Using a superconducting tunnel junction detector to measure the secondary electron emission efficiency for a microchannel plate detector bombarded by large molecular ions

An energy-sensitive superconducting tunnel junction (STJ) detector was used to measure the secondary electron emission efficiency, epsilon(e), for a microchannel plate (MCP) detector bombarded by large (up to 66 kDa), slow moving (<40 km/s) molecular ions. The method used is new and provides a more direct procedure for measuring the efficiency of secondary electron emission from a surface. Both detectors were exposed simultaneously to nearly identical ion fluxes. By exposing only a small area of the MCP detector to ions, such that the area exposed was effectively the same as the size of the STJ detector, the number of ions detected with each detector were directly comparable. The STJ detector is 100% efficient for detecting ions in the energy regime investigated and therefore it can be used to measure the detection efficiency and secondary electron emission efficiency of the MCP. The results are consistent with measurements made by other groups and provide further characterization of the loss in sensitivity noted previously when MCP detectors have been used to detect high-mass ions. Individual molecular ions of mass 66 kDa with 30 keV kinetic energy were measured to have about a 5% probability of producing one or more electrons when impacting the MCP. When ion energy was reduced to 10 keV, the detection probability decreased to 1 %. The secondary electron yield was calculated from the secondary electron emission efficiency and found to scale linearly with the mass of the impinging molecular ion and to about the fourth power of ion velocity. Secondary electrons were observed for primary ion impacts >5 km/s, regardless of mass, and no evidence of a velocity (detection) threshold was observed. Copyright 2000 John Wiley & Sons, Ltd.     

Solvent reorganization in electron and ion transfer reactions near a smooth electrified surface: a molecular dynamics study

Molecular dynamics simulations of electron and ion transfer reactions near a smooth surface are presented, analyzing the effect of the geometrical constraint of the surface and the interfacial electric field on the relevant solvation properties of both a monovalent negative ion and a neutral atom. The simulations show that, from the solvation point of view, ion adsorption is an uphill process due to the need to shed off the ion's solvation shell and displace water from the surface. Atom adsorption, on the other hand, has only a small barrier, related to the molecularity of the solvent. Both the electrostatic interaction of the ion with the solvent and the ion's solvent reorganization energy (the relevant parameter in the Marcus electron transfer theory) decrease as the surface is approached, whereas these parameters are not sensitive to the distance from the surface for the atom. This is a consequence of the importance of long-range electrostatic interactions for ion solvation and the importance of short-range interactions for atom solvation. The electric field either attracts or repels an ion to or from the surface, but the field has no influence on the solvent reorganization energy. By including the quantum-mechanical electron transfer between the metal surface and the ion/atom in solution in the MD simulation by using a model Hamiltonian, we calculated two-dimensional free energy surfaces for ion adsorption allowing for partial charge transfer, based on a fully molecular picture of ion solvation near the surface.     

Diamond surface conductivity under atmospheric conditions: theoretical approach

The electron transfer from an H-terminated diamond (100)-2 x 1 surface to a neutral or acidic water adlayer has been theoretically investigated, using quantum mechanical DFT calculations under periodic boundary conditions. A surface conductivity of p-type was found to be induced by the acidic environment. An electron transfer of 1.8 electrons per surface unit cell was observed to take place from the upper part of the diamond valence band to the lowest unoccupied molecular level of the aqueous adlayer that contains one H(3)O(+) ion. The result is a hole delocalized over the whole diamond model slab. Also, a pronounced weakening of the H(3)O(+) bonds by the interaction with the diamond surface is observed.     

电极金属和电解质溶液界面势垒研究

本文根据肖特基效应和弗兰克-康东原理得到了近似理想极化电极体系赫姆荷尔茨双电层内势垒高度和宽度与电极电荷密度间的关系式。并用Hg-HCl电极电荷密度的文献值作了具体计算。计算表明,电极电势对电子转移势垒形状的影响是很大的。     

Doppler-broadened line shapes of atomic hydrogen in a parallel-plate radio frequency discharge

Doppler-shifted atomic hydrogen emission (Balmer ) is observed from a low-frequency rf discharge through molecular hydrogen by collecting the light through a hole in one of the electrodes. Doppler shifts as large as 0.7 nm, corresponding to an energy of 540 eV or 85% of the peak applied voltage, are observed when ions are accelerated by the sheath electric field. The mechanisms for hot atom production are discussed in terms of both gas-phase and surface ion-impact phenomena. Hot atoms are produced via gas-phase ion-atom and ion-molecule collisions, as a result of simultaneous neutralization and reflection of ions at the electrode surface, and/or by sputtering of adsorbed hydrogen. As much as 30% of the atomic hydrogen emission is substantially Doppler shifted, indicating that most of the atomic emission in the sheaths is actually produced by ion impact and not by electron impact.     

Role of Nanocavity Plasmons in Tunneling Electron Induced Light Emission on and near a Molecule

By using a microscopic quantum model, we study theoretically different roles of nanocavity plasmons in scanning tunneling microscope (STM) induced light emission upon selective initial excitation of molecules or plasmons. The time evolution and spectroscopic properties of the emission from the coupled plasmon-molecule system in each case are studied using time-dependent quantum mater equations. When the STM tip is placed on the molecule to ensure direct carrier injection induced molecular excitation, the major role of the plasmons is to enhance the molecular emission via increasing its radiative decay rate, resulting in sharp molecule-specific emission peaks. On the other hand, when the STM tip is located in close proximity to the edge of the molecule but without direct carrier injection into the molecule, the role of the plasmon-molecule coupling is to cause destructive interferences between the two quantum objects, leading to the occurrence of Fano dips around the energy of the molecular exciton in the plasmonic emission spectra.     

Visualization and interpretation of attosecond electron dynamics in laser-driven hydrogen molecular ion using Bohmian trajectories

We analyze the attosecond electron dynamics in hydrogen molecular ion driven by an external intense laser field using the Bohmian trajectories. To this end, we employ a one-dimensional model of the molecular ion in which the motion of the protons is frozen. The Bohmian trajectories clearly visualize the electron transfer between the two protons in the field and, in particular, confirm the recently predicted attosecond transient localization of the electron at one of the protons and the related multiple bunches of the ionization current within a half cycle of the laser field. Further analysis based on the quantum trajectories shows that the electron dynamics in the molecular ion can be understood via the phase difference accumulated between the Coulomb wells at the two protons.     

Water-based route to colloidal Mn-doped ZnSe and core/shell ZnSe/ZnS quantum dots

Relatively monodisperse and highly luminescent Mn(2+)-doped zinc blende ZnSe nanocrystals were synthesized in aqueous solution at 100 °C using the nucleation-doping strategy. The effects of the experimental conditions and of the ligand on the synthesis of nanocrystals were investigated systematically. It was found that there were significant effects of molar ratio of precursors and heating time on the optical properties of ZnSe:Mn nanocrystals. Using 3-mercaptopropionic acid as capping ligand afforded 3.1 nm wide ZnSe:Mn quantum dots (QDs) with very low surface defect density and which exhibited the Mn(2+)-related orange luminescence. The post-preparative introduction of a ZnS shell at the surface of the Mn(2+)-doped ZnSe QDs improved their photoluminescence properties, resulting in stronger emission. A 2.5-fold increase in photoluminescence quantum yield (from 3.5 to 9%) and of Mn(2+) ion emission lifetime (from 0.62 to 1.39 ms) have been observed after surface passivation. The size and the structure of these QDs were also corroborated by using transmission electron microscopy, energy dispersive spectroscopy, and X-ray powder diffraction.     

Assisted desolvation as a key kinetic step for crystal growth

The crystallization of materials from a supersaturated solution is a fundamental chemical process. Although several very successful models that provide a qualitative understanding of the crystal growth process exist, in most cases the atomistic detail of crystal growth is not fully understood. In this work, molecular dynamics simulations of the morphologically most important surfaces of barite in contact with a supersaturated solution have been performed. The simulations show that an ordered and tightly bound layer of water molecules is present on the crystal surface. The approach of an ion to the surface requires desolvation of both the surface and the ion itself leading to an activated process that is rate limiting for two-dimensional nucleation to occur. However, desolvation on specific surfaces can be assisted by anions adsorbed on the crystal surface. This hypothesis, corroborated by crystallization and scanning electron microscopy studies, allows the rationalization of the morphology of barite crystals grown at different supersaturations.     

Vibrationally promoted electron emission from low work-function metal surfaces

We observe electron emission when vibrationally excited NO molecules with vibrational state v, in the range of 9 < or = v < or =18, are scattered from a Cs-dosed Au surface. The quantum efficiency increases strongly with v, increasing up to 10(-2) electrons per NO (v) collision, a value several orders of magnitude larger than that observed in experiments with similar molecules in the ground vibrational state. The electron emission signal, as a function of v, has a threshold where the vibrational excitation energy slightly exceeds the surface work function. This threshold behavior strongly suggests that we are observing the direct conversion of NO vibrational energy into electron kinetic energy. Several potential mechanisms for the observed electron emission are explored, including (1) vibrational autodetachment, (2) an Auger-type two-electron process, and (3) vibrationally promoted dissociation. The results of this work provide direct evidence for nonadiabatic energy-transfer events associated with large amplitude vibrational motion at metal surfaces.     

Is there a quantum definition of a molecule?

The paper surveys how chemistry has developed over the past two centuries starting from Lavoisier’s classification of the chemical elements at the end of the eighteenth century; the subsequent development of the atomic–molecular model of matter preoccupied chemists throughout the nineteenth century, while the results of the application of quantum theory to the molecular model has been the story of this century. Whereas physical chemistry originated in the nineteenth century with the measurement of the physical properties of groups of chemical compounds that chemists identified as families, the goal of chemical physics is the explanation of the facts of chemistry in terms of the principles and theories of physics. Chemical physics as such was only possible after the discovery of the quantum theory in the 1920’s. By then the first of the sub‐atomic particles had been discovered and seemingly it is no longer possible to discuss chemical facts purely in terms of atoms and molecules – one has to recognize the electron and the nucleus, the parts of atoms. The combination of classical molecular structure with the quantum properties of the electron has given us a tremendously successful account of chemistry called ‘quantum chemistry’. Yet from the perspective of the quantum theory the deepest part of chemistry, the existence of chemical isomers and the very idea of molecular structure that rationalizes it, remains a central problem for chemical physics. This revised version was published online in July 2006 with corrections to the Cover Date.     

Influences of Acid on Molecular Forms of Fluorescein and Photoinduced Electron Transfer in Fluorescein‐Dispersing Sol–Gel Titania Films

Fluorescein‐dispersing titania gel films were prepared by the acid‐catalyzed sol–gel reaction using a titanium alkoxide solution containing fluorescein. The molecular forms of fluorescein in the films, depending on its acid–base equilibria, and the complex formation and photoinduced electron transfer process between the dye and titania surface were investigated by fluorescence and photoelectric measurements. The titanium species were coordinated to the carboxylate and phenolate‐like groups of the fluorescein species. The quantum efficiencies of the fluorescence quenching and photoelectric conversion were higher upon excitation of the dianion species interacting with the titania, i.e. the dye–titania complex. This result indicated that the dianion form was the most favorable for formation of the dye–titania complex exhibiting the highest electron transfer efficiency. Using nitric acid as the catalyst, the titania surface bonded to the fluorescein instead of the adsorbed nitrate ion during the steam treatment. The dye–titania complex formation played an important role in the electron injection from the dye to the titania conduction band.     

Secondary Electron Emission from an Organic Layer with a Surface Charge

Using secondary electron emission (SEE) techniques, conditions for the traveling of electrons near a charged surface were studied. A simple analytical expression was found to relate the effective coefficient of secondary electron emission from the charged surface of an organic liquid layer with the primary-electron current. At low currents, the relationship is close to a root law, the pattern of the dependence does not change with the varying conductivity of the liquid, its thickness, and the charge spot area. This finding suggests that the effective secondary electron emission coefficient and, hence, the conditions of electron motion near a surface charge depend on the only parameter, the current density of incident electrons. According to the estimates of the dielectric permittivity of a liquid, its resistivity, and ion mobility, the effective SEE coefficient at low charging currents is formed in the ohmic mode of current flow through the liquid.     

Surface induced ionization of neutral water clusters

The paper presents the results of study of a new phenomenon — the formation of cluster ions of both signs in the scattering of neutral water clusters by solid surfaces and the appearance of a current to the target. The experiments were carried out by the nozzle molecular beam technique. The probabilities of the charge removal from the surface were measured in dependence on incident angle, cluster size, and target material. The model of the process has been proposed which incorporates 1) formation of an ion pair during ion dissociation of a vibrationally excited molecule in a water cluster colliding with the surface; 2) asymmetric neutralization of an ion pair by surface; 3) inertial removal of a cluster ion from the surface. However the measured angular and energy distribution of emitted charged particles testify to more complex mechanisms of ionization and scattering because the spatial pattern of ion emission is of rainbow character and in some cases the direction of inertial removal (along the tangential component of initial velocity) does not dominate.     

Spectral,spatial and temporal characterization of a millisecond pulsed glow discharge: copper analyte emission and ionization

Two-dimensional maps of the spatial distributions of excited and ionized sputtered copper atoms are presented for a millisecond pulsed argon glow discharge. These maps demonstrate the temporal as well as spatial dependence of different excitation and ionization processes over the pulse cycle. Transitions from the low energy electronic states for the atom, characterized by emission such as that at 324.75 nm (3.82→0.00 eV), dominate the plateau time regime at a distance of 2.5 mm from the cathode surface. These processes originate from the electron excitation of ground state copper atoms. Transitions from high-energy electronic states, such as that characterized by emission at 368.74 nm (7.16→3.82 eV), predominate during the afterpeak time regime at a distance of 5.0–6.0 mm from the cathode surface. This observation is consistent with the relaxation of highly excited copper atoms produced by electron recombination with copper ions during the afterpeak time regime. Analyses of afterpeak and plateau intensities for a series of copper emission lines indicate an electron excitation temperature equivalent to 5.78 eV at 0.8 torr and 1.5 W. Temporal profiles exhibit copper ion emission only during the plateau time regime.     

Propagator theory of quantum-wire transmission

In the tight-binding formalism, the Green function (GF) is cast in the site representation, and can be interpreted as a propagator of information from one site to another. A general propagator theory is developed that encompasses the present GF treatments of electron transport in molecular wires and the scanning tunnelling and ballistic electron emission microscopes. Finally, the question of a multi-contact quantum circuit is addressed.     

Designed Long‐Lived Emission from CdSe Quantum Dots through Reversible Electronic Energy Transfer with a Surface‐Bound Chromophore

The size‐tunable emission of luminescent quantum dots (QDs) makes them highly interesting for applications that range from bioimaging to optoelectronics. For the same applications, engineering their luminescence lifetime, in particular, making it longer, would be as important; however, no rational approach to reach this goal is available to date. We describe a strategy to prolong the emission lifetime of QDs through electronic energy shuttling to the triplet excited state of a surface‐bound molecular chromophore. To implement this idea, we made CdSe QDs of different sizes and carried out self‐assembly with a pyrene derivative. We observed that the conjugates exhibit delayed luminescence, with emission decays that are prolonged by more than 3 orders of magnitude (lifetimes up to 330 μs) compared to the parent CdSe QDs. The mechanism invokes unprecedented reversible quantum dot to organic chromophore electronic energy transfer.     

Atomic and molecular quantum mechanics by the path integral molecular dynamics method

The quantum path integral molecular dynamics method was applied to studies of excess electron localization by a Na⁺ ion and by a NaCl molecule. Spatial and energetic characterization of the ground state of the excess electron compare favorably with results of model potential calculations for Na and with SCF Cl calculations for NaCl⁻.