Excited-State Dynamics of Non-Luminescent and Luminescent π-Radicals

Recently, the potential use of organic π-radicals and related spin systems has been expanded to modern technological applications. The unique excited-state dynamics of organic π-radicals can be useful to improve the stability of photochemically unstable organic compounds, make the polarization transfer applicable to information technology, and achieve effective up-conversion of interest for luminescence bioimaging, among others. Furthermore, highly luminescent stable π-radicals have been recently reported, which are especially interesting for application in organic light-emitting devices owing to their potential to provide an internal quantum efficiency of 100 %. Thus, the excited-state nature of stable π-radicals as well as the control of their excited-state spin dynamics are emerging topics both in terms of fundamental science and related technological applications. In this minireview, we focus on the excited-state dynamics of both photostable non(weakly)-luminescent and luminescent π-radicals, which are opposites of each other. In particular, we cover the following topics: 1) effective generation of high-spin photoexcited states and control of the excited-state dynamics by using non-luminescent π-radicals, 2) unique excited-state dynamics of luminescent π-radicals and radical excimers, and 3) applications utilizing excited-state dynamics of π-radicals.     

Dynamics of scalar fields in an expanding/contracting cosmos at finite temperature

This study extends the investigation of quantum dissipative effects of a cosmological scalar field by taking into account cosmic expansion and contraction.Cheung,Drewes,Kang,and Kim calculated the effective action and quantum dissipative effects of a cosmological scalar field in a recent work,where analytical expressions for the effective potential and damping coefficient were presented using a simple scalar model with quartic interactions,and the work was conducted using Minkowski-space propagators in loop diagrams.In this work,we incorporate the Hubble expansion and contraction of the cosmic background and focus on the thermal dynamics of a scalar field in a regime where the effective potential changes slowly.Given that the Hubble parameter,H,attains a small but non-zero value,we carry out calculations to the first order in H.If we set H=0,all results match those in flat spacetime.Interestingly,we must integrate over the resonances,which in turn leads to an amplification of the effects of a non-zero H.This is an intriguing phenomenon,which cannot be uncovered in flat spacetime.The implications on particle creations in the early universe will be studied in a forthcoming study.     

Unravelling the Role of Water in Ultrafast Excited-State Relaxation Dynamics within Nano-Architectures of Chlorophyll a

Water plays a pivotal role in structural stability of supramolecular pigment assemblies designed for natural light harvesting (for example, chlorosome antenna complex) as well as their artificial analogs. However, the dynamic role of water in the context of excite-state relaxation has not been explored till date, which we report here. Using femtosecond transient absorption spectroscopy, we investigate the excited-state dynamics of two types of nano-scale assemblies of chlorophyll a with different structural motifs, rod-shaped and micellar assemblies, that depend on the water content. We show how water participates in excess energy dissipation by vibrational cooling of the non-thermally populated Q_y band at different rates in different types of clusters but exhibits no polar solvation dynamics. For the micelles, we observe a bifurcation of stimulated emission line shape, whereas a positive-to-negative switching of differential absorption is observed for the rods; both these observations are correlated with their specific structural aspects. Density functional theory calculations reveal two possible stable ground state geometries of dimers, accounting for the bifurcation of line shape in micelles. Thus, our study elucidates water-mediated structure–function relationship within these pigment assemblies.     

Variability in the noise-induced modes of climate dynamics

New features of noise-induced climate variability are revealed on the basis of the three-dimensional model derived by Saltzman and Maasch. It is shown that the climate system can be highly noise excitable and it possesses the large-amplitude fluctuations even in those regions where its akin deterministic model does not contain any self-sustained oscillations. Intermittency in small- and large amplitude climate fluctuations between different basins of attraction of a limit cycle and stable equilibria substantially influencing the climate state (from warm to cold and vice versa) are found at various noise intensities. Suddenly occurring jumps between the basins of attraction of two stable equilibria corresponding to the warm and cold climate states are statistically confirmed under a certain diapason of noise intensities. The climate system undergoes transitions between its equilibria in the presence of noise in its prognostic variables. In addition, such transitions become more likely with increasing the noise intensity.     

Tensile properties of microtubules: A study by nonlinear molecular structural mechanics modelling

A nonlinear molecular structural mechanics (MSM) model is proposed in this paper for studying the tensile properties of microtubules (MTs). In the nonlinear MSM models, the interactions between tubulin monomers in MTs are treated as nonlinear axial and torsional springs, whose stiffness coefficients are extracted from all-atom molecular dynamics simulations. The Young's modulus and fracture properties of MTs under tension extracted from the present nonlinear MSM models are found to agree well with the existing simulation and experiment results, which shows the efficiency and accuracy of the proposed nonlinear MSM models. In addition, the nonlinear MSM models are also extended to investigate the tensile properties including Young's modulus and fracture strain of MTs possessing lattice defects. The results obtained from nonlinear MSM models are utilized to develop a predictive equation for quickly predicting the tensile properties of MTs with different lattice defect levels.     

Statistics of polymer capture by a nanopore: A Brownian dynamics simulation study

We investigate the statistics of polymer capture by a nanopore using Brownian dynamics simulations. It is found that when the velocity flux is greater than a critical velocity flux, the capture picture is a random selection process, otherwise it tends to a statistical process governed by energetic considerations. In addition, the chain ends capture probability decreases as the chain length increases and satisfies a power-law scaling of P0(N)~N-0.8.     

Solvent‐Dependent Structure of the I3− Ion Derived from Photoelectron Spectroscopy and Ab Initio Molecular Dynamics Simulations

Ab initio molecular dynamics (MD) simulations of the solvation of LiI₃ in four different solvents (water, methanol, ethanol, and acetonitrile) are employed to investigate the molecular and electronic structure of the I₃^? ion in relation to X‐ray photoelectron spectroscopy (XPS). Simulations show that hydrogen‐bond rearrangement in the solvation shell is coupled to intramolecular bond‐length asymmetry in the I₃^? ion. By a combination of charge analysis and I 4 d core‐level XPS measurements, the mechanism of the solvent‐induced distortions has been studied, and it has been concluded that charge localization mediates intermolecular interactions and intramolecular distortion. The approach involving a synergistic combination of theory and experiment probes the solvent‐dependent structure of the I₃^? ion, and the geometric structure has been correlated with the electronic structure.     

Molecular scale simulations on thermoset polymers: A review

This article reviews the field of molecular simulations of thermoset polymers. This class of polymers is of interest in applications ranging from structural components for aerospace to electronics packaging and predictive simulations of their response is playing an increasing role in understanding the molecular origin of their properties and complementing experiments in the search for tailored materials for specific applications. It focuses on modeling and simulation of the process of curing to predict the molecular structure of these polymers and their thermomechanical response by all-atom molecular dynamics simulations. Results from Monte Carlo and coarse-grained simulations are briefly summarized. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2015 , 53, 103–122     

Free volume characteristics of 2,2-bistrifluoromethyl-4,5-difluoro-1,3-dioxole-co-tetrafluoroethylene copolymers: Effect of composition and molecular weight

2,2-bistrifluoromethyl-4,5-difluoro-1,3-dioxole-co-tetrafluoroethylene (PDD-TFE) copolymer is a good candidate to prepare gas separation membranes with excellent permeability due to its free volume characteristics. However, the influence of PDD-TFE copolymer structure on its free volume characteristics is less studied. In this paper, PDD-TFE copolymers with different compositions and molecular weights were synthesized, and their free volume characteristics were analyzed by positron annihilation lifetime spectroscopy and a molecular dynamics simulation. It indicated that the molar fraction of PDD in copolymers had a significant effect on free volume characteristics, while the molecular weight of copolymers exerted a slight influence on free volume when the molecular weight exceeded a critical region (intrinsic viscosity [η] > 68 ml g⁻¹). PDD-TFE copolymers with greater PDD molar fractions (i.e., 72% and 84%) showed bimodal distributions in positron lifetime and free volume size distributions, while PDD-TFE copolymers with lower PDD molar fractions (i.e., 27% and 35%) exhibited a single peak. The long-lifetime parameter τ₃ was assigned to micro-cavities formed by [-(TFE)_y-PDD-] segments and τ₄ was attributed to micro-cavities formed by [-(PDD)_x-TFE-] segments. The cis and trans transitions of PDD led to a local multilayer spiral structure with a 2.6–4.3 Å layer spacing, which would also increase the free volume of copolymers.