Characterization of Water Dissociation on α\alpha-Al2_{2}O3_{3}(11ˉ02)(1\bar{1}02): Theory and Experiment

The interaction of water with $\alpha$-alumina (i.e. $\alpha$-Al$_{2}$O$_{3}$ surfaces is important in a variety of applications and a useful model for the interaction of water with environmentally abundant aluminosilicate phases. Despite its significance, studies of water interaction with $\alpha$-Al$_{2}$O$_{3}$ surfaces other than the $(0001)$ are extremely limited. Here we characterize the interaction of water (D$_{2}$O) with a well defined $\alpha$-Al$_{2}$O$_{3}$$(1\bar{1}02)$ surface in UHV both experimentally, using temperature programmed desorption and surface-specific vibrational spectroscopy, and theoretically, using periodic-slab density functional theory calculations. This combined approach makes it possible to demonstrate that water adsorption occurs only at a single well defined surface site (the so-called 1-4 configuration) and that at this site the barrier between the molecularly and dissociatively adsorbed forms is very low: 0.06 eV. A subset of OD stretch vibrations are parallel to this dissociation coordinate, and thus would be expected to be shifted to low frequencies relative to an uncoupled harmonic oscillator. To quantify this effect we solve the vibrational Schr\"odinger equation along the dissociation coordinate and find fundamental frequencies red-shifted by more than 1,500 cm$^{\text{-1}}$. Within the context of this model, at moderate temperatures, we further find that some fraction of surface deuterons are likely delocalized: dissociatively and molecularly absorbed states are no longer distinguishable.Comment: Paper: 22 pages, 9 figures , ESI: 6 pages, 1 figur

Dynamics of water of hydration near disaccharides strongly depends on solute topology: mapping density fluctuations, rotational anisotropy and h-bond exchange mechanism around disaccharides

comunicação em posterDisaccharides such as trehalose are abundant components of cells and may alter the phase behavior or dynamics of phospholipid bilayers: for example, trehalose is a cryoprotectant of lipid bilayers. The origin of this and other effects of disaccharides on membranes is still under debate. One possibility is that some disaccharides alter the dynamics of water of hydration relative to the bulk, and that interactions between the water of hydration of disaccharides and the phospholipids lead to changes in bilayer properties. We address this issue by investigating the dynamics of water near disaccharides kojibiose and trehalose using classical atomistic molecular dynamics simulations and transition state theory. Our results indicate that the cryoprotectant trehalose and the non-cryoprotectant kojibiose differ in the rotational dynamics of their water of hydration, with the subpopulation of water molecules nearest to the central linking oxygen being significantly slower for trehalose. Interestingly, this effect results from differences in both solute chemistry and topology: identical functional groups may interact differently with water depending on the orientation of neighboring groups, in agreement with existing reports on proteins. In contrast to observations on topologically simple solutes, our results indicate that topologically complex solutes such as disaccharides induce unexpected changes in the free energy landscape associated with rotation of water molecules. These results suggest that theoretical models to predict water dynamics near solutes, relevant for example to understand how water dynamics influences protein folding or diffusion through polysaccharide brushes, must account for both solute chemistry and topology

Detecting Weak Signals from Interfaces by High Accuracy Phase-Resolved SFG Spectroscopy

Much work over the last 25 years has demonstrated that the interface-specific, alloptical technique, vibrational sum frequency generation (v-SFG) spectroscopy, is often uniquely capable of characterizing the structure and dynamics of interfacial species. The desired information in such a measurement is the complex second order susceptibility which gives rise to the nonlinear response from interfacial molecules. The ability to detect molecular species yielding only small contributions to the susceptibility is meanwhile limited by the precision by which the spectral phase and amplitude can be determined. In this study we describe a new spectrometer design that offers unprecedented phase and amplitude accuracy while significantly improving the sensitivity of the technique. Combining a full collinear beam geometry with a technique enabling the simultaneous measurement of the complex sample and reference spectrum, uncertainties in the reference phase and amplitude are shown to be greatly reduced. Furthermore, we show that using balanced detection, the signal to noise ratio can be increased by one order of magnitude. The capabilities of the spectrometer are demonstrated by the isolation of a small isotropic surface signal from the bulk dominated nonlinear optical response of z-cut quartz. The achieved precision of our spectrometer enables measurements not currently feasible in v-SFG spectroscopy.Comment: 24 pages, 5 figure

Probing the Birth and Ultrafast Dynamics of Hydrated Electrons at the Gold/Liquid Water Interface via an Optoelectronic Approach

The hydrated electron has fundamental and practical significance in radiation and radical chemistry, catalysis and radiobiology. While its bulk properties have been extensively studied, its behavior at buried solid/liquid interfaces is still unclear due to the lack of effective tools to characterize this short-lived species in between two condensed matter layers. In this study, we develop a novel optoelectronic technique for the characterization of the birth and structural evolution of solvated electrons at the metal/liquid interface with a femtosecond time resolution. We thus recorded for the first time their transient spectra (in a photon energy range from 0.31 to 1.85 eV) in situ with a time resolution of 50 fs. The transient species show state-dependent optical transition behaviors from being isotropic in the hot state to perpendicular to the surface in the trapped and solvated states. The technique will enable a better understanding of hot electron-driven reactions at electrochemical interfaces

A New Approximation Method for the Shapley Value Applied to the WTC 9/11 Terrorist Attack

The Shapley value (Shapley (1953)) is one of the most prominent one-point solution concepts in cooperative game theory that divides revenues (or cost, power) that can be obtained by cooperation of players in the game. The Shapley value is mathematically characterized by properties that have appealing real-world interpretations and hence its use in practical settings is easily justified.The down part is that its computational complexity increases exponentially with the number of players in the game. Therefore, in practical problems that consist of more that 25 players the calculation of the Shapley value is usually too time expensive. Among others the Shapley value is applied in the analysis of terrorist networks (cf. Lindelauf et al. (2013)) which generally extend beyond the size of 25 players. In this paper we therefore present a new method to approximate the Shapley value by refining the random sampling method introduced by Castro et al. (2009). We show that our method outperforms the random sampling method, reducing the average error in the Shapley value approximation by almost 30%. Moreover, our new method enables us to analyze the extended WTC 9/11 network of Krebs (2002) that consists of 69 members. This in contrast to the restricted WTC 9/11 network considered in Lindelauf et al. (2013), that only considered the operational cells consisting of the 19 hijackers that conducted theattack

A New Approximation Method for the Shapley Value Applied to the WTC 9/11 Terrorist Attack

The Shapley value (Shapley (1953)) is one of the most prominent one-point solution concepts in cooperative game theory that divides revenues (or cost, power) that can be obtained by cooperation of players in the game. The Shapley value is mathematically characterized by properties that have appealing real-world interpretations and hence its use in practical settings is easily justified.The down part is that its computational complexity increases exponentially with the number of players in the game. Therefore, in practical problems that consist of more that 25 players the calculation of the Shapley value is usually too time expensive. Among others the Shapley value is applied in the analysis of terrorist networks (cf. Lindelauf et al. (2013)) which generally extend beyond the size of 25 players. In this paper we therefore present a new method to approximate the Shapley value by refining the random sampling method introduced by Castro et al. (2009). We show that our method outperforms the random sampling method, reducing the average error in the Shapley value approximation by almost 30%. Moreover, our new method enables us to analyze the extended WTC 9/11 network of Krebs (2002) that consists of 69 members. This in contrast to the restricted WTC 9/11 network considered in Lindelauf et al. (2013), that only considered the operational cells consisting of the 19 hijackers that conducted theattack

A New Approximation Method for the Shapley Value Applied to the WTC 9/11 Terrorist Attack

The Shapley value (Shapley (1953)) is one of the most prominent one-point solution concepts in cooperative game theory that divides revenues (or cost, power) that can be obtained by cooperation of players in the game. The Shapley value is mathematically characterized by properties that have appealing real-world interpretations and hence its use in practical settings is easily justified. The down part is that its computational complexity increases exponentially with the number of players in the game. Therefore, in practical problems that consist of more that 25 players the calculation of the Shapley value is usually too time expensive. Among others the Shapley value is applied in the analysis of terrorist networks (cf. Lindelauf et al. (2013)) which generally extend beyond the size of 25 players. In this paper we therefore present a new method to approximate the Shapley value by refining the random sampling method introduced by Castro et al. (2009). We show that our method outperforms the random sampling method, reducing the average error in the Shapley value approximation by almost 30%. Moreover, our new method enables us to analyze the extended WTC 9/11 network of Krebs (2002) that consists of 69 members. This in contrast to the restricted WTC 9/11 network considered in Lindelauf et al. (2013), that only considered the operational cells consisting of the 19 hijackers that conducted the attack