A leed analysis of the (2×1)H-Ni(110) structure

A monolayer of H atoms adsorbed on Ni(110) below 180 K forms a (2×1) structure. The unit cell exhibits a glide symmetry plane and contains two adsorbed atoms. Based on a quantitative comparison between experimental and calculated LEED I/V spectra using standard R-factors the following structure was derived: On the clean Ni(110) surface the separation between the first two atomic layers, d12, is contracted by 8.5%±1.5% with respect to the bulk value; those between the second and third and the third and fourth layer, d23 and d34, are expanded by 3.5%±1.5% and 1%±1.5%, respectively—in agreement with recent other results. In the presence of the H adlayer the contraction of d12 is reduced to 4.5%±1.5%, while the expansion of d23 is not affected within the limits of accuracy. The third interlayer spacing d34 returns to its bulk value. The H atoms occupy threefold-coordinated sites formed by two Ni atoms from the first layer and one Ni atom from the second layer which confirms previous more qualitative conclusions based on He diffraction and vibrational spectroscopy. The bond lengths between H and its neighbouring Ni atoms were determined to be equal, namely 1.72±0.1 Å

Spectroscopic studies of jet-cooled AINi

Journal ArticleResonant two-photon ionization spectroscopy has been used to interrogate diatomic AlNi produced by laser vaporization of a 1:l alloy target in a supersonic molecular beam of helium. Although a large density of states in this molecule prohibits a concise elucidation of its electronic structure, the presence of discrete transitions has allowed several bands to be rotationally resolved. From the analysis of these bands the ground state has been determined as X 2?5/2, originating from the 3SA3&Nio2 configuration, and the bond length has been measured as 2.3211?0.0007 A. The dissociation energy and ionization potential of AlNi have also been determined as D0( AlNi) =2.29?0.05 eV and I.P. ( AlNi) =6.95?0.09 eV, respectively

Interaction of an aluminum atom with an alkaline earth atom: spectroscopic and ab initio investigations of AICa

Journal ArticleA spectroscopic analysis of diatomic AlCa generated by laser vaporization of a 2:1 AI:Ca metal alloy followed by supersonic expansion has been completed using resonant two-photon ionization spectroscopy. Four excited electronic states have been identified and investigated in the energy region from 13 500 to 17 900 cm-1. These are the [13.5] ?II,, the [15.8] ??, the [17.0] ??3/2(?), and the [ 17.61 2?3/2 states. From rotational analysis excited state bond lengths have been measured for three of the four excited states, and the ground state has been unambiguously determined as a ?II, state with a weighted least squares value of the ground state bond length of r"0 = 3.1479 ? 0.00 10 A. The ionization energy of the molecule has also been directly determined as 5.072?0.028 eV. Ab inirio calculations for the potential energy curves of seven low-lying states of AlCa [X ?IIr, ??+, 4?-, 4IIr, ?II,(2), ??, and X l?+ and for the X 1?+ ground electronic state of AlCa+ have been carried out. In agreement with experiment, ?II, is calculated to be the ground electronic state of the neutral molecule. The dissociation energies of AlCa (X ?II,) into Al(3s?3p?,?Po) +Ca(4s?,?S) and for AlCa+ (X ??+) into A1+(3s?,?S) +Ca(4s?,?S) are calculated to be 0.47 and 1.50 eV, respectively. The excited ??+, 4?-, 4II,, 2II(2), ??, and ??+ states are calculated to lie 0.2, 0.7, 0.7, 1.1, 1.1, and 1.1 eV above X ?IIr,, respectively, and the vertical and adiabatic ionization energies of AlCa have been calculated to be 5.03 and 4.97 eV, respectively

Interaction of an aluminum atom with a closed subshell metal atom: spectroscopic analysis of AIZn

Journal ArticleResonant two-photon ionization spectroscopy has been employed to investigate diatomic AlZn produced by laser vaporization of a 1:2 Al:Zn alloy target disk in a supersonic expansion of helium. Several discrete transitions are reported in the energy range from 18 400 to 19 100 cm-?. Most of these are assigned as members of the B ?II.?x ?II system, although an isolated band has been observed and assigned as the 2-0 band of the A ?' =0.5?X ?II 1/2 system. A pair of strongly mixed levels are identified as resulting from a homogeneous spin-orbit perturbation between the A ?' =0.5, v' =3 and the B ?II1l2, v' = 1 levels, and the perturbation matrix element has been deduced to be 8.11 cm-? for 27 Al64Zn, 8.23 cm-? for 27 Al66Zn. The ground state has been unambiguously identified as a 2rrr state with a bond length of 2.6957?0.0004 ?. Comparisons to the results of the preceding article on the spectroscopy of AlCa are also provided, along with a discussion of the chemical bonding in AlZn in relation to AlCa, AlAr, and AIKr

Spectroscopic analysis of jet-cooled AICu

Journal ArticleDiatomic AlCu has been interrogated using resonant two-photon ionization spectroscopy in a supersonic expansion of helium. The ground state is shown to be X l?+, deriving from the 3&3dgd configuration, in agreement with theoretical predictions. The closed-shell nature of this molecule results in a low density of electronic states, allowing the chemical bonding and electronic structure to be investigated in detail. Five excited electronic states have been observed and characterized, leading to a potential energy diagram based solely on experimental results. Constants experimentally determined for AlCu include a ground state bond length (r0) of 2.3389?0.0004 A, a dissociation energy, Do, of 2.315?0.012 eV, and an ionization potential of 7.065?.014 eV

Spectroscopic analysis of the open 3 d subshell transition metal aluminides: AIV, AICr, and AICo

Journal ArticleThree open 3d subshell transition metal aluminides, AlV, AICr, and AlCo, have been investigated by resonant two-photon ionization spectroscopy to elucidate the chemical bonding in these diatomic molecules. The open nature of the 3d subshell results in a vast number of excited electronic states in these species, allowing bond strengths to be measured by the observation of abrupt predissociation thresholds in a congested optical spectrum, giving D?(AlV)=1.489?0.010 eV, D?(AlCr)=2.272?0.009 eV, and D?(AlCo)= 1.844?0.002 eV. At lower excitation energies the presence of discrete transitions has permitted determinations of the ground state symmetries and bond lengths of AlV and AlCo through rotationally resolved studies, giving r-6 (AlV, ??=O)=2.620?0.004 A and r: (AlCo, ??=3)=2.3833?0.0005 A. Ionization energies were also measured for all three species, yielding IE(AIV)=6.01?0.10 eV, IE(AlCr)=5.96?0.04 eV, and IE(AlCo)=6.99?0.17 eV. A discussion of these results is presented in the context of previous work on AlCu, AlNi, AlCa, and AlZn

Interaction of the ionic liquid [BMP][TFSA] with rutile TiO2(110) and coadsorbed lithium

Aiming at a fundamental understanding of the processes at the electrode|ionic liquid interface in Li ion batteries, we investigated the interaction of the ionic liquid n-butyl-n-methylpyrrolidinium bis(trifluoromethylsulfonyl)imide [BMP][TFSA] and of Li with a reduced rutile TiO2(110) (1 × 1) surface as well as the interaction between [BMP][TFSA] and Li on the TiO2(110) surface under ultrahigh vacuum (UHV) conditions by X-ray photoelectron spectroscopy and scanning tunnelling microscopy. Between 80 K and 340 K [BMP][TFSA] adsorbs molecularly on the surface and at higher temperatures decomposition is observed, resulting in products such as Sad, Fad and TiNx. The decomposition pattern is compared to proposals based on theory. Small amounts of Li intercalate even at 80 K into TiO2(110), forming Li+ and Ti3+ species. The stoichiometry in the near surface region corresponds to Li7Ti5O12. For higher coverages in the range of several monolayers part of the Li remains on the surface, forming a Li2O cover layer. At 300 K, Ti3+ species become sufficiently mobile to diffuse into the bulk. Li post-deposition on a [BMP][TFSA] covered TiO2(110) surface at 80 K results in two competing reactions, Li intercalation and reaction with the IL, resulting in the decomposition of the IL. Upon warming up, the Ti3+ formed at low T is consumed by reaction with the IL adlayer and intermediate decomposition products. Post-deposition of [BMP][TFSA] (300 K) on a surface pre-covered with a Li2O/Li7Ti5O12 layer results in the partial reaction of [BMP][TFSA] with the Li+ and Ti3+ species, which gets completed at higher temperatures

A Tailored Systems Engineering Framework for Science and Technology Projects

As government and industry becomes subject to a wider range of technology initiatives, science and technology (S&T) research project leadership recognizes the need to incorporate more systems engineering (SE) rigor into their projects. The objective of this research is to develop a tailorable systems engineering framework for S&T project planning, execution, assessment and transition. The key deliverable is an Excel-based tool instantiating the SE framework for a wide range of S&T projects in technology development organizations. It includes a report with tailored methods based on programmatic discriminants. To develop this framework, a comprehensive understanding of SE principles is applied to several case studies across government and supporting industry-sponsored S&T activities. This research followed a six-step approach: (1) Literature Review; (2) Formulate Taxonomy; (3) Prepare Data Gathering Approach; (4) Review Case Studies; (5) Develop Tailorable SE Framework for Technology Development and Transition; and (6) Validate Framework.The framework allows S&T project leaders and engineers to customize a recommended set of SE processes, methods and tools for their specific project type, size, maturity, budget, and integration level. Recommendations for SE methods are made at a summary level, with additional details available for desired activities. References to established SE documentation is also included for further investigation of appropriate SE techniques

Influence of Additives on the Reversible Oxygen Reduction Reaction/Oxygen Evolution Reaction in the Mg²⁺‐Containing Ionic Liquid N ‐Butyl‐N ‐Methylpyrrolidinium Bis(Trifluoromethanesulfonyl)imide

The influence of different additives on the oxygen reduction reaction/oxygen evolution reaction (ORR/OER) in magnesium‐containing N ‐butyl‐N ‐methylpyrrolidinium bis(trifluoromethanesulfonyl)imide ([BMP][TFSI]) on a glassy carbon electrode was investigated to gain a better understanding of the electrochemical processes in Mg–air batteries. 18‐Crown‐6 was used as a complexing agent for Mg ions to hinder the passivation caused by their reaction with ORR products such as superoxide and peroxide anions. Furthermore, borane dimethylamine complex (NBH) was used as a potential water‐removing agent to inhibit electrode passivation by reacting with trace impurities of water. The electrochemical processes were characterized by differential electrochemical mass spectrometry to monitor the consumed and evolved O2 in the ORR/OER and determine the number of transferred electrons. Crown ether and NBH efficiently masked Mg$^{2+}$. A stochiometric excess of crown ether resulted in reduced formation of a passivation layer, whereas at too high concentrations the reversibility of the ORR/OER was diminished