A parallel multistate framework for atomistic non-equilibrium reaction dynamics of solutes in strongly interacting organic solvents

We describe a parallel linear-scaling computational framework developed to implement arbitrarily large multi-state empirical valence bond (MS-EVB) calculations within CHARMM. Forces are obtained using the Hellman-Feynmann relationship, giving continuous gradients, and excellent energy conservation. Utilizing multi-dimensional Gaussian coupling elements fit to CCSD(T)-F12 electronic structure theory, we built a 64-state MS-EVB model designed to study the F + CD3CN -> DF + CD2CN reaction in CD3CN solvent. This approach allows us to build a reactive potential energy surface (PES) whose balanced accuracy and efficiency considerably surpass what we could achieve otherwise. We use our PES to run MD simulations, and examine a range of transient observables which follow in the wake of reaction, including transient spectra of the DF vibrational band, time dependent profiles of vibrationally excited DF in CD3CN solvent, and relaxation rates for energy flow from DF into the solvent, all of which agree well with experimental observations. Immediately following deuterium abstraction, the nascent DF is in a non-equilibrium regime in two different respects: (1) it is highly excited, with ~23 kcal mol-1 localized in the stretch; and (2) not yet Hydrogen bonded to the CD3CN solvent, its microsolvation environment is intermediate between the non-interacting gas-phase limit and the solution-phase equilibrium limit. Vibrational relaxation of the nascent DF results in a spectral blue shift, while relaxation of its microsolvation environment results in a red shift. These two competing effects result in a post-reaction relaxation profile distinct from that observed when DF vibration excitation occurs within an equilibrium microsolvation environment. The parallel software framework presented in this paper should be more broadly applicable to a range of complex reactive systems.Comment: 58 pages and 29 Figure

Near-field optical imaging and spectroscopy of a coupled quantum wire-dot structure

A coupled GaAs/AlGaAs quantum wire (QWR)-dot sample grown by molecular beam epitaxy on a patterned (311)A GaAs substrate is studied by near-field spectroscopy at a temperature of 10 K with a spectral resolution of 100 µeV. The two-dimensional potential energy profiles of the sample including localized excitonic states caused by structural disorder are determined in photoluminescence measurements with a spatial resolution of 150 nm. One finds a potential barrier of 20 meV between the quantum wire and the embedding quantum well (QW) on the mesa top of the structure. This is due to local thinning of the GaAs layer. In contrast, the wire-dot interface results free of energy barriers. The spatial variation of the GaAs layer thickness provides information on the growth mechanism determined by lateral diffusion of Ga atoms which is modeled by an analytical model. By performing spatially resolved photoluminescence excitation measurements on this wire-dot structure, we present a method for investigating carrier transport in low-dimensional systems: The dot area is used as an optical marker for excitonic diffusion via QW and QWR states. The two-dimensional (2D) and 1D diffusion coefficients are extracted as a function of the temperature and discussed

Temperature-dependent near-field imaging of delocalized and localized excitons in single quantum wires

Summary form only given. Recent microphotoluminescence studies have shown that the low-temperature emission spectra of semiconductor quantum wires are dominated by localized, quasi-zero-dimensional, excitons. This implies that both the optical and transport properties of such quasi-one-dimensional (Q1D) nanostructures are similar to that of a chain of quantum dots. It also hinders the observation of some truly one-dimensional quantum effects, such as the ballistic or diffusive one-dimensional exciton transport, expected in nanostructures containing Q1D excitons that are delocalized over mesoscopic length scales. We present the first experimental evidence for such delocalized excitons in a single quantum wire. A novel coupled quantum wire-dot nanostructure is studied by low temperature near-field photoluminescence (PL) spectroscopy

Transition from ballistic to drift motion in high-field transport in GaAs

With strong THz pulses, we measure ultrafast transport of electrons, holes, and an electron-hole plasma in GaAs. The transition from ballistic to drift-like transport is strongly influenced by electron-hole scattering

Going to the exclusive show : exhibition strategies and moviegoing memories of Disneys animated feature films in Ghent (1937-1982)

This is a case study of the exploitation and experience of Disney's animated feature films from the 1930s to the 1980s in Ghent (Belgium). It is a historical study of programming practices and financial strategies which constructed childhood memories on watching Disney. The study is a contribution to a historical understanding of the implications of global distribution of film as cultural products and the counter pull of localism. Using a multi-method approach, the argument is made that the scarce screenings were strategically programmed to uplift the moviegoing experience into something out of the ordinary in everyday life. Programming and revenue data characterize the screenings as exclusive and generating high intakes. Consequently, the remembered screenings did not exhale an easy accessible social status nor an image of pervasiveness of popular childhood film, contradictory to conventional accounts of Disney's ubiquity in popular culture

Coherent oscillations of electrons in tunnel-coupled wells under ultrafast intersubband excitation

Ultrafast intersubband excitation of electrons in tunnell-coupled wells is studied depending on the structure parameters, the duration of the infrared pump and the detuning frequency. The temporal dependencies of the photoinduced concentration and dipole moment are obtained for two cases of transitions: from the single ground state to the tunnel-coupled excited states and from the tunnel-coupled states to the single excited state. The peculiarities of dephasing and population relaxation processes are also taken into account. The nonlinear regime of the response is also considered when the splitting energy between the tunnel-coupled levels is renormalized by the photoexcited electron concentration. The dependencies of the period and the amplitude of oscillations on the excitation pulse are presented with a description of the nonlinear oscillations damping.Comment: 8 pages, 12 figure

Description and Impact of Encounters With Deceased Partners or Spouses

This study investigates perceived interactions with the deceased, a phenomenon reported across societies, with 30-34% of individuals likely experiencing at least one ADC in their lifetime. Despite this prevalence, studies examining the impact of ADCs’ on those who have lost partners are limited. We present data from 70 individuals reporting partner ADCs via an online survey. Forty percent reported accelerated recovery and 42.9% confirm the ADCs’ significant influence in their grieving, with 61% expressing a desire for continued contact. ADCs, interestingly, didn’t worsen their pain. The influence on grief-related sadness varied: 41% noted no change, while 40% reported reduced sadness. Forty-seven percent ac- knowledged ADCs eased their loss acceptance. The data highlight ADCs’ substantial, po-tentially therapeutic role in grief and healing, despite varying effects on sadness and recovery.This study underscores the ADCs’ possible positive influence on bereaved partners, ad-vocating for a deeper understanding of this phenomenon in the grieving process

Aerosol midlatitude cyclone indirect effects in observations and high-resolution simulations

Aerosol-cloud interactions are a major source of uncertainty in inferring the climate sensitivity from the observational record of temperature. The adjustment of clouds to aerosol is a poorly constrained aspect of these aerosol-cloud interactions. Here, we examine the response of midlatitude cyclone cloud properties to a change in cloud droplet number concentration (CDNC). Idealized experiments in high-resolution, convection-permitting global aquaplanet simulations with constant CDNC are compared to 13 years of remote-sensing observations. Observations and idealized aquaplanet simulations agree that increased warm conveyor belt (WCB) moisture flux into cyclones is consistent with higher cyclone liquid water path (CLWP). When CDNC is increased a larger LWP is needed to give the same rain rate. The LWP adjusts to allow the rain rate to be equal to the moisture flux into the cyclone along the WCB. This results in an increased CLWP for higher CDNC at a fixed WCB moisture flux in both observations and simulations. If observed cyclones in the top and bottom tercile of CDNC are contrasted it is found that they have not only higher CLWP but also cloud cover and albedo. The difference in cyclone albedo between the cyclones in the top and bottom third of CDNC is observed by CERES to be between 0.018 and 0.032, which is consistent with a 4.6-8.3gWmg‾² in-cyclone enhancement in upwelling shortwave when scaled by annual-mean insolation. Based on a regression model to observed cyclone properties, roughly 60g% of the observed variability in CLWP can be explained by CDNC and WCB moisture flux

Structured film-viewing preferences and practices : a quantitative analysis of hierarchies in screen and content selection amongst young people in Flanders

Aleit Veenstra, Philippe Meers and Daniel Biltereyst address a specific segment of a typical small-market audience—Flemish youth film viewers. Their study “Structured Film Viewing Preferences and Practices: A Quantitative Analysis of Hierarchies in Screen and Content Selection among Young People in Flanders” deals with one of the symptomatic problems of the era of convergent audiences, the multiplication of screens used for domestic consumption of audiovisual content. Building an intriguing empirical design, Veenstra and her colleagues aim to identify patterns of screen selection and their relation to the perceived value of Hollywood, European and domestic Flemish films. Their conclusion is that there are well-articulated hierarchies applied by the audience members in the selection of both film titles and reception screens and that, to put it simply, in the case of screens, size matters

Coherent Optical polarization of Bulk GaAs Studied by Femtosecond Photon-Echo Spectroscopy

The nonlinear polarization close to the band gap of GaAs is studied by spectrally and temporally resolved four-wave mixing. Excitonic and free carrier contributions both excited within the bandwidth of the 100 fs pulses are distinguished for the first time. The excitonic part dominates at carrier densities below 1016 cm-3. At higher density, nonthermalized free carriers give rise to an additional component resonant to the pulse that shows a photon-echo-like time behavior. Monte Carlo simulations including the coherent polarization and the scattering dynamics of the carriers account for the data