Solvation dynamics in liquids and glasses

Glas maken is één van die technologieën waar de mensheid al lang gebruikt van maakt. Al zo’n vijf duizend jaar om precies te zijn. Dus je zou denken dat we inmiddels wel bijna alles weten wat er over glazen te weten valt. Nou, dat valt tegen. Zeker wanneer je de kennis die we hebben van de fysica van kristallen vergelijkt met die van glazen. Het verschil tussen glazen en kristallen is dat de moleculen waaruit deze substanties zijn opgebouwd, in een glas niet netjes geordend in een rooster zitten zoals in een kristal. Het gebrek aan orde in zo’n glas is één van de redenen dat fysici niet zoveel met glazen aankunnen. Omdat kristallen een grote interne symmetrie hebben, helpt dit bij het begrijpen van wat er op atomair en moleculair niveau allemaal gebeurt. En van daaruit kun je dan allerlei dagelijkse eigenschappen van kristallen verklaren, zoals de vorm, kleur, warmtegeleiding, hardheid, enzovoort. In mijn onderzoek heb ik me geconcentreerd op twee modellen die toegepast worden om the fysica van glazen (en vloeistoffen) te beschrijven in twee extreme omstandigheden. Die modellen heb ik getest op hun effectiviteit en de toepasbaarheid buiten het nauwe temperatuur gebied waar ze doorgaans worden gebruikt in mijn vakgebied van de niet lineaire optica. Het ene uiterste is de extreem lage temperatuur dicht bij het absolute nulpunt. Toe nu toe waren er extra parameters, matsfactoren, nodig om met het model dat bij deze temperatuur gebruikt wordt accurate voorspellingen te doen. Mijn stelling is dat je die parameters helemaal niet nodig hebt. Als je de wiskunde netter doet en ongewenste experimentele effecten uitsluit dan kun je ook zonder die parameters je onderzoeksdata prima verklaren. Het andere uiterste, de hoge temperatuur waar het glas vloeistof is geworden. Het model dat hier wordt toegepast behandelt bezit een groot aantal intern aanpasbare parameters. Het zou mooi zijn als het niet nodig is deze parameters te veranderen als de je naar andere, lagere, temperaturen gaat. Helaas, bij lagere temperaturen moet het karakter van het model aanzienlijk veranderd worden om aan te blijven sluiten bij de realiteit. Ik laat zien hoe die veranderingen bijna allemaal gerelateerd kunnen worden aan de veranderingen in de dynamica van de vloeistof die in een glas verandert. Dus met een paar aanpassingen, die min of meer voortvloeien uit bestaande glasvormingstheorie, kun je de experimenten toch prima beschrijven

Automated Feedback Can Improve Hypothesis Quality

Stating a hypothesis is one of the central processes in inquiry learning, and often forms the starting point of the inquiry process. We designed, implemented, and evaluated an automated parsing and feedback system that informed students about the quality of hypotheses they had created in an online tool, the hypothesis scratchpad. In two pilot studies in different domains (“supply and demand” from economics and “electrical circuits” from physics) we determined the parser's accuracy by comparing its judgments with those of human experts. A satisfactory to high accuracy was reached. In the main study (in the “electrical circuits” domain), students were assigned to one of two conditions: no feedback (control) and automated feedback. We found that the subset of students in the experimental condition who asked for automated feedback on their hypotheses were much more likely to create a syntactically correct hypothesis than students in either condition who did not ask for feedback

Two-Dimensional Electronic Spectroscopy of Chlorophyll a: Solvent Dependent Spectral Evolution

The interaction of the monomeric chlorophyll Q-band electronic transition with solvents of differing physical-chemical properties is investigated through two-dimensional electronic spectroscopy (2DES). Chlorophyll constitutes the key chromophore molecule in light harvesting complexes. It is well-known that the surrounding protein in the light harvesting complex fine-tunes chlorophyll electronic transitions to optimize energy transfer. Therefore, an understanding of the influence of the environment on the monomeric chlorophyll electronic transitions is important. The Q-band 2DES is inhomogeneous at early times, particularly in hydrogen bonding polar solvents, but also in nonpolar solvents like cyclohexane. Interestingly this inhomogeneity persists for long times, even up to the nanosecond time scale in some solvents. The reshaping of the 2DES occurs over multiple time scales and was assigned mainly to spectral diffusion. At early times the reshaping is Gaussian-like, hinting at a strong solvent reorganization effect. The temporal evolution of the 2DES response was analyzed in terms of a Brownian oscillator model. The spectral densities underpinning the Brownian oscillator fitting were recovered for the different solvents. The absorption spectra and Stokes shift were also properly described by this model. The extent and nature of inhomogeneous broadening was a strong function of solvent, being larger in H-bonding and viscous media and smaller in nonpolar solvents. The fastest spectral reshaping components were assigned to solvent dynamics, modified by interactions with the solute

S-COL: A Copernican turn for the development of flexibly reusable collaboration scripts

Collaboration scripts are usually implemented as parts of a particular collaborative-learning platform. Therefore, scripts of demonstrated effectiveness are hardly used with learning platforms at other sites, and replication studies are rare. The approach of a platform-independent description language for scripts that allows for easy implementation of the same script on different platforms has not succeeded yet in making the transfer of scripts feasible. We present an alternative solution that treats the problem as a special case of providing support on top of diverse Web pages: In this case, the challenge is to trigger support based on the recognition of a Web page as belonging to a specific type of functionally equivalent pages such as the search query form or the results page of a search engine. The solution suggested has been implemented by means of a tool called S-COL (Scripting for Collaborative Online Learning) and allows for the sustainable development of scripts and scaffolds that can be used with a broad variety of content and platforms. The tool’s functions are described. In order to demonstrate the feasibility and ease of script reuse with S-COL, we describe the flexible re-implementation of a collaboration script for argumentation in S-COL and its adaptation to different learning platforms. To demonstrate that a collaboration script implemented in S-COL can actually foster learning, an empirical study about the effects of a specific script for collaborative online search on learning activities is presented. The further potentials and the limitations of the S-COL approach are discussed

The use of open data as a material for learning

Open data has potential value as a material for use in learning activities. However, approaches to harnessing this are not well understood or in mainstream use in education. In this research, early adopters from a diverse range of educational projects and teaching settings were interviewed to explore their rationale for using open data in teaching, how suitable activity designs could be achieved, and the practical challenges of using open data. A thematic analysis was conducted to identify patterns and relationships in these open data-based practices that have already emerged. A document analysis of teaching materials and other related artefacts was used to augment and validate the findings. Drawing on this, common approaches and issues are identified, and a conceptual framework to support greater use of open data by educators is described. This paper also highlights where existing concepts in education and educational technology research, including inquiry-based learning, authenticity, motivation, dialogue, and personalisation can help us to understand the value and challenges of using open data in education

Ultrafast structure and dynamics in ionic liquids: 2D-IR spectroscopy probes the molecular origin of viscosity

The viscosity of imidazolium ionic liquids increases dramatically when the strongest hydrogen bonding location is methylated. In this work, ultrafast two-dimensional vibrational spectroscopy of dilute thiocyanate ion ([SCN] -) in 1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ([C4C1im][NTf2]) and 1-butyl-2,3- dimethylimidazolium bis(trifluoromethylsulfonyl)imide ([C4C 1C12im][NTf2]) shows that the structural reorganization occurs on a 26 ± 3 ps time scale and on a 47 ± 15 ps time scale, respectively. The results suggest that the breakup of local ion-cages is the fundamental event that activates molecular diffusion and determines the viscosity of the fluids. © 2014 American Chemical Society

Real-time observation of multiexcitonic states in ultrafast singlet fission using coherent 2D electronic spectroscopy.

Singlet fission is the spin-allowed conversion of a spin-singlet exciton into a pair of spin-triplet excitons residing on neighbouring molecules. To rationalize this phenomenon, a multiexcitonic spin-zero triplet-pair state has been hypothesized as an intermediate in singlet fission. However, the nature of the intermediate states and the underlying mechanism of ultrafast fission have not been elucidated experimentally. Here, we study a series of pentacene derivatives using ultrafast two-dimensional electronic spectroscopy and unravel the origin of the states involved in fission. Our data reveal the crucial role of vibrational degrees of freedom coupled to electronic excitations that facilitate the mixing of multiexcitonic states with singlet excitons. The resulting manifold of vibronic states drives sub-100 fs fission with unity efficiency. Our results provide a framework for understanding singlet fission and show how the formation of vibronic manifolds with a high density of states facilitates fast and efficient electronic processes in molecular systems.This is the author accepted manuscript. The final version is available from NPG via http://dx.doi.org/10.1038/nchem.237