The local adsorption geometry and electronic structure of alanine on Cu{110}

The adsorption of alanine on Cu {110} was studied by a combination of near edge X-ray absorption fine structure (NEXAFS) spectroscopy, X-ray photoelectron spectroscopy (XPS) and density functional theory (DFT). Large chemical shifts in the C 1s, N 1s, and O 1s XP spectra were found between the alanine multilayer and the chemisorbed and pseudo-(3 x 2) alaninate layers. From C, N, and O K-shell NEXAFS spectra the tilt angles of the carboxylate group (approximate to 26 degrees in plane with respect to [1 (1) over bar0] and approximate to 45 degrees out of plane) and the C-N bond angle with respect to [1 (1) over bar0] could be determined for the pseudo-(3 x 2) overlayer. Using this information three adsorption geometries could be eliminated from five p(3 x 2) structures which lead to almost identical heats of adsorption in the DFT calculations between 1.40 and 1.47 eV/molecule. Due to the small energy difference between the remaining two structures it is not unlikely that these coexist on the surface at room temperature. (c) 2006 Elsevier B.V. All rights reserved.

Spectroscopy of highly excited vibrational states of HCN in its ground electronic state

An experimental technique based on a scheme of vibrationally mediated photodissociation has been developed and applied to the spectroscopic study of highly excited vibrational states in HCN, with energies between 29 000 and 30 000 cm(-1). The technique consists of four sequential steps: in the first one, a high power laser is used to vibrationally excite the sample to an intermediate state, typically (0,0,4), the nu(3) mode being approximately equivalent to the C-H stretching vibration. Then a second laser is used to search for transitions between this intermediate state and highly vibrationally excited states. When one of these transitions is found, HCN molecules are transferred to a highly excited vibrational state. Third, a ultraviolet laser photodissociates the highly excited molecules to produce H and CN radicals in its A (2)Pi electronic state. Finally, a fourth laser (probe) detects the presence of the CN(A) photofragments by means of an A-->B-->X laser induced fluorescence scheme. The spectra obtained with this technique, consisting of several rotationally resolved vibrational bands, have been analyzed. The positions and rotational parameters of the states observed are presented and compared with the results of a state-of-the-art variational calculation. (C) 2004 American Institute of Physics.

Redox chemistry and electronic properties of 2,3,5,6-tetrakis(2-pyridyl)pyrazine-bridged diruthenium complexes controlled by N,C,N '-biscyclometalated ligands

To investigate the consequences of cyclometalation for electronic communication in dinuclear ruthenium complexes, a series of 2,3,5,6-tetrakis(2-pyridyl)pyrazine (tppz) bridged diruthenium complexes was prepared and studied. These complexes have a central tppz ligand bridging via nitrogen-to-ruthenium coordination bonds, while each ruthenium atom also binds either a monoanionic, N,C,N'-terdentate 2,6-bis(2'-pyridyl)phenyl (R-N boolean AND C boolean AND N) ligand or a 2,2':6',2 ''-terpyridine (tpy) ligand. The N,C,N'-, that is, biscyclometalation, instead of the latter N,N', N ''-bonding motif significantly changes the electronic properties of the resulting complexes. Starting from well-known [{Ru(tpy)}(2)(mu-tppz)](4+) (tpy = 2,2':2 '',6-terpyridine) ([3](4+)) as a model compound, the complexes [{Ru(R-N boolean AND C boolean AND N)}(mu-tppz){Ru(tpy)}](3+) (R-N boolean AND C(H)boolean AND N = 4-R-1,3-dipyridylbenzene, R = H ([4a](3+)), CO2Me ([4b](3+))), and [{Ru(R-N boolean AND C boolean AND N)}(2)(mu-tppz)](2+), (R = H ([5a](2+)), CO2Me ([5b](2+))) were prepared with one or two N,C,N'-cyclometalated terminal ligands. The oxidation and reduction potentials of cyclometalated [4](3+) and [5](2+) are shifted negatively compared to non-cyclometalated [3](4+), the oxidation processes being affected more significantly. Compared to [3](4+), the electronic spectra of [5](2+) display large bathochromic shifts of the main MLCT transitions in the visible spectral region with low-energy absorptions tailing down to the NIR region. One-electron oxidation of [3](4+) and [5](2+) gives rise to low-energy absorption bands. The comproportionation constants and NIR band shape correspond to delocalized Robin-Day class III compounds. Complexes [4a](3+) (R = H) and [4b](3+) (R = CO2Me) also exhibit strong electronic communication, and notwithstanding the large redox-asymmetry the visible metal-to-ligand charge-transfer absorption is assigned to originate from both metal centers. The potential of the first, ruthenium-based, reversible oxidation process is strongly negatively shifted. On the contrary, the second oxidation is irreversible and cyclometalated ligand-based. Upon one-electron oxidation, a weak and low-energy absorption arises.

Consequences of N,C,N '- and C,N,N '-coordination modes on electronic and photophysical properties of cyclometalated aryl ruthenium(II) complexes

The effects of isoelectronic replacement of a neutral nitrogen donor atom by an anionic carbon atom in terpyridine ruthenium(II) complexes on the electronic and photophysical properties of the resulting N,C,N'- and C,N,N'-cyclometalated aryl ruthenium(II) complexes were investigated. To this end, a series of complexes was prepared either with ligands containing exclusively nitrogen donor atoms, that is, [Ru(R-1-tpy)(R-2-tpy)](2+) (R-1, R-2 = H, CO2Et), or bearing either one N,C,N'- or C,N,N'-cyclometalated ligand and one tpy ligand, that is, [Ru(R-1-(NCN)-C-Lambda-N-Lambda)(R-2-tpy)](+) and [Ru(R-1-(CNN)-N-Lambda-N-Lambda)(R-2-tpy)](+), respectively. Single-crystal X-ray structure determinations showed that cyclometalation does not significantly alter the overall geometry of the complexes but does change the bond lengths around the ruthenium(II) center, especially the nitrogen-to-ruthenium bond length trans to the carbanion. Substitution of either of the ligands with electron-withdrawing ester functionalities fine-tuned the electronic properties and resulted in the presence of an IR probe. Using trends obtained from redox potentials, emission energies, IR spectroelectrochemical responses, and the character of the lowest unoccupied molecular orbitals from DFT studies, it is shown that the first reduction process and luminescence are associated with the ester-substituted C,N,N'-cyclometalated ligand in [Ru(EtO2C-(CNN)-N-Lambda-N-Lambda)(tpy)](+). Cyclometalation in an N,C,N'-bonding motif changed the energetic order of the ruthenium d(zx), d(yz), and d(xy) orbitals. The red-shifted absorption in the N,C,N'-cyclometalated complexes is assigned to MLCT transitions to the tpy ligand. The red shift observed upon introduction of the ester moiety is associated with an increase in intensity of low-energy transitions, rather than a red shift of the main transition. Cyclometalation in the C,N,N'-binding motif also red-shifts the absorption, but the corresponding transition is associated with both ligand types. Luminescence of the cyclometalated complexes is relatively independent of the mode of cyclometalation, obeying the energy gap law within each individual series.

Risk under performance-based contracting in the UK construction sector

As a method of procuring the services of the built environment, performance-based contracting (PBC) seeks to link the building supplier to longer term commitments than has traditionally been the case in the construction sector. By rewarding the building producer according to the way that building or structure delivers the users' requirements, rather than according to a list of assembled parts, a number of additional risks are taken by contractors, including fitness for purpose, costs and briefing. The extent to which contractors recognize these risks and their methods of dealing with them vary considerably and are influenced by their attitudes towards risk. As the risks associated with PBC are seen as large, uninsurable, and vulnerable to changing client requirements, the majority of respondents would reject the use of PBC as a method of contracting. Nevertheless, PBC may be used under particular conditions, where rewards are deemed sufficient to compensate for the additional risk to the contractor of undertaking work on the basis of a stream of payments paid over the life of a structure depending on the satisfactory performance of the building or as part of a private finance initiative.

Ownership rights in performance-based contracting: A case study of English law

Clients and contractors need to be aware of the project’s legal environment because the viability of a procurement strategy can be vitiated by legal rules. This is particularly true regarding Performance-Based Contracting (PBC) whose viability may be threatened by rules of property law: while the PBC concept does not require that the contractor transfers the ownership in the building materials used to the client, the rules of property law often lead to an automatic transfer of ownership. But does the legal environment really render PBC unfeasible? In particular, is PBC unfeasible because contractors lose their materials as assets? These questions need to be answered with respect to the applicable property law. As a case study, English property law has been chosen. Under English law, the rule which governs the automatic transfer of ownership is called quicquid plantatur solo, solo credit (whatever is fixed to the soil belongs to the soil). An analysis of this rule reveals that not all materials which are affixed to land become part of the land. This fate only occurs in relation to materials which have been affixed with the intention of permanently improving the land. Five fictitious PBC cases have been considered in terms of the legal status of the materials involved, and several subsequent legal questions have been addressed. The results suggest that English law does actually threaten the feasibility of PBC in some cases. However, it is also shown that the law provides means to circumvent the unwanted results which flow from the rules of property law. In particular, contractors who are interested in keeping their materials as assets can insist on agreeing a property right in the client’s land, i.e. a contractor’s lien. Therefore, the outcome is that English property law does not render the implementation of the PBC concept unfeasible. At a broader level, the results contribute to the theoretical framework of PBC as an increasingly used procurement strategy.

Design considerations for the multiband OFDM physical layer in consumer electronic products

The creation of Wireless Personal Area Networks (WPANs) offers the Consumer Electronics industry a mechanism to truly unwire consumer products, leading to portability and ease of installation as never seen before. WPAN's can offer data-rates exceeding those that are required to convey high quality broadcast video, thus users can easily connect to high quality video for multimedia presentations in education, libraries, advertising, or have a wireless connection at home. There have been many WPAN proposals, but this paper concentrates on ECMA-368 as this standard has the largest industrial and implementers' forum backing. This paper discusses the technology behind ECMA-368, the required numerical bandwidth, buffer memory requirements and implementation considerations while concentrating on supporting all the offered data-rates'.

Validating a new clinical subtyping scheme for delirium with electronic motion analysis

The usefulness of motor subtypes of delirium is unclear due to inconsistency in sub-typing methods and a lack of validation with objective measures of activity. The activity of 40 patients was measured with 24 h accelerometry monitoring. Patients with Diagnostic and Statistical Manual of Mental Disorders, fourth edition (DSM-IV) delirium (n = 30) were allocated into hyperactive, hypoactive and mixed motor subtypes. Delirium subtypes differed in relation to overall amount of activity, including movement in both sagittal and transverse planes. Differences were greater in the daytime and during the early evening ‘sundowning’ period. Frequency of postural changes was the most discriminating measure examined. Clinical subtypes of delirium defined by observed motor behaviour on the ward differ in electronically measured activity levels.

A study into the impact of introducing Year 5 students to university and electronic engineering

This paper demonstrates the benefits of introducing Year 5 school students to university life, encountering styles of teaching to which they would be otherwise unaccustomed; and the results of a survey conducted both before and after the study visit to determine whether the visit was beneficial to the students in academic terms.

Numerical precision requirements on the Multiband Ultra-Wideband system for practical consumer electronic devices

This paper discusses the requirements on the numerical precision for a practical Multiband Ultra-Wideband (UWB) consumer electronic solution. To this end we first present the possibilities that UWB has to offer to the consumer electronics market and the possible range of devices. We then show the performance of a model of the UWB baseband system implemented using floating point precision. Then, by simulation we find the minimal numerical precision required to maintain floating-point performance for each of the specific data types and signals present in the UWB baseband. Finally, we present a full description of the numerical requirements for both the transmit and receive components of the UWB baseband. The numerical precision results obtained in this paper can then be used by baseband designers to implement cost effective UWB systems using System-on-Chip (SoC), FPGA and ASIC technology solutions biased toward the competitive consumer electronics market(1).

Electronic voting systems in undergraduate teaching

One of the major differences undergraduates experience during the transition to university is the style of teaching. In schools and colleges most students study key stage 5 subjects in relatively small informal groups where teacher–pupil interaction is encouraged and two-way feedback occurs through question and answer type delivery. On starting in HE students are amazed by the sizes of the classes. For even a relatively small chemistry department with an intake of 60-70 students, biologists, pharmacists, and other first year undergraduates requiring chemistry can boost numbers in the lecture hall to around 200 or higher. In many universities class sizes of 400 are not unusual for first year groups where efficiency is crucial. Clearly the personalised classroom-style delivery is not practical and it is a brave student who shows his ignorance by venturing to ask a question in front of such an audience. In these environments learning can be a very passive process, the lecture acts as a vehicle for the conveyance of information and our students are expected to reinforce their understanding by ‘self-study’, a term, the meaning of which, many struggle to understand. The use of electronic voting systems (EVS) in such situations can vastly change the students’ learning experience from a passive to a highly interactive process. This principle has already been demonstrated in Physics, most notably in the work of Bates and colleagues at Edinburgh.1 These small hand-held devices, similar to those which have become familiar through programmes such as ‘Who Wants to be a Millionaire’ can be used to provide instant feedback to students and teachers alike. Advances in technology now allow them to be used in a range of more sophisticated settings and comprehensive guides on use have been developed for even the most techno-phobic staff.

The interplay between geometry, electronic structure, and reactivity of Cu-Ni bimetallic (111) surfaces

The mutual influence of surface geometry (e.g. lattice parameters, morphology) and electronic structure is discussed for Cu-Ni bimetallic (111) surfaces. It is found that on flat surfaces the electronic d-states of the adlayer experience very little influence from the substrate electronic structure which is due to their large separation in binding energies and the close match of Cu and Ni lattice constants. Using carbon monoxide and benzene as probe molecules, it is found that in most cases the reactivity of Cu or Ni adlayers is very similar to the corresponding (111) single crystal surfaces. Exceptions are the adsorption of CO on submonolayers of Cu on Ni(111) and the dissociation of benzene on Ni/Cu(111) which is very different from Ni(111). These differences are related to geometric factors influencing the adsorption on these surfaces.