Capillary rise of water in hydrophilic nanopores

We report on the capillary rise of water in three-dimensional networks of hydrophilic silica pores with 3.5nm and 5nm mean radii, respectively (porous Vycor monoliths). We find classical square root of time Lucas-Washburn laws for the imbibition dynamics over the entire capillary rise times of up to 16h investigated. Provided we assume two preadsorbed strongly bound layers of water molecules resting at the silica walls, which corresponds to a negative velocity slip length of -0.5nm for water flow in silica nanopores, we can describe the filling process by a retained fluidity and capillarity of water in the pore center. This anticipated partitioning in two dynamic components reflects the structural-thermodynamic partitioning in strongly silica bound water layers and capillary condensed water in the pore center which is documented by sorption isotherm measurements.Comment: 4 pages, 3 figure

Interface dipoles of organic molecules on Ag(111) in hybrid density-functional theory

We investigate the molecular acceptors 3,4,9,10-perylene-tetracarboxylic acid dianhydride (PTCDA), 2,3,5,6-tetra uoro-7,7,8,8-tetracyanoquinodimethane (F4TCNQ), and 4,5,9,10-pyrenetetraone (PYTON) on Ag(111) using densityfunctional theory. For two groups of the HSE(\alpha, \omega) family of exchange-correlation functionals (\omega = 0 and \omega = 0.2\AA) we study the isolated components as well as the combined systems as a function of the amount of exact-exchange (\alpha). We find that hybrid functionals favour electron transfer to the adsorbate. Comparing to experimental work-function data, we report for (\alpha) ca. 0.25 a notable but small improvement over (semi)local functionals for the interface dipole. Although Kohn-Sham eigenvalues are only approximate representations of ionization energies, incidentally, at this value also the density of states agrees well with the photoelectron spectra. However, increasing (\alpha) to values for which the energy of the lowest unoccupied molecular orbital matches the experimental electron affinity in the gas phase worsens both the interface dipole and the density of states. Our results imply that semi-local DFT calculations may often be adequate for conjugated organic molecules on metal surfaces and that the much more computationally demanding hybrid functionals yield only small improvements.Comment: submitted to New Journal of Physics (2013). More information can be found at http://th.fhi-berlin.mpg.de/site/index.php?n=Publications.Publication

Synaptic scaling - an artificial neural network regularization inspired by nature

Nature has always inspired the human spirit and scientists frequently developed new methods based on observations from nature. Recent advances in imaging and sensing technology allow fascinating insights into biological neural processes. With the objective of finding new strategies to enhance the learning capabilities of neural networks, we focus on a phenomenon that is closely related to learning tasks and neural stability in biological neural networks, called homeostatic plasticity. Among the theories that have been developed to describe homeostatic plasticity, synaptic scaling has been found to be the most mature and applicable. We systematically discuss previous studies on the synaptic scaling theory and how they could be applied to artificial neural networks. Therefore, we utilize information theory to analytically evaluate how mutual information is affected by synaptic scaling. Based on these analytic findings, we propose two flavors in which synaptic scaling can be applied in the training process of simple and complex, feedforward, and recurrent neural networks. We compare our approach with state-of-the-art regularization techniques on standard benchmarks. We found that the proposed method yields the lowest error in both regression and classification tasks compared to previous regularization approaches in our experiments across a wide range of network feedforward and recurrent topologies and data sets

Molecular dynamics of n-hexane: A quasi-elastic neutron scattering study on the bulk and spatially nanochannel-confined liquid

We present incoherent quasi-elastic neutron scattering measurements in a wavevector transfer range from 0.4 AA^{-1} to 1.6AA^{-1} on liquid n-hexane confined in cylindrical, parallel-aligned nanochannels of 6 nm mean diameter and 260 micrometer length in monolithic, mesoporous silicon. They are complemented with, and compared to, measurements on the bulk system in a temperature range from 50K to 250K. The time-of-flight spectra of the bulk liquid can be modeled by microscopic translational as well as fast localized rotational, thermally-excited, stochastic motions of the molecules. In the nano-confined state of the liquid, which was prepared by vapor condensation, we find two molecular populations with distinct dynamics, a fraction which is immobile on the time scale of 1ps to 100ps probed in our experiments and a second component with a self-diffusion dynamics slightly slower than observed for the bulk liquid. No hints of an anisotropy of the translational diffusion with regard to the orientation of the channels' long axes have been found. The immobile fraction amounts to about 5% at 250K, gradually increases upon cooling and exhibits an abrupt increase at 160K (20K below bulk crystallization), which indicates pore freezingComment: 10 pages, 7 figure

Melting and freezing of argon in a granular packing of linear mesopore arrays

Freezing and melting of Ar condensed in a granular packing of template-grown arrays of linear mesopores (SBA-15, mean pore diameter 8 nanometer) has been studied by specific heat measurements C as a function of fractional filling of the pores. While interfacial melting leads to a single melting peak in C, homogeneous and heterogeneous freezing along with a delayering transition for partial fillings of the pores result in a complex freezing mechanism explainable only by a consideration of regular adsorption sites (in the cylindrical mesopores) and irregular adsorption sites (in niches of the rough external surfaces of the grains, and at points of mutual contact of the powder grains). The tensile pressure release upon reaching bulk liquid/vapor coexistence quantitatively accounts for an upward shift of the melting/freeezing temperature observed while overfilling the mesopores.Comment: 4 pages, 4 figures, to appear as a Letter in Physical Review Letter

Acceptability and proof of concept of internet-delivered treatment for depression, anxiety, and stress in university students: protocol for an open feasibility trial

BACKGROUND: In recent years, university counseling and mental health services have reported an increase in the number of clients seeking services and in yearly visits. This trend has been observed at many universities, indicating that behavioral and mental health issues pose significant problems for many college students. The aim of this study is to assess the acceptability and proof of concept of internet-delivered treatment for depression, anxiety, and stress for university students. METHODS/DESIGN: The study is an open feasibility trial of the SilverCloud programs for depression (Space from Depression), anxiety (Space from Anxiety), and stress (Space from Stress). All three are 8-module internet-delivered CBT (iCBT) intervention programs. Participants are assigned a supporter who provides weekly feedback on progress and exercises. Participants will complete the Patient Health Questionnaire-9 (PHQ-9), Generalized Anxiety Disorder-7 (GAD-7), and stress subscale of the Depression, Anxiety, Stress Scale-21 (DASS-21) as the outcome measures for the depression, anxiety, and stress interventions, respectively. Other outcomes include measures of acceptability of, and satisfaction, with the intervention. Data will be collected at baseline, 8 weeks and 3-month follow-up. DISCUSSION: It is anticipated that the study will inform the researchers and service personnel of the programs' potential to reduce depression, anxiety, and stress in a student population as well as the protocols to be employed in a future trial. In addition, it will provide insight into students' engagement with the programs, their user experience, and their satisfaction with the online delivery format

Supported internet-delivered cognitive behavioral therapy programs for depression, anxiety, and stress in university students: open, non-randomised trial of acceptability, effectiveness, and satisfaction

BACKGROUND: Many university campuses have limited mental health services that cannot cope with the high demand. One alternative is to use internet-delivered cognitive behavioral therapy (iCBT) as a way of tackling barriers such as lack of availability and scheduling issues. OBJECTIVE: This study aimed to assess feasibility, acceptability, effectiveness, and satisfaction of a supported iCBT intervention offering 3 programs on depression, anxiety, and stress to university students. The design was an open or nonrandomized feasibility trial. METHODS: Participants were recruited from 3 counseling centers at a large midwestern University in the United States. Those agreeing to take part chose 1 of 3 iCBT programs-Space from Depression, Space from Anxiety, or Space from Stress -all comprised 8 modules of media-rich interactive content. Participants were supported throughout the trial by a trained professional. The Patient Health Questionnaire 9 (PHQ-9), Generalized Anxiety Disorder 7 (GAD-7) questionnaire, and stress subscale of the Depression Anxiety and Stress Scale (DASS-21) were completed at baseline, 8 weeks, and 3-month follow-up. A Satisfaction With Treatment (SAT) questionnaire was completed at 8 weeks, and qualitative interviews were completed by a subsample of participants at 3 months. RESULTS: A total of 102 participants were recruited, with 52 choosing Space from Anxiety, 31 choosing Space from Depression, and 19 choosing Space from Stress. Mixed-effects models showed a significant decrease in symptoms of depression (F₄=6.36, P<.001), anxiety (F₄=7.97, P<.001), and stress (F₄=8.50, P<.001) over time across all 3 programs. The largest decreases in PHQ-9 scores at 8 weeks were among participants who chose the Space from Depression program (d=0.84); at 3 months, the largest decreases in PHQ-9 scores were among those who chose the Space from Stress program (d=0.74). The largest decreases in GAD-7 scores were among those who chose the Space from Anxiety program (d=0.74 at 8 weeks and d=0.94 at 3 months). The largest decrease in DASS-21 stress subscale scores was among those who chose the Space from Stress program (d=0.49 at 8 weeks and d=1.16 at 3 months). The mean time spent using the platform per session was 27.4 min (SD 33.8), and participants completed 53% (SD 37.6) of the total program content on average. Most (37/53, 69%) participants found the programs helpful or very helpful and liked the convenience and flexibility of the intervention. Qualitative interviews (n=14) indicated the intervention met students' expectations, and they saw it as a valuable complement to face-to-face treatment. CONCLUSIONS: The iCBT programs tested in our study appear to be feasible, acceptable, and effective in a university environment. Participants described the benefits of having a flexible, supported Web-based intervention available on campus. Larger trials should be conducted to further test the effectiveness of supported Web-based interventions that give students a choice of program depending on their symptom profile.Published versio

SEOSS-Queries - a software engineering dataset for text-to-SQL and question answering tasks

Stakeholders of software development projects have various information needs for making rational decisions during their daily work. Satisfying these needs requires substantial knowledge of where and how the relevant information is stored and consumes valuable time that is often not available. Easing the need for this knowledge is an ideal text-to-SQL benchmark problem, a field where public datasets are scarce and needed. We propose the SEOSS-Queries dataset consisting of natural language utterances and accompanying SQL queries extracted from previous studies, software projects, issue tracking tools, and through expert surveys to cover a large variety of information need perspectives. Our dataset consists of 1,162 English utterances translating into 166 SQL queries; each query has four precise utterances and three more general ones. Furthermore, the dataset contains 393,086 labeled utterances extracted from issue tracker comments. We provide pre-trained SQLNet and RatSQL baseline models for benchmark comparisons, a replication package facilitating a seamless application, and discuss various other tasks that may be solved and evaluated using the dataset. The whole dataset with paraphrased natural language utterances and SQL queries is hosted at figshare.com/s/75ed49ef01ac2f83b3e2

Preferred orientation of n-hexane crystallized in silicon nanochannels: A combined x-ray diffraction and sorption isotherm study

We present an x-ray diffraction study on n-hexane in tubular silicon channels of approximately 10 nm diameter both as a function of the filling fraction f of the channels and as a function of temperature. Upon cooling, confined n-hexane crystallizes in a triclinic phase typical of the bulk crystalline state. However, the anisotropic spatial confinement leads to a preferred orientation of the confined crystallites, where the crystallographic direction coincides with the long axis of the channels. The magnitude of this preferred orientation increases with the filling fraction, which corroborates the assumption of a Bridgman-type crystallization process being responsible for the peculiar crystalline texture. This growth process predicts for a channel-like confinement an alignment of the fastest crystallization direction parallel to the long channel axis. It is expected to be increasingly effective with the length of solidifying liquid parcels and thus with increasing f. In fact, the fastest solidification front is expected to sweep over the full silicon nanochannel for f=1, in agreement with our observation of a practically perfect texture for entirely filled nanochannels

A Benchmark of GW Methods for Azabenzenes: Is the GW Approximation Good Enough?

Many-body perturbation theory in the GW approximation is a useful method for describing electronic properties associated with charged excitations. A hierarchy of GW methods exists, starting from non-self-consistent G0W0, through partial self-consistency in the eigenvalues (ev-scGW) and in the Green function (scGW0), to fully self-consistent GW (scGW). Here, we assess the performance of these methods for benzene, pyridine, and the diazines. The quasiparticle spectra are compared to photoemission spectroscopy (PES) experiments with respect to all measured particle removal energies and the ordering of the frontier orbitals. We find that the accuracy of the calculated spectra does not match the expectations based on their level of self-consistency. In particular, for certain starting points G0W0 and scGW0 provide spectra in better agreement with the PES than scGW