Manifestation of site energy landscapes for ion transport in borate glasses.

The potential energy landscape of lithium borate glass of composition Li3B7O12 has been investigated by the charge attachment induced transport (CAIT) technique. Here, native lithium ions have been replaced by foreign alkali ions, M+ = K+, Rb+, Cs+. All experiments exhibit a pronounced decrease of native ion diffusion coefficients over more than 4 orders of magnitude with decreasing local population of Li+. The energy landscape is modelled by a site energy distribution (SED) with a concentration dependent Fermi energy of the native Li+ ions. The width of the populated part of the SED is found to be 250 meV (FWHM). The conclusion is made possible by a combination of a macroscopic ion replacement experiment with a Nernst-Planck-Poisson modelling of concentration depth profiles measured by secondary ion mass spectrometry (SIMS). Possible generalizations of macroscopic transport theory to match an Onsager ansatz are discussed.

Ion molecule reactions in the HBr+ + CH4 system: a combined experimental and theoretical study.

Reactions in the system HBr+ + CH4 have been investigated inside a guided ion-beam apparatus under single-collision conditions. The HBr+ is vibrational and rotational state selected in the electronic X2Π1/2 state created by (2+1)-REMPI. Due to the exitation scheme employed different rotational states of the HBr+ are accessible. Four reaction channels have been observed. The cross section, σ, for the exothermic proton transfer channel (PT) decreases with increasing collision energy, steeper than predicted by the Langevin model. The cross section also decreases with increasing rotational energy in the HBr+, with the effect of the rotational energy being stronger than that of translational energy. The cross section for the endothermic charge transfer (CT) increased with increasing collision energy. The energy dependence is well reproduced by a simple line of center (loc) model. Although the bromine transfer (BT) is exothermic the observed cross section increased with increasing collision energy due to an activation barrier on the potential energy surface (PES). Analysis by a modified loc model suggest the relevance of an angle dependence of σ. The cross section for the endothermic hydrogen atom abstraction (HA) exhibits a maximum at 2 eV Ecm. The measured cross sections are rationalized by means of reaction dynamics simulations which show good agreement with the experimental cross sections. The dynamics simulations are carried out with a machine learning potential that is developed and benchmarked with ab initio molecular dynamics simulation. The absolute cross sections predicted by reaction dynamics simulations are well within the same order of magnitude while reproducing the trends over three different collision energies for all four reaction channels. Furthermore, the simulations demonstrate various reaction mechanisms for these reaction channels, including a very interesting HBr+ orientation selectivity for the BT reaction channel.

Ion-molecule reactions in the HBr+ + HCl (DCl) system: a combined experimental and theoretical study.

Reactions in the system HBr+ + HCl (DCl) were investigated inside a guided ion-beam apparatus under single-collision conditions. In the HBr+ + HCl system, the proton transfer (PTHCl) and charge transfer (CT) are observable. In the HBr+ + DCl system, proton transfer (PTDCl) and deuterium abstraction (DA) are accessible. The cross sections for all reaction channels were measured as a function of the collision energy Ecm and of the rotational energy Erot of the ion. The rotationally state-selective formation of the ionic species was realized by resonance-enhanced multiphoton ionization (REMPI). As expected, the PT-channels are exothermic, and the cross section decreases with increasing collision energy for both PTHCl and PTDCl. The cross section for DA also decreases with an increasing Ec.m.. In the case of a considerably endothermic CT-channel, the reaction efficiency increases with increasing collision energy but has an overall much smaller cross sections compared to PT and DA reactions. Both PT-reactions are hindered by ion rotation, whereas DA is independent of Erot. The CT-channel shows a rotational enhancement near the thermochemical threshold. The experiment is complemented by theory, using ab initio molecular dynamics (AIMD, also known as direct dynamics) simulations and taking the rotational enhancement of HBr+ into account. The simulations show good agreement with the experimental results. The cross section of PTHCl decreases with an increase of the rotational energy. Furthermore, the absolute cross sections are in the same order of magnitude. The CT channel shows no reactions in the simulation.

Coincident measurement of photo-ion circular dichroism and photo-electron circular dichroism in 1-phenylethylamine.

Here, we report the coincident measurement of PICD and PECD effects in 1-phenylethylamine upon multiphoton ionization. Both photo-ion circular dichroism (PICD) and photo-electron circular dichroism (PECD) are methods to distinguish enantiomers. In PICD, a difference in total ion yields upon multiphoton ionization with circular polarized light is measured, whereas, in PECD, circular dichroism is observed in the angular distribution of the photoelectrons. Here, we report on our continuous effort to measure the PICD and PECD effects in coincidence, i.e. simultaneously under the same measurement conditions using a home-built photoion-photoelectron coincidence spectrometer. Pure samples of R-(+)-1-phenylethylamine and S-(-)-1-phenylethylamine have been photo-ionized using a femtosecond laser operated at 394 nm.

The Potential Energy Profile of the HBr+ + HCl Bimolecular Collision.

Recently, the HBr+ + HCl bimolecular reaction has been exploited by guided ion beam studies to probe the effect of rotational excitations and collision energies on the dynamics of the ion-molecule reactions. The current manuscript employs high-level ab initio calculations and reports the potential energy of pathways leading to various products, including HBr + HCl+, H2Cl+ + Br, H2Br+ + Cl, and H2 + BrCl+. The study shows that the intermediates involved in this reaction are connected by low-lying transition states, thus frequent isomerizations and diverse products are expected. Further, this manuscript screens the performance of 192 different combinations of computationally efficient methods and basis sets in order to identify the optimal quantum chemical method for further dynamics simulations.

Photoelectron Circular Dichroism in the Photodetachment of Amino Acid Anions.

The chirality of chemical compounds is of undisputed importance in science and technology. In particular with respect to pharmacological application most molecules of interest cannot be accessed by the powerful techniques developed in recent years for gas phase analytes. Here, we demonstrate that the combination of electrospray ionization (ESI) with the detection of photoelectron circular dichroism (PECD) provides access to chirality information applicable to molecular materials with negligible vapor pressure, for example, amino acids. To this end, glutamic acid and 3,4-dihydroxyphenylalanine (DOPA) have been electrosprayed into the source of a chirality spectrometer, where photodetachment is enforced and the PECD is detected. The technique can be expected to be conceptually applicable to all chemical systems with chirality based on molecular properties.

Qualitative and Quantitative Distinction of ortho-, meta-, and para-Fluorotoluene by Means of Chirped Femtosecond Laser Ionization.

Femtosecond-laser ionization mass spectrometry (fs-LIMS) is demonstrated to be a powerful analytical method providing access to the qualitative distinction of structural isomers of ortho-, meta-, and para-fluorotoluene. The key point of the approach presented is a systematic variation of the spectral phase of the fs-laser pulses, which characteristically affects the fragmentation pattern observed in the mass spectra. Variation of the linear chirp parameter is also helpful for rationalizing the fragmentation mechanism. Ultimately two ternary mixtures of the three title isomers are quantitatively analyzed in situ with an accuracy of 5% for the molar fractions.

Coincident measurement of photo-ion circular dichroism and photo-electron circular dichroism.

Two methods of laser-induced mass-selective chiral analysis based on circular dichroism have been reported in the literature: photo-ion circular dichroism (PICD) and photo-electron circular dichroism (PECD). In PICD, a difference in total ion yields upon multiphoton ionization with circular polarized light is measured, whereas in PECD, the circular dichroism is observed in the angular distribution of the photoelectrons. Here, we report the first coincident measurement of the PICD and PECD effects. A home-built photoion-photoelectron coincidence spectrometer has been used to measure both the PICD and the PECD effects simultaneously under the same measurement conditions. Pure samples of R- and S-methyloxirane have been photo-ionized using a femtosecond laser operation at 396 nm.

Self-Reactions in the HBr+ (DBr+) + HBr System: A State-Selective Investigation of the Role of Rotation.

Self-reactions observed in the HBr+ (DBr+) + HBr system have been investigated using a guided ion-beam experiment under single-collision conditions. The reaction channels observed are proton transfer/hydrogen abstraction (PT/HA) in the case of HBr+ and deuteron transfer/hydrogen abstraction (DT/HA) and charge transfer (CT) in the case of DBr+. HBr+/DBr+ ions have been formed with rotational energies selected using the resonance-enhanced multiphoton ionization (REMPI) formation process. Cross sections have been measured as a function of the rotational energy of the ion, Erot, and of the center-of-mass collision energy, Ecm. In the region of low rotational energies, the cross section for both PT/HA and DT/HA decreases with increasing ion rotation. In this region, the cross section for CT increases with increasing ion rotation. For higher rotational energies, the cross section increases with increasing ion rotation for PT/HA and less pronounced for DT/HA. The cross section for CT becomes independent of ion rotation for high rotational energies. Since all reaction channels are exothermic, all cross sections decrease with increasing Ecm.

Theoretical Study of the Dynamics of the HBr+ + CO2 → HOCO+ + Br Reaction.

The dynamics of the HBr+ + CO2 → HOCO+ + Br reaction was recently investigated with guided ion beam experiments under various excitations (collision energy of the reactants, rotational and spin-orbital states of HBr+, etc.), and their impacts were probed through the change of the cross section of the reaction. The potential energy profile of this reaction has also been accurately characterized by high-level ab initio methods such as CCSD(T)/CBS, and the UMP2/cc-pVDZ/lanl08d has been identified as an ideal method to study its dynamics. This manuscript reports the first ab initio molecular dynamics simulations of this reaction at two different collision energies, 8.1 kcal/mol and 19.6 kcal/mol. The cross sections measured from the simulations agree very well with the experiments measured with HBr+ in the 2∏1/2 state. The simulations reveal three distinct mechanisms at both collision energies: direct rebound (DR), direct stripping (DS), and indirect (Ind) mechanisms. DS and Ind make up 97% of the total reaction. The dynamics of this reaction is also compared with nucleophilic substitution (SN2) reactions of X- + CH3Y → CH3X + Y- type. In summary, this research has revealed interesting dynamics of the HBr+ + CO2 → HOCO+ + Br reaction at different collision energies and has laid a solid foundation for using this reaction to probe the impact of rotational excitation of ion-molecule reactions in general.

Site energy distribution of sodium ions in a sodium rubidium borate glass.

A charge attachment induced transport experiment has been conducted on a Na+ and Rb+ containing glass employing an external Rb+ ion beam. Native Na+ ions are replaced by external Rb+ ions giving rise to a pronounced concentration depth profile as measured by time-of-flight secondary ion mass spectrometry. From the theoretical analysis of this concentration profile a unique site energy distribution (SED) of mobile Na+ ions in the glass is derived. The full width at half maximum of the populated part of this SED is 0.32 eV. The mechanism involves Na+ sites being vacated top-down and being filled by Rb+ also top down. Therefore, the Fermi energy of Na+ ions decreases with ongoing experiment, while that of the Rb+ ions stays constant. Agreement between experiment and the Nernst-Planck-Poisson theory for describing the transport is reached by assuming that both the migration and the chemical diffusion driven contribution to the total flux depend on the local concentration.

Charge attachment induced transport - bulk and grain boundary diffusion of potassium in PrMnO3.

The transport of potassium through praseodymium-manganese oxide (PrMnO3; PMO) has been investigated by means of the charge attachment induced transport (CAIT) technique. To this end, potassium ions have been attached to the front side of a 250 nm thick sample of PMO. The majority of the potassium ions become neutralized at the surface of the PMO, while some of the potassium ions diffuse through. Ex situ analysis of the sample by time-of-flight secondary ion mass spectrometry (ToF-SIMS) reveals pronounced concentration profiles of the potassium, which is indicative of diffusion. Two diffusion coefficients have been obtained, namely, the bulk diffusion coefficient and the diffusion coefficient associated with the grain boundaries. The latter conclusion is supported by transmission electron microscopy of thin lamella cut out from the sample, which reveals twin grain boundaries reaching throughout the entire sample as well as model calculations.

Bombardment induced ion transport - part IV: ionic conductivity of ultra-thin polyelectrolyte multilayer films.

The dependence of the ionic conductance of ultra-thin polyelectrolyte multilayer (PEM) films on the temperature and the number of bilayers has been investigated by the recently developed low energy bombardment induced ion transport (BIIT) method. To this end multilayers of alternating poly(sodium 4-styrene sulfonate) (PSS) and poly(allylamine hydrochloride) (PAH) layers were deposited on a metal electrode and subsequently bombarded by a low energy potassium ion beam. Ions are transported through the film according to the laws of electro-diffusion towards a grounded backside electrode. They are neutralized at the interface between the polymer film and the metal electrode. The detected neutralization current scales linearly with the acceleration potential of the ion beam indicating Ohmic behavior for the (PAH/PSS)x multilayer, where x denotes the number of bilayers. The conductance exhibits a non-monotonic dependence on the number of bilayers, x. For 2 ≤ x ≤ 8 the conductance increases non-linearly with the number of bilayers. For x ≥ 8 the conductance decreases with increasing number of bilayers. The variation of the conductance is rationalized by a model accounting for the structure dependence of the conductivity. The thinnest sample for which the conductance has been measured is the single bilayer reflecting properties dominated by the interface. The activation energy for the ion transport is 0.49 eV.

Self-reactions in the HCl(+) (DCl(+)) + HCl system: a state-selective investigation of the role of rotation.

The self-reaction of state-selected HCl(+) (DCl(+)) ions with HCl has been investigated in a guided ion beam setup. The absolute cross sections for proton transfer and deuteron transfer decrease with increasing center of mass collision energy, Ec.m.. The cross section for charge transfer (DCl(+) + HCl) exhibits a maximum at Ec.m. = 0.5 eV. The cross section for PT and DT decrease significantly with increasing rotational angular momentum in the molecular ion, for the PT the cross section increases again for the highest angular momentum investigated. The rotational dependence of the cross section is rationalized by a simple model in which both the collision energy and part of the rotational energy are available for the reaction. The contribution of the rotation to the total energy available itself depends on the collision energy.

Ion transport through polyelectrolyte multilayers.

Polyelectrolyte multilayer (PEM) films and capsules loaded with ion-sensitive fluorophores can be used as ion-sensors for many applications including measurements of intracellular ion concentration. Previous studies have shown the influence of the PEM films/shells on the specific response of encapsulated ion-sensitive fluorophores. PEM shells are considered as semipermeable barriers between the environment and the encapsulated fluorophores. Parameters such as the time response of the encapsulated sensor can be affected by the porosity and charge of the PEM shell. In this study, the time response of an encapsulated pH-sensitive fluorophore towards pH changes in the surrounding environment is investigated. Furthermore, the conductance of PEM films for potassium ions is determined.

Bond-dissociation energies of cations--pushing the limits to quantum state resolution.

Currently available concepts for measuring the bond-dissociation energy of cations D(o) are reviewed. Starting from the traditional approach of directly measuring the threshold energy for the appearance of fragment ions, attention is directed towards indirect measurements, where threshold energies are obtained by extrapolation of, for example, rate constants k(E) or kinetic energy release (KER) data to the threshold of interest. More recent high precision techniques again utilize direct measurements, for example, of the disappearance energy of the parent ion. Most precise data are obtained from quantum state resolved measurements of the dissociation energy, where the threshold energy is bracketed by the existing quantum states above and below the threshold. Ultimately the limits can even be pushed beyond the bracketing limit, by investigating steps on the lineshape of homogeneously broadened single rotational transitions.

Hydrogen scrambling in ethane induced by intense laser fields: statistical analysis of coincidence events.

Two-body Coulomb explosion processes of ethane (CH(3)CH(3)) and its isotopomers (CD(3)CD(3) and CH(3)CD(3)) induced by an intense laser field (800 nm, 1.0 × 10(14) W/cm(2)) with three different pulse durations (40 fs, 80 fs, and 120 fs) are investigated by a coincidence momentum imaging method. On the basis of statistical treatment of the coincidence data, the contributions from false coincidence events are estimated and the relative yields of the decomposition pathways are determined with sufficiently small uncertainties. The branching ratios of the two body decomposition pathways of CH(3)CD(3) from which triatomic hydrogen molecular ions (H(3)(+), H(2)D(+), HD(2)(+), D(3)(+)) are ejected show that protons and deuterons within CH(3)CD(3) are scrambled almost statistically prior to the ejection of a triatomic hydrogen molecular ion. The branching ratios were estimated by statistical Rice-Ramsperger-Kassel-Marcus calculations by assuming a transition state with a hindered-rotation of a diatomic hydrogen moiety. The hydrogen scrambling dynamics followed by the two body decomposition processes are discussed also by using the anisotropies in the ejection directions of the fragment ions and the kinetic energy distribution of the two body decomposition pathways.

Analysis of chirality by femtosecond laser ionization mass spectrometry.

Recent progress in the field of chirality analysis employing laser ionization mass spectrometry is reviewed. Emphasis is given to femtosecond (fs) laser ionization work from the author's group. We begin by reviewing fundamental aspects of determining circular dichroism (CD) in fs-laser ionization mass spectrometry (fs-LIMS) discussing an example from the literature (resonant fs-LIMS of 3-methylcyclopentanone). Second, we present new data indicating CD in non-resonant fs-LIMS of propylene oxide.

Photoelectron Circular Dichroism of Electrosprayed Gramicidin Anions.

Many sophisticated approaches for analyzing properties of chiral matter have been developed in recent years. But in general, the available chiroptical methods are limited to either solvated or small gaseous molecules. Studying the chirality of large biopolymers in the gas phase, including aspects of the secondary structure, becomes accessible by combining the electrospray ionization technique with chiroptical detection protocols. Here, laser-induced photodetachment from gramicidin anions, a peptide consisting of 15 amino acids has been investigated. The angular distribution of photoelectrons is demonstrated to be sensitive to the substitution of protons by cesium ions, which is accompanied by a conformational change. The photoelectron circular dichroism (PECD) is -0.5% for bare gramicidin, whereas gramicidin with several Cs+ ions attached exhibits a PECD of +0.5%. The results are complemented and supported by ion mobility studies. The presented approach offers the prospect of studying chirality and the secondary structure of various biopolymers.

Circular dichroism in ion yields employing femtosecond laser ionization-the role of laser pulse duration.

The circular dichroism (CD) induced by femtosecond laser pulse excitation of 3-methyl-cyclopentanone has been investigated by means of experiment and theory as a function of the laser pulse duration. In the experiment the CD in ion yields is measured by femtosecond laser ionization via a one-photon resonant excited state. In the theoretical part the CD is calculated by solving laser driven quantum electron dynamics for the same resonant excitation based on ab initio electronic structure calculations employing a complete description of the electric field-electric dipole and magnetic field-magnetic dipole interactions. Both the experimentally measured CD in ion yields and the calculated CD in excited state populations exhibit a marked increase of the CD for pulse duration increasing from 50 fs to about 200 fs. Beyond 200 fs pulse duration the CD levels off. The combination of experimental and theoretical evidences indicates that the CD decreases with increasing laser intensity connected to the increased coupling between the excited states.