Incident 0.5 to 2.5 MeV charged particle beams were used to ionize the inner-shells of selected targets and study their subsequent emission of characteristic x-rays. ⁹Be⁺ ions were used to examine K-shell x-ray production from thin F, Na, Al, Si, P, Cl, and K targets, L-shell x-ray production from thin Cu, An, Ge, Br, Zr and Ag targets, and M-shell x-ray production from thin Pr, Nd, Eu, Dy, Ho, Hf, W, Au, Pb and Bi targets. L-shell x-ray production cross sections were also measured for ²⁷Al⁺ ions incident upon Ni, Cu, Zn, As, Zr, and Pd targets. M-shell x-ray production cross sections were measure for ²⁷Al⁺ and ⁴⁰Ar⁺ ions incident upon Pr, Nd, Gd, Dy, Lu, Hf, Au, Pb, Bi, and U targets. These measurements were performed using the 2.5 MV Van de Graaff accelerator at North Texas State University. The x-rays were detected with a Si(Li) detector whose efficiency was determined by fitting a theoretical photon absorption curve to experimentally measure values. The x-ray yields were normalized to the simultaneously measured Rutherford backscattered (RBS) yields which resulted in an x-ray production cross section per incident ion. The RBS spectrum was obtained using a standard surface barrier detector calibrated for to account for the "pulse height defect." The experimental results are compared to the predictions of both the first Born and ECPSSR theories; each of which is composed of two parts, the direct ionization (DI) of the target electron to the continuum and the capture (EC) of the target electron to the projectile. The first Born describes DI by the Plane-Wave-Born-Approximation (PWBA) and EC by the Oppenheimer-Brinkman-Kramers treatment of Nikolaev (OBKN). ECPSSR expands upon the first Born by using perturbed (PSS) and relativistic (R) target electron wave functions in addition to considering the energy loss (E) of the projectile in the target and its deviation from straight line trajectory (Coulomb deflection (C)). The measurements presented show that the first Born theories overestimate the measured results rather significantly for all experiments using the ⁹Be beams to examine the inner shell x-rays, while the ECPSSR predictions fir the measured data much better. For incident ²⁷Al and ⁴⁰Ar ions, the measured results are not predicted by the theories. The first Born generally over-predicts the data for low target atomic numbers while under-predicting at high atomic numbers. The ECPSSR theory greatly under-predicts the results (factors of 10³ to 10²⁰). Reasons for this behavior are discussed as well as suggestions for future experiments.

No description available.

The soft x-rays (wavelengths less than 30 nm) emitted by the sun are responsible for the production of high energy photoelectrons in the D and E regions of the ionosphere, where they deposit most of their energy. The photoelectrons created by this process are the main drivers for dissociation of nitrogen ($N_2$) molecules in the altitude range below 200 km. The dissociation of $N_2$ is one of main mechanisms responsible for the production of nitric oxide (NO) at these altitudes. These processes are important to understand because NO plays a critical role in controlling the temperatures of various regions of Earth's atmosphere. In order to estimate the dissociation rate of $N_2$ we need its dissociation cross-sections. The dissociation cross-sections of $N_2$ due to inelastic collisions with electrons is primarily es- timated from the cross-sections of its excitation states (using predissociation factors) and dissociative ionization channels. Predissociation is the transition without emission of radi- ation from a stable excited state to an unstable excited state of a molecule that leads to dissociation. Unfortunately, the lack of cross-section data, particularly at high electron en- ergies and of higher excited states of N 2 and N 2 + , introduces uncertainty in the dissociation cross-section and subsequently the dissociation rate calculation, which leads to uncertainties in the NO production rate. We have updated a photoelectron model with thoroughly-revised electron impact cross- section data of all major species and experimentally determined predissociation factors. The dissociation rates of $N_2$ using this model are compared to the dissociation rates obtained using another existing (Solomon and Qian [2005]) model. A parameterized version of the updated dissociation rates are used in a one-dimensional global average thermospheric/ ionospheric model, ACE1D (Atmospheric Chemistry and Energetics), to obtain the updated production rates of NO. In the final chapter, we use the ACE1D model to show that the energies deposited by the solar soft x-rays in the lower thermosphere at altitudes between 100 -150 km affect the temperature of the Earth's thermosphere at altitudes well above 300 km. By turning off the input solar flux in the different wavelength bins of the model iteratively, we are able to demonstrate that the maximum change in exospheric temperature is due to changes in the soft solar x-ray bins. We also show, using the thermodynamic heat equation, that the molecular diffusion via non-thermal photoelectrons is the main source of heat transfer to the upper ionosphere/thermosphere. Moreover, these temperature changes and heating effects of the solar soft x-rays are comparable to that of the much stronger He II 30.4nm emission. Finally, we show that the uncertainties in the solar flux irradiance at these soft x-rays wavelengths result in corresponding uncertainties in the modeled exospheric temperature, and these uncertainties increase substantially with increased solar activity. / Doctor of Philosophy / The radiation from the sun covers a wide range of the electromagnetic spectrum. The soft x-rays with wavelengths less than 30 nm are the most energetic and variable part of the spectrum, and would have detrimental effects on humans were they not absorbed by the atmosphere. The absorption of soft x-rays by the Earth's atmosphere at altitudes near 100- 150 km creates ionized and energized particles. These energetic changes can affect and even damage the satellites in low Earth orbit, and can cause radio communication blackouts and radiation storms (large quantities of energetic particles, protons and electrons accelerated by processes at and near the Sun). Therefore, we need to have good models that can quantify these changes in order to correctly predict their effects on our atmosphere, and help to mitigate any harmful effects. The soft x-rays and the extreme ultraviolet (EUV) are responsible for ionization of the major neutral species, $N_2$ , $O_2$ and O, in the Earth's atmosphere, which leads to the production of ions and energetic photoelectrons. These high energy photoelectrons can cause further ion- ization, excitation and dissociation. We study the dissociation of $N_2$ by these photoelectrons to create neutral N atoms. The N atoms created via this process combine with the $O_2$ in the atmosphere to produce nitric oxide (NO), which is one of the most important minor constituents because of its role in regulating atmospheric heating/cooling. The production of NO peaks near 106 km altitude, where most of the energy of the soft x-rays are deposited. However, they also affect the temperature of the upper atmosphere well above this altitude. This is because the energy of the photoelectrons is conducted to the upper atmosphere by collisions of electrons and ions with ambient neutral atoms and molecules, thus increasing their temperature. In this study, we use modeling of soft x-ray irradiance, photoelectron ionization, excitation and dissociation rates and atmospheric neutral temperature to quantify the effects of soft x-rays on the Earth's atmosphere.

In this dissertation, different approaches have been employed to address the quest of understanding the formation and growth mechanisms of carbon-containing molecular ions with relevance to astrochemistry. Ion mobility mass spectrometry and DFT computations were used to investigate how a second nitrogen in the pyrimidine ring will affect the formation of a covalent bond between the benzene radical cation and the neutral pyrimidine molecule, after it was shown that a stable covalent adduct can be formed between benzene radical cation and the neutral pyridine. Evidence for the formation of a more stable covalent adduct between the benzene radical cation and the pyrimidine is reported here. The effect of substituents on substituted-benzene cations on their solvation by an HCN solvent was also investigated using ion mobility mass spectrometry and DFT computations were also investigated. We looked at the effect of the presence of electron-withdrawing substituents in fluorobenzene, 1,4 di- fluorobenzene, and benzonitrile on their solvation by up to four HCN ligands, and compared it to previous work done to determine the solvation chemistry of benzene and phenylacetylene by HCN. We report here the observed increase in the binding of the HCN molecule to the aromatic ring as the electronegativity of the substituent increased. We also show in this dissertation, DFT calculations that reveal the formation of both hydrogen-bonded and electrostatic isomers, of similar energies for each addition to the ions respectively. The catalytic activity of the 1st and 2nd row TM ions towards the polymerization of acetylene done using the reflectron time of flight mass spectrometry and DFT calculations is also reported in this dissertation. We explain the variation in the observed trend in C-H/C-C activity of these ions. We also report the formation of carbide complexes by Zr+, Nb+, and Mo+, with the acetylene ligands, and show the thermodynamic considerations that influence the formation of these dehydrogenated ion-ligand complexes. Finally, we show in this dissertation, a novel ionization technique that we employed to generate ions that could be relevant to the interstellar and circumstellar media using the reflectron time of flight mass spectrometry.

V této práci je prezentována studie fragmentačního procesu zvolené molekuly a jeho vztah ke složení fragmentačních produktů. Práce je zaměřená na výpočet fragmentační energie molekuly pomocí ab initio kvantově chemických metod, metodou „density functional theory (DFT)“ a také srovnáním s experimentem. Je prezentován vliv výpočetní metody, bázového setu, a geometrie molekuly na simulaci. Byla porovnána fragmentace methylfenylsilanu (MPS), dimethylfenylsilanu (DMPS), a trimetylfenylsilanu (TMPS). Fragmentace byla iniciována monochromatickým elektronovým svazkem (EII). Hmotnostní spektrometrie byla využita ke studiu složení fragmentačních produktů MPS a TMPS. Fragmentační produkty MPS a TMPS měřené v rámci této práce byly doplněny o experimentální studii DMPS, která byla prezentována v literatuře. Takto byla získána řada molekul, které jsou strukturně podobné, ale mají výrazně rozdílné chování během fragmentace. Pomocí měření účinného průřezu byly měřeny disociační energie vazeb a tyto disociační energie byly vypočteny pomocí metody DFT. Kombinací teoretického výpočtu metodou DFT a experimentálního měření jsme poukázali na společné rysy a na rozdíly ve fragmentačním schématu všech tří molekul. Navrhli jsme odštěpení dvou vodíkových atomů během plazmově indukovaného fragmentačního procesu. Vodíky mohou být odštěpeny pomocí dvou mechanismů: i. odštěpení dvou vodíků jeden po druhém a ii. odštěpení molekuly H2 v jednom kroku. Z profilů energie dokážeme určit, který mechanismus bude v tom konkrétním případě pravděpodobnější. Předpokládaný mechanismus je v korelaci s experimentálními výsledky fragmentace zjištěnými z hmotnostních spekter.