Transient behavior of a nonequilibrium plasma formed by merged beams

A low density, low temperature plasma formed by two merged beams of electrons and ions at near zero relative velocity is studied by solving a set of time-dependent rate equations. In particular, we investigate the role played by the radiative recombination (RR) and three-body recombination (TBR) on the population of excited states during the initial stage of plasma rearrangement and relaxation. It is found in the case of hydrogenic plasmas that low-lying states are filled predominantly by RR, while high Rydberg states are populated mainly by TBR. As the plasma further relaxes, the collisional excitation and de-excitation, and radiative decays become important, filling the median excited states. The dependence of the TBR and RR rates on ionic chargeZ is discussed to extend the result to plasmas of highZ ions.     

Intramolecular Path Determination of Active Electrons on Push-Pull Oligocarbazole Dyes-Sensitized Solar Cells

Several push-pull oligocarbazole dye-sensitizers have been studied using theoretical methods in order to better understand the relationship between structural electronic or optical properties and intramolecular path of active electrons during the ionization and injection processes. DFT/TD-DFT calculations were performed on a series of five dye sensitizers. They differ by the presence of electron donating group (EDG) by inductive effect (noted+I) or electron releasing group (ERG) by mesomeric effect (noted+M) or electron withdrawing group by inductive effect (noted-I) on the pushed part of the dyes studied. Our work focused on the internal distribution of electrons in the different parts of dye that are the push/pull moieties and the π -bridge. The study concerned the ground state, the electronic transition process and the excited state. In each situation, the fragment acting in the ionization or transition phenomena were identified. In the ground state, the electrons of the push part appear to be the least bound because they have the highest probabilities of ionization. In the excited state, the ionized atoms are essentially positioned in the pushing part and some neighboring atoms of the bridge. In the electronic transition, the active atoms are located in the π -conjugated part but only on the side adjacent to the acceptor group. To arrive to this conclusion, we optimized the structures of the five dyes in their ground and excited states. We calculated the atomic charges, the wavelengths and intensities of electronic transitions in the visible domain, the reorganization energies as well as the oxidation potential. It appears that +M donor ligands improve the performance of a dye because the great distribution of atoms to be ionized in the push parts.     

Measured and modeled enhancement of transition metal emissions in the d.c. plasma jet

Enhancement of sensitive transition metal lines by a sodium matrix is measured in a 3-electrode d.c. plasma jet. Spiking with 0.43 M NaCI causes enhancement by factors of 1.85–2.92 in ionic lines and of 1.22–1.99 in atomic lines for eight of the structurally related analyte elements, but suppresses Zn I and Zn II emissions by about 25 %. Emission response to NaCI of lines within the same spectrum, or between different spectra of like ionization stage, can be simulated to 15 % and 20–25 %, respectively, by approximations linear in energy differences. For ionic lines these differences are the absolute value of the line excitation potential minus the energy of the ion state most readily pumped by Penning ionization by argon. For atomic lines it is the difference between emitting state excitation potential and the first ionization potential. Analyses of the experimental data strongly suggest that: (1) Na acts mainly to pertub radiative transfer rather than collisional redistribution processes; (2) population pumping of excited analyte states is largely driven by Penning ionization; (3) accelerated radiative cooling due to Na is manifested in a lowering of local kinetic temperature; (4) to a first-order of approximation, ambipolar diffusion, analyte-Na collisions of the second kind, and analyte ground state spin, do not influence emission line enhancement by easily ionized elements (EIE). Approximations are developed for predicting transition metal enhancements by arbitrary Na doping concentrations, and means are sketched for extending the method to other analyte group/EIE combinations. Practical implications of the work are noted.     

Estimation of the degree of ionization and the proportion of excited atoms in flame atomic spectrometry: a steady state approach

Summary A model is presented for the ionization of elements during flame atomic spectrometry, based on successive excitation of the electron to higher energy levels and finally the ionized state. The model is discussed in terms of a steady state involving thermal excitation, ionization, collisional excitation and collisional charge transfer interactions within the flame. Expressions are derived for the fraction ionized, and the fraction excited in terms of the rate constants for thermal excitation and radiative relaxation of the excited state. Data are presented showing good agreement between calculated and literature values for the fraction ionized for representative Group I and Group II elements.     

Theory for the optical properties of small Hg n clusters

The static and dynamical polarizabilities of the Hg-dimer are calculated by using a Hubbard Hamiltonian to describe the electronic structure. The Hamiltonian is diagonalized exactly within a subspace of second-quantized electronic states from which only multiply ionized atomic configurations have been excluded. With this approximation we can describe the most important electronic transitions including the effect of charge fluctuations. We analyze the polarizability as a function of the intraatomic Coulomb interaction which represents the repulsion between electrons. We obtain that this interaction results in strong electronic correlations in the excited states and increases the first excitation energy of the dimer by 0.8 eV in comparison to a calculation which neglects correlations, resulting in a better agreement with the experiment.     

Study of the Anode Region of a DC Glow Discharge by a Spatially One-Dimensional Hybrid Method

The anode region of a dc glow discharge at low pressure and current is studied by a new self-consistent, spatially one-dimensional hybrid method. The method consists of the coupled solution of the steady-state fluid equations of electrons, ions, and excited atoms and the Poisson equation using the electron transport properties as well as the excitation and ionization frequencies from a strict solution of the non-uniform kinetic equation of the electrons. Results such as the electric potential, the electron velocity distribution function, and the densities of the charge carriers and excited atoms are reported for the anode region of neon glow discharges. Physical properties of the plasma in the anode region known from experiments have been confirmed by the model such as the occurrence of the anode fall, a formation of plateau-like areas of the potential profile in front of the anode, the anode dark space, and the anode glow.     

A nearly complete system of average crystallographic ionic radii and its use for determining ionization potentials

Available systems of empirical (crystallographic) ionic radii are compared. All these systems turn out to be compatible if the O^2? radius is taken to be 0.140 nm. The choice of the oxygen ionic radius is dictated by the equality of the metal ion-oxygen ion distances in oxide crystals and the metal ion-oxygen atom distances in crystal hydrates and concentrated aqueous solutions. In all systems of empirical ionic radii under consideration, the uncertainty of determination of ionic radii is 0.002–0.005 nm. A new method of determination of the ionic radii of elements in unusual valence states is suggested: from the empirical dependence of the electron density at an atom in a given valence state on the atomic radius, a two-parameter equation relating the ionic radii of Period 4–7 elements in two valence states is derived, which allows one to calculate the ionic radius that cannot be determined by crystallography because of the lack of stable compounds in this valence state. Ionic radii are calculated for all Period 4–7 elements in all valence states. They constitute a nearly complete system of ionic radii. There is a linear relationship between the atomic nucleus charge and the inverse ionic radius. It is shown that the square root of the ionization potential is a linear function of the inverse ionic radius. The as yet experimentally unknown ionization potentials of 78 ions of different elements are estimated.     

Theoretical-experimental study of formic acid photofragmentation in the valence region

Photoionization and photofragmentation studies of formic acid (HCOOH) are performed for the valence shell electron ionization process. The total and partial ion yield of gaseous HCOOH were collected as a function of photon energy in the ultraviolet region, between 11.12 and 19.57 eV. Measurements of the total and partial ion yield of gaseous formic acid molecule are performed with a time-of-flight mass spectrometer at the Synchrotron Light Brazilian Laboratory. Density functional theory and time dependent density functional theory are employed to calculate the ground and excited electronic state energies of neutral and ionic formic acid as well as their fragments and normal vibration modes. The ionization potential energies, the stability of electronic excited states of HCOOH(+), and the energies of opening fragmentation channels are estimated from theoretical-experimental analysis. Additionally, the main formic acid photofragmentation pathways by exposition of photons within that energy range are determined experimentally. These produced ions primarily have the following mass/charge ratios: 46 (HCOOH(+)), 45 (COOH(+)), 29 (HCO(+)), and 18 (H(2)O(+)).     

Strong-field ionization and dissociation studies on small early transition metal carbide clusters via time-of-flight mass spectrometry

In this work, we report experimental results from the strong-field ionization and subsequent Coulomb explosion of narrow distributions of small (<40 atoms) heteronuclear clusters composed of transition metal (Ti, V, Cr, Nb, or Ta) and carbon atoms. Analysis of the resulting multiply charged ions was performed through time-of-flight mass spectrometry, and evidence regarding ionization dynamics was obtained. The data reveal the presence of enhanced ionization during exposure to the ultrashort (～100 fs) pulse resulting in the formation of ions possessing significantly higher charge states than those predicted from atomic species. Regardless of the transition metal species, we observe the absorption of similar amounts of energy from the external field, as indicated by the maximum observed charge states in each experiment. These results are compared to our previously reported study on the strong-field ionization of transition metal oxide clusters. We observe identical maximum observable charge states for each of the transition metal species resulting from both metal oxide and metal carbide clusters.     

Visualizations of transition dipoles, charge transfer, and electron-hole coherence on electronic state transitions between excited states for two-photon absorption

The one-photon absorption (OPA) properties of donor-pi-bridge-acceptor-pi-bridge-donor (D-pi-A-pi-D)-type 2,1,3-benzothiadiazoles (BTD) were studied with two dimensional (2D) site and three dimensional (3D) cube representations. The 2D site representation reveals the electron-hole coherence on electronic state transitions from the ground state. The 3D representation shows the orientation of transition dipole moment with transition density, and the charge redistribution on the excited states with charge difference density. In this paper, we further developed the 2D site and 3D cube representations to investigate the two-photon absorption (TPA) properties of D-pi-A-pi-D-type BTD on electronic transitions between excited states. With the new developed 2D site and 3D cube representations, the orientation of transition dipole moment, the charge redistribution, and the electron-hole coherence for TPA of D-pi-A-pi-D-type BTD on electronic state transitions between excited states were visualized, which promote deeper understanding to the optical and electronic properties for OPA and TPA.     

Emission and sputtering characteristics of Ne-Ar mixed gas glow discharge plasmas.

The emission characteristics of several Cu lines emitted from a Ne-Ar mixed gas glow discharge plasma were investigated. The addition of small amounts of Ar to a Ne plasma increases the sputtering rate of a Cu sample because Ar ions, which work as the impinging ions for cathode sputtering, are predominantly produced through Penning ionization collisions between Ne metastables and Ar atoms. Ar addition also elevates the number density of electrons in the plasma. These changes occurring in the Ne-Ar mixed gas plasma result in enhanced emission intensities of the Cu lines. The Cu II 270.10-nm and the Cu II 224.70-nm lines yield different intensity dependence on the Ar partial pressure added. This phenomenon is because these Cu II lines are excited principally through different charge transfer processes: collisions with Ne ions for the Cu II 270.10-nm line and collisions with Ar ions for the Cu II 224.70-nm line. The shape of sputtered craters in the Ne-Ar glow discharge plasma was measured. The depth resolution was improved when Ar was added to a Ne plasma because the crater bottoms were flatter with larger Ar partial pressures.     

金属-配体复合物的金属到配体、配体到配体电荷转移的可视化

利用三种方法可视化化了Ru（II）ammine的金属到配体的电荷转移．首先原子分辨的态密度显示HoM0上的密度主要在Ru上,LUMo上的态密度在ammine上,这说明Ru上激发的电子会转移到ammine配体上．第二,电荷差异密度揭示了所有的窄穴都在Ru上,所有的电子都在ammine上．第三,跃迁密度矩阵揭示了Ru和Hammine上的电子空穴对的相关性．这三种方法也用来研究Os（bpy）2（pop）Cl的金属到配体的电荷转移和Alq3配体到配体的电荷转移．     

Photoinduced dynamics of hydrated adenine clusters

We studied the photoinduced dynamics of hydrated adenine clusters by multiphoton ionization techniques. The majority of the hydrated adenine monomers are found to experience dissociative ionization, where the adenine monomer ions are produced due to the fragmentation of the water solvents by three-photon process. Due to fast internal conversion from the electronic states reached by the first photon, the fragmentation takes place in the vibrationally excited electronic ground state and in the vibrationally excited ionic states. Thus, the abundance of the hydrated adenine monomer ion depends on the excitation photon energy, possibly because the lifetime of the intermediate states is different and an internal conversion competes with direct ionization. In addition, a significant amount of protonated adenine monomer is observed. This indicates that the proton transfer is followed by the fragmentation in the hydrated adenine clusters. The abundance of the protonated adenine monomer also depends on the excitation photon energy mainly due to the ionization efficiency of the parent species.     

Spectroscopic properties of gallium arsenide tetramers: Ga2As2, Ga2As2+ and Ga2As2-

Spectroscopic properties of the low-lying electronic states of Ga2As2 and its ions are studied using the complete active-space self-consistent field (CASSCF) and density function theory (DFT) followed by the coupled-cluster single and double substitutions (including triple excitations) (CCSD(T)) calculations. The stability of low-lying electronic states is examined by computing vibrational frequency. The energies of the ground states and a number of excited electronic states have been computed to predict the spectra of Ga2As2 and its ions. The ionization energy, electronic affinity, and atomization energy are estimated at the CCSD(T)/6-311+G(d) level and compared with the available experimental results.     

On the time scale of internal energy relaxation of AP-MALDI and nano-ESI Ions in a quadrupole ion trap

Recently reported results (Konn et al. [14]) on the collisional cooling of atmospheric pressure matrix assisted laser desorption ionization (AP-MALDI) and nano-electrospray ionization (nano-ESI) generated ions in a quadrupole ion trap mass spectrometer (QITMS) are inconsistent with measured collisional cooling rates. The work reported here presents a re-examination of those previous results. Collision induced dissociation (CID) has been used to probe various properties of ions contained in a QITMS. It is shown experimentally that when trapping large numbers of ions, an effective dc trapping voltage is induced that varies with changes in the size of the ion cloud. A decrease in the resonant frequency for maximum CID efficiency is observed as the cool time between parent ion isolation and CID is increased. Ion trajectories in a QITMS are simulated to demonstrate how ion density changes over the course of parent ion isolation. The effect of space charge on ion motion is simulated, and Fourier transformations of ion axial motion plus simple calculations corroborate the experimentally observed transient frequency shifts. The relative stability of ions formed by AP-MALDI and nano-ESI is compared under low charge density conditions. These data show that the ions have reached equilibrium internal energy and, thus, that differences in dissociation onsets and “50% fragmentation efficiency points” between the ionization mechanisms are due to the formation of distinct ion conformations as previously shown in reference [28]. The conclusions of Konn et al. [14] are based on invalid experimental procedures as well as inappropriate comparisons of QITMS data to low-pressure FT-ICR data.     

Emission characteristics of Grimm-style glow discharge plasmas with helium matrix plasma gas containing small amounts of nitrogen

Glow discharge plasmas with helium–(0–16%) nitrogen mixed gas were investigated as an excitation source in optical emission spectrometry. The addition increases the sputtering rate as well as the discharge current, because nitrogen molecular ions, which act as primary ions for the cathode sputtering, are produced through Penning-type ionization collisions between helium metastables and nitrogen molecules. The intensity of a silver atomic line, Ag I 338.29 nm, is monotonically elevated along with the nitrogen partial pressure added. However, the intensities of silver ionic lines, such as Ag II 243.78 nm and Ag II 224.36 nm, gave different dependence from the intensity of the atomic line: Their intensities had maximum values at a nitrogen pressure of 30 Pa when the helium pressure and the discharge voltage were kept at 2000 Pa and 1300 V. This effect is principally because the excitations of these ionic lines are caused by collisions of the second kind with helium excited species such as helium metastables and helium ion, which are quenched through collisions with nitrogen molecules added to the helium plasma. The sputtering rate could be controlled by adding small amounts of nitrogen to the helium plasma, whereas the cathode sputtering hardly occurs in the pure helium plasma.     

Emission characteristics of Grimm-style glow discharge plasmas with helium matrix plasma gas containing small amounts of nitrogen

Glow discharge plasmas with helium–(0–16%) nitrogen mixed gas were investigated as an excitation source in optical emission spectrometry. The addition increases the sputtering rate as well as the discharge current, because nitrogen molecular ions, which act as primary ions for the cathode sputtering, are produced through Penning-type ionization collisions between helium metastables and nitrogen molecules. The intensity of a silver atomic line, Ag I 338.29 nm, is monotonically elevated along with the nitrogen partial pressure added. However, the intensities of silver ionic lines, such as Ag II 243.78 nm and Ag II 224.36 nm, gave different dependence from the intensity of the atomic line: Their intensities had maximum values at a nitrogen pressure of 30 Pa when the helium pressure and the discharge voltage were kept at 2000 Pa and 1300 V. This effect is principally because the excitations of these ionic lines are caused by collisions of the second kind with helium excited species such as helium metastables and helium ion, which are quenched through collisions with nitrogen molecules added to the helium plasma. The sputtering rate could be controlled by adding small amounts of nitrogen to the helium plasma, whereas the cathode sputtering hardly occurs in the pure helium plasma.     

An Anderson impurity model for efficient sampling of adiabatic potential energy surfaces of transition metal complexes

We present a model intended for rapid sampling of ground and excited state potential energy surfaces for first-row transition metal active sites. The method is computationally inexpensive and is suited for dynamics simulations where (1) adiabatic states are required "on-the-fly" and (2) the primary source of the electronic coupling between the diabatic states is the perturbative spin-orbit interaction among the 3d electrons. The model Hamiltonian we develop is a variant of the Anderson impurity model and achieves efficiency through a physically motivated basis set reduction based on the large value of the d-d Coulomb interaction U(d) and a Lanczos matrix diagonalization routine to solve for eigenvalues. The model parameters are constrained by fits to the partial density of states obtained from ab initio density functional theory calculations. For a particular application of our model we focus on electron transfer occurring between cobalt ions solvated by ammonium, incorporating configuration interaction between multiplet states for both metal ions. We demonstrate the capability of the method to efficiently calculate adiabatic potential energy surfaces and the electronic coupling factor we have calculated compares well to previous calculations and experiment. (