Ion-surface Collisions Research Articles

Adsorbate-induced effects on the H− ion collisions with Na/Ag(111) and K/Ag(111) surfaces

The H− ion survival probabilities following on-top collisions with Na adsorbates deposited on Ag(111) at low coverage, are investigated for a wide range of exit angles from 20° to 90° measured from surface, and for various incident ion energies. A wave packet propagation approach is used in these calculations. The survival probabilities exhibit a series of well-defined peaks located at certain exit angles, that are indicative of avoided crossings between the various energy levels involved in the projectile/adsorbate/surface interaction. Both image states and the back-and-forth electronic motion between the ion projectile and the adsorbate/surface system contribute to the electronic population recaptured during the exit trajectory. For ion-surface collisions away from the on-top configuration, but in the close vicinity of adsorbates, a model is proposed to describe the variation of the H− projectile's distance of closest approach to the adsorbate-covered Ag(111) surface in terms of the ion's impact point on surface, e.g., starting from the on-top collision with a single adsorbate and gradually moving away, towards the “clean” surface. The distance of closest approach is a key factor in calculating correctly the ion survival probabilities in the close region around the adsorbate, where the scattered ion fractions are affected the most. Results are shown for H− in interaction with K/Ag(111).

Influence of single adsorbed atoms on charge exchange during ion-surface collisions

Partial and final projectile charge states are theoretically analyzed after ${\mathrm{Li}}^{+}$ ions frontally collide with a single-layer graphene surface with potassium atoms adsorbed on it, in the very low deposition limit where the adsorbed atoms negligibly interact with each other. We applied a model based on first principles that accounts for all the details of the surface and is used to describe the resonant charge exchange processes occurring in binary collisions between the projectile and the adsorbate, and between the projectile and the C atoms of the graphene surface located in the surroundings of the adsorption site. Completely different neutral fraction dependences with the outgoing velocity are found for the projectiles scattered by the adsorbate and by carbon atoms located far from the adsorbed atom. In addition, an important influence of the adsorbate is perceived in the neutralization of projectiles colliding with the first and second set of carbon atoms nearest to the adsorption site. For C atoms located at middle-range distances (\ensuremath{\sim}6.7 \AA{}), the final charge state of the projectile is not affected by the adsorbate presence, even when an effective interaction between the projectile and the K adsorbed atom is revealed via appreciable projectile level widths.

Critical implications of ion-surface energy accommodation and neutralization mechanism in hollow cathode physics

Self-heating thermionic hollow cathodes are essential components in modern plasma thrusters. To fully understand their operation, three interdependent physical domains must be considered: plasma discharge physics, thermal response of the cathode structure, and chemical evolution of plasma exposed surfaces. In this work, we develop the first self-consistently coupled plasma–thermal–chemical simulation platform for hollow cathode operation using lanthanum hexaboride (LaB6) and Xe and study its performance against our experimentally determined temperature measurements. Results show that the customary assumptions of single-step resonant neutralization and full energy accommodation in ion-surface collisions fail to reproduce our empirical observations. We propose a two-step neutralization mechanism that consists of resonant neutralization to the first excited state of xenon followed by Auger de-excitation to the ground state, along with system specific accommodation factors. In this way, the agreement between the results of the simulations and experiments was achieved. These fundamental processes could govern neutralization in other cathode technologies where low work function emitters are employed and should therefore be accounted for in physical models. In addition, the new simulation platform allows us to better estimate the equilibrium work function of LaB6 hollow cathode emitters. In the cathode studied here, we found that the effective work function is 2.25 eV, which is significantly lower than previous estimates, and leads to better than expected cathode material performance with important implications for space missions.

Interaction of Small Hydrocarbons with Fusion Relevant Beryllium Thin Films

Ion-surface collision studies are carried out with small deuterated hydrocarbon cations i.e. CDx + with x = 2-4 colliding with fusion relevant Beryllium (Be) thin films with ions incident energy as low as 0 eV and as high as Ein = 100 eV. Be films are coated on stainless steel surface by the technique of Thermionic Vacuum Arc (TVA); a novel thin film deposition method with primary as well distinguished characteristic of control of ion flux and respective dose towards the substrate. Prior to scattering, methane-d4 99 atom % D is ionized by electron impact and ions are mass and energy analyzed. Ionization and collisions are performed in ultra high vacuum conditions. In these kinds of collision experiments, we have recorded secondary ion mass spectra and plotted respective incident energy resolved abundances of secondary product ions. Relative abundances in percentage of total secondary ions are plotted and it is observed that such beryllium films can accumulate charged hydrocarbon layers as surface adsorbates. These self assembled layers play a primary role in surface-scattering of primary ions. Moreover, it is seen that bond dissociation energy in lighter hydrocarbons is higher than that for heavier species and shows primarily that the deuterium atoms are loosely bounded to carbon atoms in heavier hydrocarbons than in lighter ones.

Ion Imaging of Native Protein Complexes Using Orthogonal Time-of-Flight Mass Spectrometry and a Timepix Detector.

Native mass spectrometry (native MS) has emerged as a powerful technique to study the structure and stoichiometry of large protein complexes. Traditionally, native MS has been performed on modified time-of-flight (TOF) systems combined with detectors that do not provide information on the arrival coordinates of each ion at the detector. In this study, we describe the implementation of a Timepix (TPX) pixelated detector on a modified orthogonal TOF (O-TOF) mass spectrometer for the analysis and imaging of native protein complexes. In this unique experimental setup, we have used the impact positions of the ions at the detector to visualize the effects of various ion optical parameters on the flight path of ions. We also demonstrate the ability to unambiguously detect and image individual ion events, providing the first report of single-ion imaging of protein complexes in native MS. Furthermore, the simultaneous space- and time-sensitive nature of the TPX detector was critical in the identification of the origin of an unexpected TOF signal. A signal that could easily be mistaken as a fragment of the protein complex was explicitly identified as a secondary electron signal arising from ion-surface collisions inside the TOF housing. This work significantly extends the mass range previously detected with the TPX and exemplifies the value of simultaneous space- and time-resolved detection in the study of ion optical processes and ion trajectories in TOF mass spectrometers.

Ion Mobility and Surface Collisions: Submicrometer Capillaries Can Produce Native-like Protein Complexes.

The use of submicrometer capillaries for nanoelectrospray ionization of native proteins and protein complexes effectively reduces the number of nonspecific salt adducts to biological molecules, therefore increasing the apparent resolution of a mass spectrometer without any further instrument modifications or increased ion activation. However, the increased interaction between proteins and the surface of the capillary has been shown to promote protein expansion and therefore loss of native structure. Here, we compare the effect of micrometer and submicrometer sized capillaries on the native structures of the protein complexes streptavidin, concanavalin A, and C-reactive protein under charge reducing conditions. We observe that the use of submicrometer capillaries did not result in a significantly higher charge state distribution, indicative of expansion, when compared to micrometer sized capillaries for complexes in 100 mM ammonium acetate and 100 mM triethylammonium acetate and for streptavidin in 200 mM ammonium acetate with no charge reduction. Additionally, no significant differences in collision cross sections were observed using ion mobility mass spectrometry. Finally, the dissociation behaviors of protein complexes ionized using micrometer and submicrometer capillaries were compared to determine if any structural perturbation occurred during ionization. Protein complexes from both capillary sizes displayed similar surface-induced dissociation patterns at similar activation energies. The results suggest that submicrometer capillaries do not result in significant changes to protein complex structure under charge reducing conditions and may be used for native mass spectrometry experiments. Submicrometer capillaries can be used to resolve small mass differences of biological systems on a QTOF platform; however, a laser tip puller is required for pulling reproducible submicrometer capillaries, and disruption in spray due to clogging was observed for larger protein complexes.

Mimicking Polymer Surfaces Using Cyclohexyl- and Perfluorocyclohexyl-Terminated Self-Assembled Monolayers

This article describes the synthesis of two cyclohexyl-terminated alkanethiols (HCyHnSH; n = 10 and 11) and their fluorinated analogs C6F11(CH2)nSH (n = 10 and 11; FCyHnSH). These ring-terminated adsorbates were used to generate self-assembled monolayers (SAMs) on gold surfaces to serve as model polymeric interfaces on metal substrates. The corresponding SAMs were characterized using ellipsometry, X-ray photoelectron spectroscopy (XPS), polarization modulation infrared reflection–absorption spectroscopy (PM-IRRAS), and contact angle goniometry. While the ellipsometric thicknesses were consistent with monolayer formation, analysis by XPS indicated that the HCyHnSH SAMs exhibited greater packing densities than their fluorocarbon analogs. However, PM-IRRAS spectra revealed that the underlying methylene units in the HCyHnSH SAMs were less conformationally ordered than their fluorocarbon analogs. In all the characterizations, no discernible “odd–even” effect was observed in either the HCyHnSH or the FCyHnSH SAMs, plausibly due to the bulkiness and conformational flexibility of the chain termini. Interestingly, comparison of the contact angles of a wide range of contacting liquids on these SAMs and their polymeric analogs, polyethylene (PE) and polytetrafluoroethylene (PTFE), found that these liquids exhibited similar wettability on the HCyHnSH SAMs and PE surfaces, and separately on the FCyHnSH SAMs and PTFE surfaces. These results suggest that these SAMs can successfully act as mimics of nanoscale polymer films and can be used in future studies (e.g., ion-surface collisions and plasma modification) without concerns of surface reconstruction.

Experimental and theoretical investigation of overall energy deposition in surface-induced unfolding of protein ions.

Recent advances in native mass spectrometry have enabled its use to probe the structure of and interactions within biomolecular complexes. Surface-induced dissociation, in which inter- and intramolecular interactions are disrupted following an energetic ion-surface collision, is a method that can directly interrogate the topology of protein complexes. However, a quantitative relationship between the ion kinetic energy at the moment of surface collision and the internal energy deposited into the ion has not yet been established for proteins. The factors affecting energy deposition in surface-induced unfolding (SIU) of protein monomers were investigated and a calibration relating laboratory-frame kinetic energy to internal energy developed. Protein monomers were unfolded by SIU and by collision-induced unfolding (CIU). CIU and SIU cause proteins to undergo the same unfolding transitions at different values of laboratory-frame kinetic energy. There is a strong correlation between the SIU and CIU energies, demonstrating that SIU, like CIU, can largely be understood as a thermal process. The change in internal energy in CIU was modeled using a Monte Carlo approach and theory. Computed values of the overall efficiency were found to be approximately 25% and used to rescale the CIU energy axis and relate nominal SIU energies to internal energy. The energy deposition efficiency in SIU increases with mass and kinetic energy from a low of ∼20% to a high of ∼68%, indicating that the effective mass of the surface increases along with the mass of the ion. The effect of ion structure on energy deposition was probed using multiple stages of ion activation. Energy deposition in SIU strongly depends on structure, decreasing as the protein is elongated, due to decreased effective protein-surface collisional cross section and increased transfer to rotational modes.

Multiple scattering and inelastic energy loss in the case of ion–surface collisions

Multiple scattering at grazing angles of incidence is shown to affect the value of inelastic energy loss determined from the position of the quasi-single scattering peak on the energy scale.

Tuning Charge Transfer in Ion-Surface Collisions at Hyperthermal Energies.

Charge exchange in ion-surface collisions may be influenced by surface adsorbates to alter the charge state of the scattered projectiles. We show here that the positive-ion yield, observed during ion scattering on metal surfaces at low incident energies, is greatly enhanced by adsorbing electronegative species onto the surface. Specifically, when beams of N(+) and O(+) ions are scattered off of clean Au surfaces at hyperthermal energies, no positive ions are observed exiting. Partial adsorption of F atoms on the Au surface, however, leads to the appearance of positively charged primary ions scattering off of Au, a direct result of the increase in the Au work function. The inelastic energy losses for positive-ion exits are slightly larger than the corresponding ionization energies of the respective N and O atoms, which suggest that the detected positive ions are formed by surface reionization during the hard collision event.

Effect of basic residue on the kinetics of peptide fragmentation examined using surface-induced dissociation combined with resonant ejection

In this work, resonant ejection coupled with surface-induced dissociation (SID) in a Fourier transform ion cyclotron resonance mass spectrometer is used to examine fragmentation kinetics of two singly protonated hexapeptides, RYGGFL and KYGGFL, containing the basic arginine residue and less basic lysine residue at the N-terminus. The kinetics of individual reaction channels at different collision energies are probed by applying a short ejection pulse (1ms) in resonance with the cyclotron frequency of a selected fragment ion and varying the delay time between ion-surface collision and resonant ejection while keeping total reaction delay time constant. Rice-Ramsperger-Kassel-Marcus (RRKM) modeling of the experimental data provides accurate threshold energies and activation entropies of individual reaction channels. Substitution of arginine with less basic lysine has a pronounced effect on the observed fragmentation kinetics of several pathways, including the b2 ion formation, but has little or no effect on formation of the b5+H2O fragment ion. The combination of resonant ejection SID, time- and collision energy-resolved SID, and RRKM modeling of both types of experimental data provides a detailed mechanistic understanding of the primary dissociation pathways of complex gaseous ions.

Formation of HCN+ in heterogeneous surface reactions

SynopsisMass spectrometric studies of ion-surface collisions between low-energy (20-100 eV) ions of N+2, N+ [1] and NH+ and hydrocarbon-covered room-temperature and heated surfaces of tungsten, carbon-fiber-composite, and beryllium showed significant increase of the ion yield at m/z 27 that was not observed in analogous collisions of Ar+. This increase is ascribed to formation of HCN+ in heterogeneous reactions between the nitrogen-containing projectile ions and the surface hydrocarbons.

Importance of considering helium excited states inHe+scattering by an aluminum surface

The ${\mathrm{He}}^{+}/\mathrm{Al}$ system is a very interesting projectile-surface combination which was thought initially as an example of a pure Auger neutralization mechanism. Then, because of the measured reionization explained by the antibonding interaction of the projectile state with the core target states, the resonant charge exchange with the band states was considered as another important contribution to the neutralization. Nevertheless, by only considering the neutralization to the ground state of helium, the measured ion survival probability is still overestimated. On the other hand, measurements of electron emission from an Al surface bombarded by He positive ions suggested the possibility of occupied excited states of helium due to the ion-surface collision. In this work, we also include the excited states of He within the time-dependent scattering process in which both neutralization mechanisms, resonant and Auger, are simultaneously contemplated. Our starting point is a multiorbital Anderson Hamiltonian projected over the selected space of ground and excited atomic configurations. An extra term related to the Auger mechanism is added to this Hamiltonian. A difference with previous works is that this approach includes the electron spin and, therefore, the spin fluctuation statistics in the charge-exchange process is correctly taken into account. We find a notable improvement in the agreement with the experiments and also that the interference between both mechanisms is not dramatic.

Chemical modification of graphene via hyperthermal molecular reaction.

Chemical functionalization of graphene is achieved by hyperthermal reaction with azopyridine molecular ions. The one-step, room temperature process takes place in high vacuum (10(-7) mbar) using an electrospray ion beam deposition (ES-IBD) setup. For ion surface collisions exceeding a threshold kinetic energy of 165 eV, molecular cation beams of 4,4'-azobis(pyridine) covalently attach to chemical vapor deposited (CVD) graphene. A covalent functionalization degree of 3% of the carbon atoms of graphene is reached after 3-5 h of ion exposure of 2 × 10(14) azopyridinium/cm(2) of which 50% bind covalently. This facile approach for the controlled modification of graphene extends the scope of candidate species that would not otherwise react via existing conventional methods.

Active conformation control of unfolded proteins by hyperthermal collision with a metal surface.

The physical and chemical properties of macromolecules like proteins are strongly dependent on their conformation. The degrees of freedom of their chemical bonds generate a huge conformational space, of which, however, only a small fraction is accessible in thermal equilibrium. Here we show that soft-landing electrospray ion beam deposition (ES-IBD) of unfolded proteins allows to control their conformation. The dynamics and result of the deposition process can be actively steered by selecting the molecular ion beam's charge state or tuning the incident energy. Using these parameters, protein conformations ranging from fully extended to completely compact can be prepared selectively on a surface, as evidenced on the subnanometer/amino acid resolution level by scanning tunneling microscopy (STM). Supported by molecular dynamics (MD) simulations, our results demonstrate that the final conformation on the surface is reached through a mechanical deformation during the hyperthermal ion surface collision. Our experimental results independently confirm the findings of ion mobility spectrometry (IMS) studies of protein gas phase conformations. Moreover, we establish a new route for the processing of macromolecular materials, with the potential to reach conformations that would be inaccessible otherwise.

New approach for studying slow fragmentation kinetics in FT-ICR: Surface-induced dissociation combined with resonant ejection

We introduce a new approach for studying the kinetics of large ion fragmentation in the gas phase by coupling surface-induced dissociation (SID) in a Fourier transform ion cyclotron resonance mass spectrometer with resonant ejection of selected fragment ions using a relatively short (5ms) ejection pulse. The approach is demonstrated for singly protonated angiotensin III ions excited by collisions with a self-assembled monolayer of alkylthiol on gold (HSAM). The overall decomposition rate and rate constants of individual reaction channels are controlled by varying the kinetic energy of the precursor ion in a range of 65–95eV. The kinetics of peptide fragmentation are probed by varying the delay time between ion activation by collision and short (5ms) resonant ejection of selected fragment ions at a constant total reaction time of 150s. RRKM modeling indicates that the shape of the kinetics plots is strongly affected by the shape and position of the energy deposition function (EDF) describing the internal energy distribution of the ion following ion-surface collision. Modeling of the kinetics data provides detailed information on the shape of the EDF and energy and entropy effects of individual reaction channels.

Ion–surface collisions in mass spectrometry: Where analytical chemistry meets surface science

This article presents a personal perspective regarding the development of key concepts in understanding hyperthermal collisions of polyatomic ions with surfaces as a unique tool for mass spectrometry applications. In particular, this article provides a historic overview of studies focused on understanding the phenomena underlying surface-induced dissociation (SID) and mass-selected deposition of complex ions on surfaces. Fast energy transfer in ion–surface collisions makes SID especially advantageous for structural characterization of large complex molecules, such as peptides, proteins, and protein complexes. Soft, dissociative, and reactive landing of mass-selected ions provide the basis for preparatory mass spectrometry. These techniques enable precisely controlled deposition of ions on surfaces for a variety of applications. This perspective article shows how basic concepts developed in the 1920s and 1970s have evolved to advance promising mass-spectrometry-based applications.

Dynamics of ion–molecule reactions from beam experiments: A historical survey

A historical survey of beam scattering studies of ion–molecule reactions from the sixties up to the present time is presented. The centers of research that developed key instrumentation for these studies and early achievements in characterizing basic collisional mechanisms in scattering experiments are reviewed. Important classes of cation–molecule reaction dynamics, impulsive atom-transfer, reaction complexes, electron transfer (charge transfer) dynamics and the dynamics of negative ion–molecule reactions are described. Selected specific examples of ion–molecule reaction dynamics, including multiply-charged and ion-surface collisions, are briefly presented.

Energetics and dynamics of dissociation of deprotonated peptides: Fragmentation of angiotensin analogs

We present a first study of the energetics and dynamics of dissociation of deprotonated peptides using time- and collision-energy resolved surface-induced dissociation (SID) experiments. SID of four model peptides (RVYIHPF, HVYIHPF, DRVYIHPF, and DHVYIHPF) was studied using a specially designed Fourier transform ion cyclotron resonance mass spectrometer (FT-ICR MS) configured for studying ion-surface collisions. Energy and entropy effects for the overall decomposition of the precursor ion were deduced by modeling the time- and collision energy-resolved survival curves using an RRKM based approach developed in our laboratory. The results were compared to the energetics and dynamics of dissociation of the corresponding protonated species. We demonstrate that acidic peptides are less stable in the negative mode because of the low threshold associated with the kinetically hindered loss of H 2O from [M−H] − ions. Comparison between the two basic peptides indicates that the lower stability of the [M−H] − ion of RVYIHPF as compared to HVYIHPF towards fragmentation is attributed to the differences in fragmentation mechanisms. Specifically, threshold energy associated with losses of NH 3 and NHCNH from RVYIHPF is lower than the barrier for backbone fragmentation that dominates gas-phase decomposition of HVYIHPF. The results provide a first quantitative comparison between the energetics and dynamics of dissociation of [M+H] + and [M−H] − ions of acidic and basic peptides.

Nano hillock and complex crater formation by low-energy proton implantation with incident angle into lithium niobate single crystal

The formation of nano-size hillocks and simple and complex craters was observed as a result of ion–surface collisions with a lithium niobate single crystal on proton implantation. The low-energy ion implantation process is considered as a controllable and versatile tool for surface and near-surface modifications down to an atomic scale as an alternative to the swift heavy ion irradiation effect. Lithium niobate samples implanted by proton ions with a low energy of 120 keV at various fluences (1015 and 1016 protons/cm2) were studied using atomic force microscopy (AFM). The images of surface modification appear as simple and complex crater formation in the case of incident ions at normal to the surface. Varying the angle of incidence to θ=30° with respect to the normal to the surface, hillocks and multi-hillocks were observed. The complex craters with central uplifted, cone-shaped hillocks with a height of up to 4.3 nm are surrounded by low-height (1 nm) rims. The hillock height varies from a few nanometers to 16 nm with the basal diameter from 200 to 340 nm depending on the ion implantation conditions. The complex crater and hillock formation on the lithium niobate sample surface at the collision spot with the impact of incident angle is discussed.