Memory effects and static disorder reduce information in single-molecule signals

A key theoretical challenge posed by single-molecule studies is the inverse problem of deducing the underlying molecular dynamics from the time evolution of low-dimensional experimental observables. Toward this goal, a variety of low-dimensional models have been proposed as descriptions of single-molecule signals, including random walks with or without conformational memory and/or with static or dynamics disorder. Differentiating among different models presents a challenge, as many distinct physical scenarios lead to similar experimentally observable behaviors such as anomalous diffusion and nonexponential relaxation. Here we show that information-theory-based analysis of single-molecule time series, inspired by Shannon's work studying the information content of printed English, can differentiate between Markov (memoryless) and non-Markov single-molecule signals and between static and dynamic disorder. In particular, non-Markov time series are more predictable and thus can be compressed and transmitted within shorter messages (i.e. have a lower entropy rate) than appropriately constructed Markov approximations, and we demonstrate that in practice the LZMA compression algorithm reliably differentiates between these entropy rates across several simulated dynamical models.

Transition from spin glass to paramagnetism in the magnetic properties of PrAu2Si2

It is unexpected that a spin-glass transition, which generally occurs only in system with some form of disorder, was observed in the ThCr2Si2-type compound PrAu2Si2 at a temperature of 3 K. This puzzling phenomenon was later explained based on a novel dynamic frustration model that does not involve static disorder. We present the results of re-verification of the reported spin-glass behaviors by measuring the physical properties of three polycrystalline PrAu2Si2 samples annealed under different conditions. Indeed, in the sample annealed at 827 ◦C for one week, a spin-glass transition does occur at a temperature of T f~2.8 K as that reported previously in the literature. However, it is newly found that the spin-glass effect is actually more pronounced in the as-cast sample, and almost completely disappears in the well-annealed (at 850 ◦C for 4 weeks) sample. The annealing effect observed in PrAu2Si2, that is, spin glass to paramagnetism transition is discussed by comparing with earlier results reported on the same system and other isomorphic compounds.

Heterogeneous Pair Approximation of Methanol Oxidation on TiO2 Reveals Two Reaction Pathways

We propose a novel method to simulate the chemical kinetics of methanol oxidation on the rutile TiO2(110) surface. This method must be able to capture the effects of static disorder (site-to-site variations in the rate constants), as well as dynamic correlation (interdependent probabilities of finding reactants and products next to each other). Combining the intuitions of the mean-field steady state (MFSS) method and the pair approximation (PA), we consider representative pairs of sites in a self-consistent bath of the average pairwise correlation. Pre-averaging over the static disorder in one site of each pair makes this half heterogeneous pair approximation (HHPA) efficient enough to simulate systems of several species and calibrate rate constants. According to the simulated kinetics, a static disorder in the hole transfer steps suffices to reproduce the stretched exponentials in the observed kinetics. The identity of the dominant hole scavenger is found to be temperature-dependent -- the methoxy anion at 80 K and the methanol molecule at 180 K. Moreover, two distinct groups of 5-coordinate titanium (Ti5c) sites emerge -- a high-activity group and a low-activity group -- even though no such division exists in the rate constants. Since the division is quite insensitive to the type of static disorder, the emergence of the two groups might play a significant role in a variety of photocatalytic processes on TiO2.

Intrinsically disordered proteins: modes of binding with emphasis on disordered domains

Our notions of protein function have long been determined by the protein structure–function paradigm. However, the idea that protein function is dictated by a prerequisite complementarity of shapes at the binding interface is becoming increasingly challenged. Interactions involving intrinsically disordered proteins (IDPs) have indicated a significant degree of disorder present in the bound state, ranging from static disorder to complete disorder, termed ‘random fuzziness’. This review assesses the anatomy of an IDP and relates how its intrinsic properties permit promiscuity and allow for the various modes of interaction. Furthermore, a mechanistic overview of the types of disordered domains is detailed, while also relating to a recent example and the kinetic and thermodynamic principles governing its formation.

A universal Urbach rule for disordered organic semiconductors

In crystalline semiconductors, absorption onset sharpness is characterized by temperature-dependent Urbach energies. These energies quantify the static, structural disorder causing localized exponential-tail states, and dynamic disorder from electron-phonon scattering. Applicability of this exponential-tail model to disordered solids has been long debated. Nonetheless, exponential fittings are routinely applied to sub-gap absorption analysis of organic semiconductors. Herein, we elucidate the sub-gap spectral line-shapes of organic semiconductors and their blends by temperature-dependent quantum efficiency measurements. We find that sub-gap absorption due to singlet excitons is universally dominated by thermal broadening at low photon energies and the associated Urbach energy equals the thermal energy, regardless of static disorder. This is consistent with absorptions obtained from a convolution of Gaussian density of excitonic states weighted by Boltzmann-like thermally activated optical transitions. A simple model is presented that explains absorption line-shapes of disordered systems, and we also provide a strategy to determine the excitonic disorder energy. Our findings elaborate the meaning of the Urbach energy in molecular solids and relate the photo-physics to static disorder, crucial for optimizing organic solar cells for which we present a revisited radiative open-circuit voltage limit.

Influence of static disorder of charge transfer state on voltage loss in organic photovoltaics

Spectroscopic measurements of charge transfer (CT) states provide valuable insight into the voltage losses in organic photovoltaics (OPVs). Correct interpretation of CT-state spectra depends on knowledge of the underlying broadening mechanisms, and the relative importance of molecular vibrational broadening and variations in the CT-state energy (static disorder). Here, we present a physical model, that obeys the principle of detailed balance between photon absorption and emission, of the impact of CT-state static disorder on voltage losses in OPVs. We demonstrate that neglect of CT-state disorder in the analysis of spectra may lead to incorrect estimation of voltage losses in OPV devices. We show, using measurements of polymer:non-fullerene blends of different composition, how our model can be used to infer variations in CT-state energy distribution that result from variations in film microstructure. This work highlights the potential impact of static disorder on the characteristics of disordered organic blend devices.

A Universal Urbach Rule for Disordered Organic Semiconductors

In crystalline semiconductors, the sharpness of the absorption spectrum onset is characterized by temperature-dependent Urbach energies. These energies quantify the static, structural disorder causing localized exponential tail states, and the dynamic disorder due to electron-phonon scattering. The applicability of this exponential-tail model to molecular and amorphous solids has long been debated. Nonetheless, exponential fittings are routinely applied to the analysis of the sub-gap absorption of organic semiconductors alongside Gaussian-like spectral line-shapes predicted by non-adiabatic Marcus theory. Herein, we elucidate the sub-gap spectral line-shapes of organic semiconductors and their blends by temperature-dependent quantum efficiency measurements in photovoltaic structures. We find that the Urbach energy associated with singlet excitons universally equals the thermal energy regardless of static disorder. These observations are consistent with absorption spectra obtained from a convolution of Gaussian density of excitonic states weighted by a Boltzmann factor. A generalized Marcus charge transfer model is presented that explains the absorption spectral line-shape of disordered molecular matrices, and we also provide a simple strategy to determine the excitonic disorder energy. Our findings elaborate the true meaning of the dynamic Urbach energy in molecular solids and deliver a way of relating the photo-physics to static disorder, crucial for optimizing molecular electronic devices such as organic solar cells.