LH2. Predictions are given for the equilibrium emittance, using the new expression, for seven low Z materials at muon momenta of 140, 200 and 240 MeV/c. Theories which predict the distribution of multiple scattering angles are briefly reviewed, focusing on Moliere theory and its variants, which are the most widely-used theories. The distributions predicted by these theories are used in most Monte Carlo codes but their implementation is not transparent, especially regarding the treatment of scatters with atomic electrons, which are important in low Z materials. A simple Monte Carlo model to predict multiple scattering distributions was developed that correctly treats scatters off electrons. The model gives very good agreement with measurements by the MuScat Experiment. Investigations were made into the possibility of measuring multiple scattering in MICE Step IV, both with and without the magnetic field. Preliminary results suggest that measurements are easier with no magnetic field, where tracks are straight. Corrections to account for the resolution of the scintillating-fibre trackers are required in both cases, but these are substantially smaller when straight tracks are used.