108 research outputs found
The shortcomings of semi-local and hybrid functionals: what we can learn from surface science studies
A study of the adsorption of CO on late 4d and transition metal (111)
surfaces (Ru, Rh, Pd, Ag, Os, Ir, and Pt) considering atop and hollow site
adsorption is presented. The applied functionals include the gradient corrected
PBE and BLYP functional, and the corresponding hybrid Hartree-Fock density
functionals HSE and B3LYP. We find that PBE based hybrid functionals
(specifically HSE) yield, with the exception of Pt, the correct site order on
all considered metals, but they also considerably overestimate the adsorption
energies compared to experiment. On the other hand, the semi-local BLYP
functional and the corresponding hybrid functional B3LYP yield very
satisfactory adsorption energies and the correct adsorption site for all
surfaces. We are thus faced with a Procrustean problem: the B3LYP and BLYP
functionals seem to be the overall best choice for describing adsorption on
metal surfaces, but they simultaneously fail to account well for the properties
of the metal, vastly overestimating the equilibrium volume and underestimating
the atomization energies. Setting out from these observations, general
conclusions are drawn on the relative merits and drawbacks of various
semi-local and hybrid functionals. The discussion includes a revised version of
the PBE functional specifically optimized for bulk properties and surface
energies (PBEsol), a revised version of the PBE functional specifically
optimized to predict accurate adsorption energies (rPBE), as well as the
aforementioned BLYP functional. We conclude that no semi-local functional is
capable to describe all aspects properly, and including non-local exchange also
only improves some, but worsens other properties.Comment: 12 pages, 6 figures; to be published in New Journal of Physic
You took the words right out of my mouth:Dual-fMRI reveals intra- and inter-personal neural processes supporting verbal interaction.
Verbal communication relies heavily upon mutual understanding, or common ground. Inferring the intentional states of our interaction partners is crucial in achieving this, and social neuroscience has begun elucidating the intra- and inter-personal neural processes supporting such inferences. Typically, however, neuroscientific paradigms lack the reciprocal to-and-fro characteristic of social communication, offering little insight into the way these processes operate online during real-world interaction. In the present study, we overcame this by developing a “hyperscanning” paradigm in which pairs of interactants could communicate verbally with one another in a joint-action task whilst both undergoing functional magnetic resonance imaging simultaneously. Successful performance on this task required both interlocutors to predict their partner's upcoming utterance in order to converge on the same word as each other over recursive exchanges, based only on one another's prior verbal expressions. By applying various levels of analysis to behavioural and neuroimaging data acquired from 20 dyads, three principal findings emerged: First, interlocutors converged frequently within the same semantic space, suggesting that mutual understanding had been established. Second, assessing the brain responses of each interlocutor as they planned their upcoming utterances on the basis of their co-player's previous word revealed the engagement of the temporo-parietal junctional (TPJ), precuneus and dorso-lateral pre-frontal cortex. Moreover, responses in the precuneus were modulated positively by the degree of semantic convergence achieved on each round. Second, effective connectivity among these regions indicates the crucial role of the right TPJ in this process, consistent with the Nexus model. Third, neural signals within certain nodes of this network became aligned between interacting interlocutors. We suggest this reflects an interpersonal neural process through which interactants infer and align to one another's intentional states whilst they establish a common ground
CO adsorption on neutral iridium clusters
The adsorption of carbon monoxide on neutral iridium clusters in the size
range of n = 3 to 21 atoms is investigated with infrared multiple photon
dissociation spectroscopy. For each cluster size only a single v(CO) band is
present with frequencies in the range between 1962 cm-1 (n = 8) and 1985 cm-1
(n = 18) which can be attributed to an atop binding geometry. This behaviour is
compared to the CO binding geometries on clusters of other group 9 and 10
transition metals as well as to that on extended surfaces. The preference of Ir
for atop binding is rationalized by relativistic effects on the electronic
structure of the later 5d metals
Identification and design principles of low hole effective mass p-type transparent conducting oxides
The development of high-performance transparent conducting oxides is critical to many technologies from transparent electronics to solar cells. Whereas n-type transparent conducting oxides are present in many devices, their p-type counterparts are not largely commercialized, as they exhibit much lower carrier mobilities due to the large hole effective masses of most oxides. Here we conduct a high-throughput computational search on thousands of binary and ternary oxides and identify several highly promising compounds displaying exceptionally low hole effective masses (up to an order of magnitude lower than state-of-the-art p-type transparent conducting oxides), as well as wide band gaps. In addition to the discovery of specific compounds, the chemical rationalization of our findings opens new directions, beyond current Cu-based chemistries, for the design and development of future p-type transparent conducting oxides.United States. Office of Naval Research (Award N00014-11-1-0212
A rapidly-reversible absorptive and emissive vapochromic Pt(II) pincer-based chemical sensor
Selective, robust and cost-effective chemical sensors for detecting small volatile-organic compounds (VOCs) have widespread applications in industry, healthcare and environmental monitoring. Here we design a Pt(II) pincer-type material with selective absorptive and emissive responses to methanol and water. The yellow anhydrous form converts reversibly on a subsecond timescale to a red hydrate in the presence of parts-per-thousand levels of atmospheric water vapour. Exposure to methanol induces a similarly-rapid and reversible colour change to a blue methanol solvate. Stable smart coatings on glass demonstrate robust switching over 104 cycles, and flexible microporous polymer membranes incorporating microcrystals of the complex show identical vapochromic behaviour. The rapid vapochromic response can be rationalised from the crystal structure, and in combination with quantum-chemical modelling, we provide a complete microscopic picture of the switching mechanism. We discuss how this multiscale design approach can be used to obtain new compounds with tailored VOC selectivity and spectral responses
ExoClock Project. III. 450 New Exoplanet Ephemerides from Ground and Space Observations
The ExoClock project has been created to increase the efficiency of the Ariel mission. It will achieve this by continuously monitoring and updating the ephemerides of Ariel candidates, in order to produce a consistent catalog of reliable and precise ephemerides. This work presents a homogenous catalog of updated ephemerides for 450 planets, generated by the integration of ∼18,000 data points from multiple sources. These sources include observations from ground-based telescopes (the ExoClock network and the Exoplanet Transit Database), midtime values from the literature, and light curves from space telescopes (Kepler, K2, and TESS). With all the above, we manage to collect observations for half of the postdiscovery years (median), with data that have a median uncertainty less than 1 minute. In comparison with the literature, the ephemerides generated by the project are more precise and less biased. More than 40% of the initial literature ephemerides had to be updated to reach the goals of the project, as they were either of low precision or drifting. Moreover, the integrated approach of the project enables both the monitoring of the majority of the Ariel candidates (95%), and also the identification of missing data. These results highlight the need for continuous monitoring to increase the observing coverage of the candidate planets. Finally, the extended observing coverage of planets allows us to detect trends (transit-timing variations) for a sample of 19 planets. All the products, data, and codes used in this work are open and accessible to the wider scientific community
ExoClock Project III: 450 new exoplanet ephemerides from ground and space observations
The ExoClock project has been created with the aim of increasing the
efficiency of the Ariel mission. It will achieve this by continuously
monitoring and updating the ephemerides of Ariel candidates over an extended
period, in order to produce a consistent catalogue of reliable and precise
ephemerides. This work presents a homogenous catalogue of updated ephemerides
for 450 planets, generated by the integration of 18000 data points from
multiple sources. These sources include observations from ground-based
telescopes (ExoClock network and ETD), mid-time values from the literature and
light-curves from space telescopes (Kepler/K2 and TESS). With all the above, we
manage to collect observations for half of the post-discovery years (median),
with data that have a median uncertainty less than one minute. In comparison
with literature, the ephemerides generated by the project are more precise and
less biased. More than 40\% of the initial literature ephemerides had to be
updated to reach the goals of the project, as they were either of low precision
or drifting. Moreover, the integrated approach of the project enables both the
monitoring of the majority of the Ariel candidates (95\%), and also the
identification of missing data. The dedicated ExoClock network effectively
supports this task by contributing additional observations when a gap in the
data is identified. These results highlight the need for continuous monitoring
to increase the observing coverage of the candidate planets. Finally, the
extended observing coverage of planets allows us to detect trends (TTVs -
Transit Timing Variations) for a sample of 19 planets. All products, data, and
codes used in this work are open and accessible to the wider scientific
community.Comment: Recommended for publication to ApJS (reviewer's comments
implemented). Main body: 13 pages, total: 77 pages, 7 figures, 7 tables. Data
available at http://doi.org/10.17605/OSF.IO/P298
Recommended from our members
ExoClock Project. III. 450 New Exoplanet Ephemerides from Ground and Space Observations
The ExoClock project has been created to increase the efficiency of the Ariel mission. It will achieve this by continuously monitoring and updating the ephemerides of Ariel candidates, in order to produce a consistent catalog of reliable and precise ephemerides. This work presents a homogenous catalog of updated ephemerides for 450 planets, generated by the integration of ∼18,000 data points from multiple sources. These sources include observations from ground-based telescopes (the ExoClock network and the Exoplanet Transit Database), midtime values from the literature, and light curves from space telescopes (Kepler, K2, and TESS). With all the above, we manage to collect observations for half of the postdiscovery years (median), with data that have a median uncertainty less than 1 minute. In comparison with the literature, the ephemerides generated by the project are more precise and less biased. More than 40% of the initial literature ephemerides had to be updated to reach the goals of the project, as they were either of low precision or drifting. Moreover, the integrated approach of the project enables both the monitoring of the majority of the Ariel candidates (95%), and also the identification of missing data. These results highlight the need for continuous monitoring to increase the observing coverage of the candidate planets. Finally, the extended observing coverage of planets allows us to detect trends (transit-timing variations) for a sample of 19 planets. All the products, data, and codes used in this work are open and accessible to the wider scientific community
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