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A preceding paper [M. Dhar, J. A. Dickinson, and M. A. Berg, J. Chem. Phys. 159, 054110 (2023)] shows how to remove additive noise from an experimental time series, allowing both the equilibrium distribution of the system and its Green’s function to be recovered. The approach is based on nonlinear-correlation functions and is fully nonparametric: no initial model of the system or of the noise is needed. However, single-molecule spectroscopy often produces time series with either photon or photon-counting noise. Unlike additive noise, photon noise is signal-size correlated and quantized. Photon counting adds the potential for bias. This paper extends noise-corrected-correlation methods to these cases and tests them on synthetic datasets. Neither signal-size correlation nor quantization is a significant complication. Analysis of the sampling error yields guidelines for the data quality needed to recover the properties of a system with a given complexity. We show that bias in photon-counting data can be corrected, even at the high count rates needed to optimize the time resolution. Using all these results, we discuss the factors that limit the time resolution of single-molecule spectroscopy and the conditions that would be needed to push measurements into the submicrosecond region. 

Single-molecule and related experiments yield time series of an observable as it fluctuates due to thermal motion. In such data, it can be difficult to distinguish fluctuating signal from fluctuating noise. We present a method of separating signal from noise using nonlinear-correlation functions. The method is fully nonparametric: No a priori model for the system is required, no knowledge of whether the system is continuous or discrete is needed, the number of states is not fixed, and the system can be Markovian or not. The noise-corrected, nonlinear-correlation functions can be converted to the system’s Green’s function; the noise-corrected moments yield the system’s equilibrium-probability distribution. As a demonstration, we analyze synthetic data from a three-state system. The correlation method is compared to another fully nonparametric approach—time binning to remove noise, and histogramming to obtain the distribution. The correlation method has substantially better resolution in time and in state space. We develop formulas for the limits on data quality needed for signal recovery from time series and test them on datasets of varying size and signal-to-noise ratio. The formulas show that the signal-to-noise ratio needs to be on the order of or greater than one-half before convergence scales at a practical rate. With experimental benchmark data, the positions and populations of the states and their exchange rates are recovered with an accuracy similar to parametric methods. The methods demonstrated here are essential components in building a complete analysis of time series using only high-order correlation functions. 

In a supercooled liquid, the crossover temperature Tc separates a high-temperature region of diffusive dynamics from a low-temperature region of activated dynamics. A molecular-dynamics simulation of all-atom, flexible o-terphenyl [J. Phys. Chem. B 117, 12898 (2013)] is analyzed with advanced statistical methods to reveal the molecular features associated with this crossover. The simulations extend to an α-relaxation time of 14 μs (272.5 K), two-orders of magnitude slower than at Tc (290 K). At Tc and below, a distinct state emerges that immediately precedes an orientational jump. Compared to the initial, tightly caged state, this jump-precursor state has a looser cage, with solid-angular excursions of 0.054–0.0125×4π sr. At Tc (290 K), rate heterogeneity is already the dominant cause of stretched relaxation. Exchange within the distribution of rates is faster than α-relaxation at Tc, but becomes equal to it at the lowest temperature simulated (272.5 K). The results trend toward a recent experimental observation near the glass transition (243 K) [Phys. Rev. E 98, 040603(R) (2018)], which saw exchange substantially slower than α-relaxation. Overall, the dynamic crossover comprises multiple phenomena: the development of heterogeneity, an increasing jump size, an emerging jump-precursor state, and a lengthening exchange time. The crossover is neither sharp, nor a simple superposition of the high- and low-temperature regimes; it is a broad region that contains unique and complex phenomena. 

The chemical and physical properties of microstructured materials vary with position. The photophysics of solute molecules can measure these local properties, but they often show multiple rates (rate dispersion), which complicates the interpretation. In the case of micelles, rate dispersion in a solute’s anisotropy decay has been assigned to either local anisotropy or heterogeneity in the local viscosity. To resolve this conflict, the rotation of PM597 molecules in SDS micelles has been measured by polarized MUPPETS (multiple population-period transient spectroscopy). This 2D technique shows that heterogeneity is strong and that local anisotropy is minimal. The results suggest that on a subnanosecond timescale, the solute sees only one strong fluctuation of the micelle structure. The anisotropic, average structure only emerges on longer timescales.