Ab Initio-Based Modeling of Thermodynamic Cyclic Voltammograms: A Benchmark Study on Ag(100) in Bromide Solutions.

Experimental cyclic voltammograms (CVs) measured in the slow scan rate limit can be entirely described in terms of the thermodynamic equilibrium quantities of the electrified solid-liquid interface. They correspondingly serve as an important benchmark for the quality of first-principles calculations of interfacial thermodynamics. Here, we investigate the partially drastic approximations made presently in computationally efficient calculations for the well-defined showcase of an Ag(100) model electrode in Br-containing electrolytes, where the nontrivial part of the CV stems from the electrosorption of Br ions. We specifically study the entanglement of common approximations in the treatment of solvation and field effects, as well as in the way macroscopic averages of the two key quantities, namely, the potential-dependent adsorbate coverage and electrosorption valency, are derived from the first-principles energetics. We demonstrate that the combination of energetics obtained within an implicit solvation model and a perturbative second order account of capacitive double layer effects with a constant-potential grand-canonical Monte Carlo sampling of the adsorbate layer provides an accurate description of the experimental CV. However, our analysis also shows that error cancellation at lower levels of theory may equally lead to good descriptions even though key underlying physics such as the disorder-order transition of the Br adlayer at increasing coverages is inadequately treated.

Characters matter: How narratives shape affective responses to risk communication.

INTRODUCTION: Whereas scientists depend on the language of probability to relay information about hazards, risk communication may be more effective when embedding scientific information in narratives. The persuasive power of narratives is theorized to reside, in part, in narrative transportation. PURPOSE: This study seeks to advance the science of stories in risk communication by measuring real-time affective responses as a proxy indicator for narrative transportation during science messages that present scientific information in the context of narrative. METHODS: This study employed a within-subjects design in which participants (n = 90) were exposed to eight science messages regarding flood risk. Conventional science messages using probability and certainty language represented two conditions. The remaining six conditions were narrative science messages that embedded the two conventional science messages within three story forms that manipulated the narrative mechanism of character selection. Informed by the Narrative Policy Framework, the characters portrayed in the narrative science messages were hero, victim, and victim-to-hero. Natural language processing techniques were applied to identify and rank hero and victim vocabularies from 45 resident interviews conducted in the study area; the resulting classified vocabulary was used to build each of the three story types. Affective response data were collected over 12 group sessions across three flood-prone communities in Montana. Dial response technology was used to capture continuous, second-by-second recording of participants' affective responses while listening to each of the eight science messages. Message order was randomized across sessions. ANOVA and three linear mixed-effects models were estimated to test our predictions. RESULTS: First, both probabilistic and certainty science language evoked negative affective responses with no statistical differences between them. Second, narrative science messages were associated with greater variance in affective responses than conventional science messages. Third, when characters are in action, variation in the narrative mechanism of character selection leads to significantly different affective responses. Hero and victim-to-hero characters elicit positive affective responses, while victim characters produce a slightly negative response. CONCLUSIONS: In risk communication, characters matter in audience experience of narrative transportation as measured by affective responses.

Electron Transfer Methods in Open Systems.

Utilization of electron transfer methods for description of quantum transport is popular due to simplicity of the formulation and its ability to account for basic physics of electron exchange between the system and baths. At the same time, the necessity to go beyond simple golden rule-type expressions for rates was indicated in the literature and ad hoc formulations were proposed. Similarly, kinetic schemes for quantum transport beyond the usual second-order Lindblad/Redfield considerations were discussed. Here we utilize recently introduced the nonequilibrium Hubbard Green's function diagrammatic technique to analyze the construction of rates in open systems. We show that previous considerations for rates of second and fourth order can be obtained as a particular case of zero- and second-order Green's function diagrammatic series with bare diagrams. We discuss limitations of previous considerations, stress advantages of the Hubbard Green's function approach in constructing the rates, and indicate that standard dressing of the diagrams is a natural way to account for additional baths/degrees of freedom in the formulation of generalized expressions for the rates.

Cultural Theory of Risk as a Heuristic for Understanding Perceptions of Oil and Gas Development in Eastern Montana, USA.

This paper applies Douglas' cultural theory of risk to understand perceptions of risk associated with oil and gas development in eastern Montana. Based on the analysis of interviews with 36 rural residents, findings show the dominant perception of risk is most closely aligned with an Individualist worldview. Despite direct experience with oil or wastewater spills, most interviewees described spills as "no big deal", viewed nature as resilient, and felt that the economic benefits outweigh negative impacts. Cultural theory was a useful heuristic for understanding this dominant worldview, as well as identifying points of deviation. For example, interviewees discussed the benefits of landowner associations - a more Egalitarian approach to dealing with oil companies. Some landowners relied on external authorities (e.g., sheriff) when dealing with oil companies, revealing a Hierarchical approach to issues they face. Interviewees expressed frustration with the lack of enforcement of existing regulations, which can be interpreted as either support for - or indictment of - Hierarchical solutions. While the Individualist worldview is dominant, our qualitative analysis reveals the complex tensions at work among rural residents. The results suggest areas where policymakers, advocacy groups, and residents may find common ground to address potential environmental and health risks.