Relativistic contributions to single and double core electron ionization energies of noble gases

We have performed relativistic calculations of single and double core 1s hole states of the noble gas atoms in order to explore the relativistic corrections and their additivity to the ionization potentials. Our study unravels the interplay of progression of relaxation, dominating in the single and double ionization potentials of the light elements, versus relativistic one-electron effects and quantum electrodynamic effects, which dominate toward the heavy end. The degree of direct relative additivity of the relativistic corrections for the single electron ionization potentials to the double electron ionization potentials is found to gradually improve toward the heavy elements. The Dirac-Coulomb Hamiltonian is found to predict a scaling ratio of ～4 for the relaxation induced relativistic energies between double and single ionization. Z-scaling of the computed quantities were obtained by fitting to power law. The effects of nuclear size and form were also investigated and found to be small. The results indicate that accurate predictions of double core hole ionization potentials can now be made for elements across the full periodic table.     

Photofragmentation study of hexamethyldisiloxane following core ionization and direct double ionization

X-ray photoelectron spectroscopy and Auger spectroscopy studies of gas-phase hexamethyldisiloxane (HMDSO) are presented. The photodissociation of this molecule is studied using various experimental coincidence techniques. We compare the fragmentation pathways observed after core ionization followed by Auger decay and after valence double photoionization of the molecule. A strongly selective production of the doubly charged tetramethyldisiloxane ion is observed in the low binding-energy regions. Theoretical calculations are carried out to tentatively explain the stability of the produced dication.     

The Auger electron spectrum of water vapour

The Auger electron spectrum of water vapour has been recorded and analyzed. For the analysis, an approximate formula for calculating the intensities of the Auger electron lines is derived. It is shown, that the calculated intensities along with theoretical energies of the Auger transitions account well for the observed spectrum. In particular, new assignments in terms of transitions to triplet final states are suggested.     

Inner-shell single and double ionization potentials of aminophenol isomers

A comprehensive study of single and double core ionization potentials of the aminophenol molecule is reported. The role of relaxation, correlation, relativistic, and basis set effects in these potentials is clarified. Special attention is paid to the isomer dependence of the single and double core ionization potentials. Some of them are also compared with the respective values of the phenol and aniline molecules. It is shown that the core level single ionization potentials of the para-, meta-, and ortho-aminophenol molecules differ only slightly from each other, rendering these structural isomers challenging to distinguish for conventional x-ray photoelectron spectroscopy. In contrast, the energy needed to remove two core electrons from different atoms depends noticeably on the mutual arrangement and even on the relative orientations of the hydroxyl and amine groups. Together with the electrostatic repulsion between the two core holes, relaxation effects accompanying double core ionization play a crucial role here. The pronounced sensitivity of the double ionization potentials, therefore, enables a spectroscopic characterization of the electronic structure of aminophenol isomers by means of x-ray two-photon photoelectron spectroscopy.     

Ionization and double ionization of small water clusters

The valence ionization and double ionization spectra of the water molecule, of the water dimer, and the cyclic water clusters (H2O)3 and (H2O)4 are calculated by ab initio Green's function methods and discussed in some detail. Particular attention is paid to the analysis of the development of the spectra with increasing cluster size. Electronic decay following inner valence ionization is addressed and a crude estimate for the kinetic energy spectrum of the secondary electrons is given for the clusters.     

高岭石与水分子相互作用的理论研究

为从微观角度深入探讨单个水分子与高岭石最易解理晶面不同暴露末端的作用特点,本工作通过密度泛函理论的计算方法对不同吸附形态的水分子与不同暴露末端的稳定作用构型进行几何结构与电子结构分析.吸附能的计算结果表明水分子在铝氧八面体羟基作为暴露末端的表面上最稳定的吸附方式为水分子的氧原子和氢原子分别与相邻两个羟基的氢原子和氧原子...     

High throughput production of single core double emulsions in a parallelized microfluidic device

Double emulsions are useful templates for microcapsules and complex particles, but no method yet exists for making double emulsions with both high uniformity and high throughput. We present a parallel numbering-up design for microfluidic double emulsion devices, which combines the excellent control of microfluidics with throughput suitable for mass production. We demonstrate the design with devices incorporating up to 15 dropmaker units in a two-dimensional or three-dimensional array, producing single-core double emulsion drops at rates over 1 kg day(-1) and with diameter variation less than 6%. This design provides a route to integrating hundreds of dropmakers or more in a single chip, facilitating industrial-scale production rates of many tons per year.     

Biocompatible microcapsules with a water core templated from single emulsions

We use single emulsions as templates to fabricate monodisperse biocompatible microcapsules with a water core. These microcapsules are fabricated using FDA-approved polymer and non-toxic solvents and are of great use in drugs, cosmetics and foods.     

Calculated Auger emission spectrum of ammonia

Doubly ionized states of ammonia are calculated with Roothaan's symmetry-restricted open-shell SCF method. A GTO basis of double-ζ quality is used. Calculated energies compare well with previous calculations for the lowest doubly ionized states. Auger emission intensities are estimated using an analogy with the experimental Auger spectrum of neon.     

Evolution of the vibrational spectrum of ammonia from single molecule to bulk

Ammonia clusters (NH3)n (n=2-10(4)) have been assembled inside helium droplets and studied via infrared laser spectroscopy. The studied spectral range of 3100-3500 cm(-1) covers the nu1 and nu3 fundamental stretching bands as well as the 2nu4 overtone of the bend of ammonia molecules. The results show strong coupling of the 2nu4 overtone with the fundamental vibrations for all cluster sizes except dimers. The intensity of the nu3 band relative to the total intensity in the spectrum increases from about 30% to about 80% upon increase of the average cluster size from n=5 to n=10(4). We attributed this effect to the concomitant decrease in the fraction of the surface molecules. The results indicate that ammonia clusters obtained in He droplets have a compact structure and that inner molecules in the clusters have similar hydrogen-bonded coordination as in the crystalline form of ammonia. This surprising result is ascribed to a directionality of the hydrogen bond, which guides the low temperature growth of the cluster in He droplets.     

Auger decay of molecular double core-hole state

We report on theoretical Auger electron kinetic energy distribution originated from sequential two-step Auger decays of molecular double core-hole (DCH) state, using CH(4), NH(3), and H(2)CO molecules as representative examples. For CH(4) and NH(3) molecules, the DCH state has an empty 1s inner-shell orbital and its Auger spectrum has two well-separated components. One is originated from the 1st Auger transition from the DCH state to the triply ionized states with one core hole and two valence holes (CVV states) and the other is originated from the 2nd Auger transition from the CVV states to quadruply valence ionized (VVVV) states. Our result on the NH(3) Auger spectrum is consistent with the experimental spectrum of the DCH Auger decay observed recently [J. H. D. Eland, M. Tashiro, P. Linusson, M. Ehara, K. Ueda, and R. Feifel, Phys. Rev. Lett. 105, 213005 (2010)]. In contrast to CH(4) and NH(3) molecules, H(2)CO has four different DCH states with C1s(-2), O1s(-2), and C1s(-1)O1s(-1) (singlet and triplet) configurations, and its Auger spectrum has more complicated structure compared to the Auger spectra of CH(4) and NH(3) molecules. In the H(2)CO Auger spectra, the C1s(-1)O1s(-1) DCH → CVV Auger spectrum and the CVV → VVVV Auger spectrum overlap each other, which suggests that isolation of these Auger components may be difficult in experiment. The C1s(-2) and O1s(-2) DCH → CVV Auger components are separated from the other components in the H(2)CO Auger spectra and can be observed in experiment. Two-dimensional Auger spectrum, representing a probability of finding two Auger electrons at specific pair of energies, may be obtained by four-electron coincidence detection technique in experiment. Our calculation shows that this two-dimensional spectrum is useful in understanding contributions of CVV and VVVV states to the Auger decay of molecular DCH states.     

Modifications of DCDHF single molecule fluorophores to impart water solubility

A series of dicyanomethylenedihydrofuran (DCDHF) fluorophores with different hydrophilic groups were synthesized and their photophysical properties and water solubilities were measured. Significant water solubility was achieved without compromising desirable photophysical properties, permitting applications of these fluorophores in biological systems.     

单笼形水分子簇中心水分子对类型关系

随机产生单笼形水分子簇(H2O)n(n=8~36),经分类统计后发现,在笼形水分子簇中,其1221,1212,2121和2112四类氢键的个数与水分子和氢键总数之间有定量关系,且1212类氢键的个数与2121类的氢键始终相等.如果笼形水分子簇中某一类氢键数已知,则它的其余三类氢键的个数也随即确定.     

Interplay between Auger and ionization processes in nanocrystal quantum dots

We study the interplay between Auger effects and ionization processes in the limit of strong electronic confinement in core/shell CdSe/ZnS semiconductor nanocrystal quantum dots. Spectrally resolved fluorescence decay measurements reveal a monotonic increase of the photoluminescence decay rate on excitation density. Our results suggest that Auger recombination accelerates ionization processes that lead to the occupation of dark, nonemissive nanocrystal states. A model is proposed in the quantized Auger regime describing these experimental observations and providing an estimate of the Auger assisted ionization rates.     

Photoelectron circular dichroism in core level ionization of randomly oriented pure enantiomers of the chiral molecule camphor

The inner-shell photoionization of unoriented camphor molecules by circularly polarized light has been investigated from threshold to a photoelectron kinetic energy of approximately 65 eV. Photoelectron spectra of the carbonyl C 1s orbital, recorded at the magic angle of 54.7 degrees with respect to the light propagation direction, show an asymmetry of up to 6% on change of either the photon helicity or molecular enantiomer. These observations reveal a circular dichroism in the angle resolved emission with an asymmetry between forward and backward scattering (i.e., 0 degrees and 180 degrees to the light beam) which can exceed 12%. Since the initial state is an atomiclike spherically symmetric orbital, this strongly suggests that the asymmetry is caused by final-state effects dependent on the chiral geometry of the molecule. These findings are confirmed by electron multiple scattering calculations of the photoionization dynamics in the electric-dipole approximation.     

Imaging of tautomerism in a single molecule

Fluorescence imaging is used to visualize directly the transfer of two inner hydrogen atoms in single porphycene molecules. This reaction leads to a chemically equivalent but differently oriented structure and hence results in a rotation of the transition dipole moments. By probing single immobilized molecules with an azimuthally polarized laser beam in the focal spot of a confocal microscope we observe ring-like emission patterns, possible only for a chromophore with two nearly orthogonal transition dipole moments. Numerical simulations of the observed emission patterns yield a value of 72 degrees for the angle between the S0-S1 transition moments in the two tautomeric forms.