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Time resolved Small Angle X-ray Scattering (SAXS) experiments on detonating explosives have been conducted at Argonne National Laboratory's Advanced Photon Source Dynamic Compression Sector. The purpose of the experiments is to measure the SAXS patterns at tens of ns to a few ls behind the detonation front. Corresponding positions behind the detonation front are of order 0.1-10 mm. From the scattering patterns, properties of the explosive products relative to the time behind the detonation front can be inferred. This report describes how the time and distance from the x-ray probe location to the detonation front is calculated, as well as the uncertainties and sources of uncertainty associated with the calculated times and distances. [ABSTRACT FROM AUTHOR]

The effects of solvent on molecular processes such as excited state relaxation and photochemical reaction often occurs in a nonequilibrium regime. Dynamic processes such as these can be simulated using excited state molecular dynamics. In this work, we describe methods of simulating nonequilibrium solvent effects in excited state molecular dynamics using linear-response time-dependent density functional theory and apparent surface charge methods. These developments include a propagation method for solvent degrees of freedom and analytical energy gradients for the calculation of forces. Molecular dynamics of acetaldehyde in water or acetonitrile are demonstrated where the solute-solvent system is out of equilibrium due to photoexcitation and emission. [ABSTRACT FROM AUTHOR]

This study describes variational energy expressions and analytical excited state energy gradients for time-dependent self-consistent field methods with polarizable solvent effects. Linear response, vertical excitation, and state-specific solvent models are examined. Enforcing a variational ground state energy expression in the state-specific model is found to reduce it to the vertical excitation model. Variational excited state energy expressions are then provided for the linear response and vertical excitation models and analytical gradients are formulated. Using semiempirical model chemistry, the variational expressions are verified by numerical and analytical differentiation with respect to a static external electric field. Analytical gradients are further tested by performing microcanonical excited state molecular dynamics with p-nitroaniline. [ABSTRACT FROM AUTHOR]

We implement and examine three excited state solvent models in time-dependent self-consistent field methods using a consistent formalism which unambiguously shows their relationship. These are the linear response, state specific, and vertical excitation solvent models. Their effects on energies calculated with the equivalent of COSMO/CIS/AM1 are given for a set of test molecules with varying excited state charge transfer character. The resulting solvent effects are explained qualitatively using a dipole approximation. It is shown that the fundamental differences between these solvent models are reflected by the character of the calculated excitations. [ABSTRACT FROM AUTHOR]

The optical response of semiconducting monolayer transition-metal dichalcogenides (TMDCs) is dominated by strongly bound excitons that are stable even at room temperature. However, substrate-related effects such as screening and disorder in currently available specimens mask many anticipated physical phenomena and limit device applications of TMDCs. Here, we demonstrate that that these undesirable effects are strongly suppressed in suspended devices. Extremely robust (photogain > 1,000) and fast (response time < 1 ms) photoresponse allow us to study, for the first time, the formation, binding energies, and dissociation mechanisms of excitons in TMDCs through photocurrent spectroscopy. By analyzing the spectral positions of peaks in the photocurrent and by comparing them with first-principles calculations, we obtain binding energies, band gaps and spin-orbit splitting in monolayer TMDCs. For monolayer MoS2, in particular, we obtain an extremely large binding energy for band-edge excitons, Ebind ⩾ 570 meV. Along with band-edge excitons, we observe excitons associated with a van Hove singularity of rather unique nature. The analysis of the source-drain voltage dependence of photocurrent spectra reveals exciton dissociation and photoconversion mechanisms in TMDCs. [ABSTRACT FROM AUTHOR]

We report 65 T magnetoabsorption spectroscopy of exciton Rydberg states in the archetypal monolayer semiconductor WSe2. The strongly field-dependent and distinct energy shifts of the 2s, 3s, and 4s excited neutral excitons permits their unambiguous identification and allows for quantitative comparison with leading theoretical models. Both the sizes (via low-field diamagnetic shifts) and the energies of the ns exciton states agree remarkably well with detailed numerical simulations using the nonhydrogenic screened Keldysh potential for 2D semiconductors. Moreover, at the highest magnetic fields, the nearly linear diamagnetic shifts of the weakly bound 3s and 4s excitons provide a direct experimental measure of the exciton's reduced mass mr = 0.20 ± 0.01m0. [ABSTRACT FROM AUTHOR]