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Publication# Spectroscopy and dynamics at liquid water interfaces

Abstract

This thesis is a detailed description of three experimental investigations on aqueous interfaces. All projects made use of the microjet technology or the more recently developed flat-jet technique which enables the implementation of liquid water in vacuum chambers. In the first study presented here we show that a flat-jet created from the impingement of two liquid microjets generates a laminar turbulence-free water-water interface. By colliding a Luminol solution microjet with another microjet of hydrogen peroxide solution, the chemiluminescence of Luminol reveals where the liquids mix in the flat-jet. The liquids readily mix in the rims of the flat-jet, while in the middle part the different liquids only meet via diffusion. Flat-jets are stationary systems such that the longitudinal flow direction translates into a time dimension, providing access to the interface in different total interaction times ranging from 10 to 200 µs. This timescale is difficult to access by current techniques. The water-vacuum interface is the next topic, in which we have studied aqueous solutions using microjets and photoelectron spectroscopy (MJ-PES). For the first time, we have experimentally demonstrated the implementation of an absolute photoelectron energy reference in MJ-PES. We could show that there is a concentration-dependent shift of valence bands which were previously (without this absolute energy reference) undetectable. Even though this study was done using a tabletop He plasma light source, it creates the foundation of absolute energy referencing for MJ-PES works done in, e.g., synchrotron laboratories. Lastly, we have built an experimental apparatus to investigate the water-gas interface. Such interfaces are ubiquitous in nature but lack direct experimental works on the molecular scale, namely scattering studies. This is largely due to the technical difficulty imposed by the high vapour pressure of water. The dense layer of vapour shields the liquid surface in such a way that conventional molecular beams cannot travel to and from the liquid surface without interacting with the vapour phase, destroying the initial and final states required to understand the surface scattering event at the quantum level (transmission probability of ~e^(-100)). We propose an alternative method to this: by approaching the molecular beam source and the water flat-jet to a distance of 200 µm or less, the probability of scattering solely at the liquid surface becomes realistic. We have performed preliminary experiments using the developed apparatus.

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Water

Water is an inorganic compound with the chemical formula . It is a transparent, tasteless, odorless, and nearly colorless chemical substance, and it is the main constituent of Earth's hydrosphere and

Aqueous solution

An aqueous solution is a solution in which the solvent is water. It is mostly shown in chemical equations by appending (aq) to the relevant chemical formula. For example, a solution of table salt, o

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High-energy particle physics is going through a crucial moment of its history, one in which it can finally aspire to give a precise answer to some of the fundamental questions it has been conceived for. On the one side, the theoretical picture describing the elementary strong and electroweak interactions below the TeV scale, the Standard Model, has been well consolidated over the decades by the observation and the precise characterization of its constituents. On the other hand, the enormous technological potentialities nowadays available, and the skills accumulated in decades of collider experiments with increasingly high complexity, render for the first time plausible the possibility of addressing complicated and conceptually deep questions like the ones at hand. The best incarnation of this high level of sophistication is the CERN Large Hadron Collider (LHC), the most powerful experimental apparatus ever built, which is designed to shed light on the true nature of fundamental interactions at energies never attained before, and which has already started to open a new era in physics with the recent discovery of the longed-for Higgs boson, a true milestone for the human knowledge as well as one of the most important discoveries in the modern epoch. The knowledge that has been and is going to be reached in these crucial years would of course not be conceivable without a deep interplay between the theoretical and the experimental efforts. In particular, on the theoretical side, not only there are wide groups of researchers devoted to building possible extensions to the Standard Model, which draws the guidelines of current and future experiments, but also there is a vast community whose research is rather aimed at the precise predictions of all the physical observables that could be measured at colliders, and at the systematic improvement of the approximations that currently constrain such predictions. On top of representing the state-of-the-art of the human understanding of the properties that regulate elementary-particle interactions and of the formalisms that describe them, the developments of this line of research have an immediate and significant impact on experiments. Firstly, these detailed calculations are the very theoretical predictions against which experimental data are compared, so they are crucial in establishing the validity or not of the theories according to which they are performed. Secondly, the signals one wants to extract from data at modern colliders are so tiny and difficult to single out that the experimental searches themselves need be supplemented by a detailed work of theoretical modelling and simulation. In this respect, high-precision computations play an essential role in all analysis strategies devised by experimental collaborations, and in many aspects of the detector calibration. It is clear that, for theoretical computations to be useful in experimental analyses and simulations, the predictions they yield should be reliable for all possible configurations of the particles to be detected. Thus the key feature for the present theoretical collider physics is not particularly the computation of observables with high precision only in a limited region of the phase space, but the capability of combining (‘matching’) in a consistent way different approaches, each of which is reliable in a particular kinematic regime. With this perspective, matching techniques represent one of the most promising and successful theoretical frameworks currently available, and are considered as eminently valuable tools both on the theoretical and on the experimental sides. Matched computations are based on a perturbation-theory approach for the description of configurations in which the scattering products are well separated and/or highly energetic: in particular the precision currently attained for all but a few of the relevant processes within the Standard Model is the next-to-leading order (NLO) in powers of the strong quantum-chromodynamics (QCD) coupling constant αS; for the description of configurations in which the particles outgoing the collisions are close to each other and/or have low energy, it can be shown that the perturbation-theory expansion breaks down, and then a complementary method, like the parton shower Monte Carlo (PSMC), has instead to be employed. The task of matching is precisely that of giving a prediction that interpolates between the two approaches in a smooth and theoretically-consistent way. This thesis is focused on MC@NLO, a high-energy physics formalism capable of matching computations performed at the NLO in QCD to PSMC generators, in such a way as to retain the virtues of both approaches while discarding their mutual deficiencies. In particular, the thesis reports on the work successfully achieved in extending MC@NLO from its original numerical implementation, tailored on the HERWIG PSMC, to the other main PSMC programs currently employed by experimental collaborations, PYTHIA and Herwig++, confirming the advocated universality of the method. Differences in the various realizations are explained in detail both at the formal level and through the simulation of various Standard-Model reactions. Moreover we describe how the MC@NLO framework has been developed so as to render its implementation automatic with respect to the physics process one is about to simulate: beyond yielding an enormous increase in its potential for present and future collider phenomenology, and upgrading the standard of precision for high-energy computations to the NLO+PSMC level, this development allows for the first time the application of the MC@NLO formalism to a huge number of relevant and highly complicated reactions, through an implementation which is also easily usable by people well-outside the community of experts in QCD calculations. As example of this new version, called aMC@NLO, recent results are presented for complex scattering processes, involving four or five final-state particles. Finally, possible extensions of the framework to theories beyond the Standard Model, like the supersymmetric version of QCD, are briefly introduced.

Livia Eleonora Bove Kado, Umbertoluca Ranieri

We model, via classical molecular dynamics simulations, the plastic phase of ice VII across a wide range of the phase diagram of interest for planetary investigations. Although structural and dynamical properties of plastic ice VII are mostly independent on the thermodynamic conditions, the hydrogen bond network (HBN) acquires a diverse spectrum of topologies distinctly different from that of liquid water and of ice VII simulated at the same pressure. We observe that the HBN topology of plastic ice carries some degree of similarity with the crystal phase, stronger at thermodynamic conditions proximal to ice VII, and gradually lessening when approaching the liquid state. Our results enrich our understanding of the properties of water at high pressure and high temperature and may help in rationalizing the geology of water-rich planets. Published under an exclusive license by AIP Publishing.

Giovanni Migliorati, Fabio Nobile

Motivated by the numerical treatment of parametric and stochastic PDEs, we analyze the least-squares method for polynomial approximation of multivariate functions based on random sampling according to a given probability measure. Recent work has shown that in the univariate case, the least-squares method is quasi-optimal in expectation in [A. Cohen, M A. Davenport and D. Leviatan. Found. Comput. Math. 13 (2013) 819–834] and in probability in [G. Migliorati, F. Nobile, E. von Schwerin, R. Tempone, Found. Comput. Math. 14 (2014) 419–456], under suitable conditions that relate the number of samples with respect to the dimension of the polynomial space. Here “quasi-optimal” means that the accuracy of the least-squares approximation is comparable with that of the best approximation in the given polynomial space. In this paper, we discuss the quasi-optimality of the polynomial least-squares method in arbitrary dimension. Our analysis applies to any arbitrary multivariate polynomial space (including tensor product, total degree or hyperbolic crosses), under the minimal requirement that its associated index set is downward closed. The optimality criterion only involves the relation between the number of samples and the dimension of the polynomial space, independently of the anisotropic shape and of the number of variables. We extend our results to the approximation of Hilbert space-valued functions in order to apply them to the approximation of parametric and stochastic elliptic PDEs. As a particular case, we discuss “inclusion type” elliptic PDE models, and derive an exponential convergence estimate for the least-squares method. Numerical results confirm our estimate, yet pointing out a gap between the condition necessary to achieve optimality in the theory, and the condition that in practice yields the optimal convergence rate.

2015