A classical reactive potential for molecular clusters of sulphuric acid and water

We present a two-state empirical valence bond (EVB) potential describing interactions between sulphuric acid and water molecules and designed to model proton transfer between them within a classical dynamical framework. The potential has been developed in order to study the properties of molecular clusters of these species, which are thought to be relevant to atmospheric aerosol nucleation. The particle swarm optimisation method has been used to fit the parameters of the EVB model to density functional theory (DFT) calculations. Features of the parametrised model and DFT data are compared and found to be in satisfactory agreement. In particular, it is found that a single sulphuric acid molecule will donate a proton when clustered with four water molecules at 300 K and that this threshold is temperature dependent

Effects of scopolamine on matching to sample paradigm and related tests in human subjects

This was a double-blind placebo-controlled study with a cross-over design to examine the effects of scopolamine on cognitive functions in young healthy subjects. Scopolamine hydrobromide was administered subcutaneously to 12 subjects (mean +/- SD age 23.8 +/- 2.2 years) at doses of 0.3 and 0.6 mg in comparison with two placebo conditions. Scopolamine at both doses produced marked sedation as rated by subjects and an observer. In the continuous performance test, vigilance was impaired by both doses of scopolamine. The span of apprehension test showed differing results (only the high dose of scopolamine showed a performance decrement only in the three-character version of the span of apprehension test). Significant impairment by both doses of scopolamine was seen in immediate and delayed free recall, continuous visual recognition, running word recognition and running picture recognition. While scopolamine caused a significant slowing in average reaction times for simultaneous matching as well as for delayed matching, subjects made more errors under scopolamine compared to placebo only in delayed matching, not in simultaneous matching. Also, the main outcome of matching to sample showed significant effects only in delayed matching, not in simultaneous matching. Notable in this study is the incongruity between the simultaneous matching test and the span of apprehension test on the one hand and the other cognitive tests used on the other. These results demonstrated that scopolamine has a greater effect on memory than on attention. Thus, the scopolamine-induced effects in the present study seem to be more relevant to Alzheimer's disease in an advanced phase than to normal aging. Copyright (C) 2003 S. Karger AG, Basel

Effects of a three-week executive control training on adaptation to task difficulty and emotional interference

Intact executive functions are characterized by flexible adaptation to task requirements, while these effects are reduced in internalizing disorders. Furthermore, as executive functions play an important role in emotion regulation, deficits in executive functions may contribute to symptom generation in psychological disorders through increased emotional interference. Thus, the present study investigated transfer effects of a three-week executive control training on adaptation to task difficulty and emotional interference in healthy participants (n = 24) to further explore the training’s suitability for clinical application. To assess the adaptation to task difficulty, the proportion congruency effect on behavioral data (response times, error rates) and ERP measures (N2, CRN) was assessed in a flanker task with varying frequency of incompatible trials (25%, 75%). To quantify emotional interference, flanker stimuli were superimposed on neutral or negative pictures. Replicating previous results, the training increased interference control as indexed by decreased response times and errors rates, increased N2 amplitude and decreased CRN amplitude in incompatible trials after training. Proportion congruency effects were weaker than expected and not affected by the training intervention. The training lead to a shift in the time-point of emotional interference: before training negative pictures lead to a reduction in CRN amplitude, while after training this reduction was observed for the N2. This pattern illustrates that the training leads to a change in task processing mode from predominant response-related cognitive control to predominant stimulus-related cognitive control (N2), indicating a proactive processing mode.Peer Reviewe

Cognitive control is quickly adapted to actual task requirements despite misleading context cues—Evidence from the N2, CRN, and ERN

Cognitive control is flexibly adapted to task requirements in healthy individuals. Medio-frontal negativities in the event-related potential of the electroencephalogram can serve as indicators of cognitive control. With increasing conflict frequency, stimulus-locked control, as indexed by the N2, is increased and response-locked control, as indexed by the correct-related negativity, is reduced. On the behavioral level, this shift is associated with improved conflict resolution as evident in reduced response times and error rates in incompatible trials and a reduced response time congruency effect. Cognitive control adaptation might be implemented through experience-based task sets specifying advantageous processing strategies. Here, we investigated whether the cognitive control task set will be sustained when coupled with a contextual cue, even when the initial task requirements are no longer present. A flanker task with two conflict frequency conditions (25% incompatible and 75% incompatible trials) was presented. In the training phase, the conflict frequency conditions were paired with a distinct context cue (i.e., background color). In the test phase, the previously associated cues were again presented, but conflict frequency was identical in both conditions (50% incompatible trials). Although typical cognitive control adaptation was observed in the training phase on the behavioral and event-related potentials level, this pattern was not sustained in the test phase. Thus, the present study provides further evidence that cognitive control is flexibly adapted to task requirements even in the presence of misleading cues

Anomalously Strong Effect of the Ion Sign on the Thermochemistry of Hydrogen Bonded Aqueous Clusters of Identical Chemical Composition

The sign preference of hydrogen bonded aqueous ionic clusters X±(H2O)i (n =1–5, X = F; Cl; Br) has been investigated using the Density Functional Theory and ab initio MP2 method. The present study indicates the anomalously large difference in formation free energies between cations and anions of identical chemical composition. The effect of vibrational anharmonicity on stepwise Gibbs free energy changes has been investigated, and possible uncertainties associated with the harmonic treatment of vibrational spectra have been discussed

Molecular simulations of heterogeneous ice nucleation. II. Peeling back the layers

Coarse grained molecular dynamics simulations are presented in which the sensitivity of the ice nucleation rate to the hydrophilicity of a graphene nanoflake is investigated. We find that an optimal interaction strength for promoting ice nucleation exists, which coincides with that found previously for a face centered cubic (111) surface. We further investigate the role that the layering of interfacial water plays in heterogeneous ice nucleation and demonstrate that the extent of layering is not a good indicator of ice nucleating ability for all surfaces. Our results suggest that to be an efficient ice nucleating agent, a surface should not bind water too strongly if it is able to accommodate high coverages of water

Molecular simulations of heterogeneous ice nucleation. I. Controlling ice nucleation through surface hydrophilicity

Ice formation is one of the most common and important processes on earth and almost always occurs at the surface of a material. A basic understanding of how the physicochemical properties of a material’s surface affect its ability to form ice has remained elusive. Here, we use molecular dynamics simulations to directly probe heterogeneous ice nucleation at a hexagonal surface of a nanoparticle of varying hydrophilicity. Surprisingly, we find that structurally identical surfaces can both inhibit and promote ice formation and analogous to a chemical catalyst, it is found that an optimal interaction between the surface and the water exists for promoting ice nucleation. We use our microscopic understanding of the mechanism to design a modified surface in silico with enhanced ice nucleating ability