The effect of reciprocal-space sampling and basis set quality on the calculated conductance of a molecular junction

We perform density functional theory and non-equilibrium Green's function calculations of the conductance of a gold wire and a 1,4-phenylenedimethanethiol (XYL) molecule adsorbed between Au(111) electrodes using the TranSIESTA software package. The effect of varying different computational parameters is investigated. We find that the conductance is more sensitive to the reciprocal-space sampling grid than the quality of the basis set employed. The conductance can vary up to a factor of five as a result of the choice of computational parameters. We report a set of computational parameters that yields a well-converged conductance value

Effect of dipole moment on current-voltage characteristics of single molecules

We perform empirical calculations of the tunneling current through various small organic molecules sandwiched between gold electrodes by using the Wenzel-Kramers-Brillouin (WKB) approximation. The barrier to tunneling is taken to be the work function of gold and calculated from a first principles electronic structure code. The current-voltage characteristics of these molecules are compared in the context of existing first principles and experimental results. In this model the surface dipole moment, induced by the adsorbed molecule, can have a significant effect on the current and hence dipole moments may be an important property for prediction of the conductance characteristics of a molecule. © 2006 IEEE

A new class of self-assembled monolayers on gold using an alkynyl group as a linker

The geometry and energetics for adsorption of ethynylbenzene on Au(111) have been studied using Density Functional Theory. The alkynyl group, following removal of the terminal H atom, adsorbs covalently to the surface in the fcc hollow site with a bond energy of about 70 kcal.mol-1. Intermediate adsorption states are also possible via a hydrogen 1,2 shift to form a surface-bound vinylidene, or through the opening of the C-C triple bond without removing the hydrogen atom. © 2006 IEEE

Adsorption of amine compounds on the Au(111) surface: A density functional study

A Density Functional Theory study of the adsorption energetics of various amine compounds on the gold-(111) surface revealed that preferential binding occurs in under-coordinated sites. The largest binding energy is obtained when a gold adatom is placed in the fee position and the amine positioned with the nitrogen above the adatom. The results are compared with previous calculations for thiols, phosphines, and ethynylbenzene molecules to provide a meaningful comparison within a consistent computational framework. The systematic increase in binding energy with methyl group substitution previously observed for phosphine compounds is not observed for the amine analogues. The binding energy of the amines is considerably lower than that for thiols and binding is indicated for only the adatom geometry-a result consistent with experimental data. © 2007 American Chemical Society

Electron tunneling through alkanedithiol molecules

We report on first principles calculations of the tunneling current across n-alkanedithiol molecules (n = 4,6,8,10,12) sandwiched between two Au {111} electrodes. The conductance drops exponentially with increased chain length with decay parameter βn= 0.9. The results are compared with scanning tunneling microscopy measurements on decanedithiol and with other n-alkanedithiol (n = 6,8,10) results in the literature. The theoretical results are found to be an order of magnitude larger than experimental values but follow the same trend. However, two additional, more realistic, geometries are modeled by changing the bond type and by combining the first-principles results with a Wentzel-Kramer-Brillouin (WKB) expression for tunneling across the air gap that is invariably present during scanning tunneling microscopy (STM) measurements. These results are more compatible with the experimental data

Exploring the performance of molecular rectifiers: Limitations and factors affecting molecular rectification

There has been significant work investigating the use of molecules as nanoscale rectifiers in so-called "molecular electronics". However, less attention has been paid to optimizing the design parameters of molecular rectifiers or to their inherent limitations. Here we use a barrier tunneling model to examine the degree of rectification that can be achieved and to provide insight for the design and development of molecules with optimum rectification responses. © 2007 American Chemical Society

Chains of large gaps between primes

Let $p_n$ denote the $n$-th prime, and for any $k \geq 1$ and sufficiently large $X$, define the quantity $$G_k(X) := \max_{p_{n+k} \leq X} \min( p_{n+1}-p_n, \dots, p_{n+k}-p_{n+k-1} ),$$ which measures the occurrence of chains of $k$ consecutive large gaps of primes. Recently, with Green and Konyagin, the authors showed that $$G_1(X) \gg \frac{\log X \log \log X\log\log\log\log X}{\log \log \log X}$$ for sufficiently large $X$. In this note, we combine the arguments in that paper with the Maier matrix method to show that $$G_k(X) \gg \frac{1}{k^2} \frac{\log X \log \log X\log\log\log\log X}{\log \log \log X}$$ for any fixed $k$ and sufficiently large $X$. The implied constant is effective and independent of $k$.Comment: 16 pages, no figure

Prioritising Targets for School-Based ADHD Interventions: A Delphi Survey

AbstractMany studies have investigated the effectiveness of school-based ADHD interventions at modifying different social, emotional and behavioural target outcomes. However, there is a lack of evidence about which targets stakeholders perceive to be most important. This study sought to obtain consensus on which outcomes are perceived to be most important. A total of 114 people with ADHD, educational professionals, parents of children with ADHD, clinicians and researchers participated in a Delphi survey with 3 rounds. The importance of 52 intervention targets was rated on a scale from 0 to 8 (8 being extremely important). Consensus was reached if &gt;70% of a stakeholder group rated a target as between 6–8 and &lt;15% rated it as 0–2. Targets were dropped from subsequent rounds if more than 50% of stakeholder groups rated it as 0–5. Targets that all four stakeholder groups reached consensus on in any round were automatically included in our final outcome set. Comments were analysed using Thematic Analysis. All four stakeholder groups reached consensus on the importance of seven targets: ability to pay attention, conflict with teachers and peers, executive functioning, global functioning and quality of life, inattention symptoms, organisation skills and self-esteem. Four overarching themes were identified: Complexity of ADHD, Relationships, School Context, and What ADHD means to me. School-based ADHD interventions should target outcomes identified as most important to those who stand to benefit from such interventions. Some outcomes prioritised by our participants have not yet been targeted in school-based ADHD interventions. Implications of our findings for intervention and research design are discussed.</jats:p

Transitions of care from child and adolescent mental health services to adult mental health services (TRACK Study) : a study of protocols in Greater London

Background: Although young people's transition from Child and Adolescent Mental Health Services (CAMHS) to Adult Mental Health Services (AMHS) in England is a significant health issue for service users, commissioners and providers, there is little evidence available to guide service development. The TRACK study aims to identify factors which facilitate or impede effective transition from CAHMS to AMHS. This paper presents findings from a survey of transition protocols in Greater London. Methods: A questionnaire survey (Jan-April 2005) of Greater London CAMHS to identify transition protocols and collect data on team size, structure, transition protocols, population served and referral rates to AMHS. Identified transition protocols were subjected to content analysis. Results: Forty two of the 65 teams contacted (65%) responded to the survey. Teams varied in type (generic/targeted/in-patient), catchment area (locality-based, wider or national) and transition boundaries with AMHS. Estimated annual average number of cases considered suitable for transfer to AMHS, per CAMHS team (mean 12.3, range 0–70, SD 14.5, n = 37) was greater than the annual average number of cases actually accepted by AMHS (mean 8.3, range 0–50, SD 9.5, n = 33). In April 2005, there were 13 active and 2 draft protocols in Greater London. Protocols were largely similar in stated aims and policies, but differed in key procedural details, such as joint working between CAHMS and AMHS and whether protocols were shared at Trust or locality level. While the centrality of service users' involvement in the transition process was identified, no protocol specified how users should be prepared for transition. A major omission from protocols was procedures to ensure continuity of care for patients not accepted by AMHS. Conclusion: At least 13 transition protocols were in operation in Greater London in April 2005. Not all protocols meet all requirements set by government policy. Variation in protocol-sharing organisational units and transition process suggest that practice may vary. There is discontinuity of care provision for some patients who 'graduate' from CAMHS services but are not accepted by adult services

Implementation of routine outcome measurement in child and adolescent mental health services in the United Kingdom: a critical perspective

The aim of this commentary is to provide an overview of clinical outcome measures that are currently recommended for use in UK Child and Adolescent Mental Health Services (CAMHS), focusing on measures that are applicable across a wide range of conditions with established validity and reliability, or innovative in their design. We also provide an overview of the barriers and drivers to the use of Routine Outcome Measurement (ROM) in clinical practice