Influence of environment induced correlated fluctuations in electronic coupling on coherent excitation energy transfer dynamics in model photosynthetic systems

Two-dimensional photon-echo experiments indicate that excitation energy transfer between chromophores near the reaction center of the photosynthetic purple bacterium Rhodobacter sphaeroides occurs coherently with decoherence times of hundreds of femtoseconds, comparable to the energy transfer time scale in these systems. The original explanation of this observation suggested that correlated fluctuations in chromophore excitation energies, driven by large scale protein motions could result in long lived coherent energy transfer dynamics. However, no significant site energy correlation has been found in recent molecular dynamics simulations of several model light harvesting systems. Instead, there is evidence of correlated fluctuations in site energy-electronic coupling and electronic coupling-electronic coupling. The roles of these different types of correlations in excitation energy transfer dynamics are not yet thoroughly understood, though the effects of site energy correlations have been well studied. In this paper, we introduce several general models that can realistically describe the effects of various types of correlated fluctuations in chromophore properties and systematically study the behavior of these models using general methods for treating dissipative quantum dynamics in complex multi-chromophore systems. The effects of correlation between site energy and inter-site electronic couplings are explored in a two state model of excitation energy transfer between the accessory bacteriochlorophyll and bacteriopheophytin in a reaction center system and we find that these types of correlated fluctuations can enhance or suppress coherence and transfer rate simultaneously. In contrast, models for correlated fluctuations in chromophore excitation energies show enhanced coherent dynamics but necessarily show decrease in excitation energy transfer rate accompanying such coherence enhancement. Finally, for a three state model of the Fenna-Matthews-Olsen light harvesting complex, we explore the influence of including correlations in inter-chromophore couplings between different chromophore dimers that share a common chromophore. We find that the relative sign of the different correlations can have profound influence on decoherence time and energy transfer rate and can provide sensitive control of relaxation in these complex quantum dynamical open systems

Noncognitive Factors Affecting Academic Achievement of Juvenile Delinquents

The present study provides a description and analysis of the plight of first-time detained juvenile delinquents in the United States and the impact of noncognitive attributes and academic achievement on grades. Juvenile delinquents have poor outcomes as adults in higher rates of drug abuse, poor high school graduation rates, and lowered employment well into adulthood. The research questions examined the correlation among the noncognitive attributes of grit, academic self-concept, mental health, and self-esteem, academic achievement, and English and Mathematics grades for first-time detained juvenile delinquents aged 10-18. A multiple regression analysis of archival records of students in a short-term juvenile detention center was conducted. Findings showed three predictor variables were statistically significant and influenced academic performance measured by grades: verbal ability, social self-esteem, and prosocial skills. For juvenile delinquents (n = 72; males = 58, females = 14) aged 10-18 (M =15.3; SD = 1.6; range 10-18), the three predictor variables predicted English grades (adjusted R2 = .280) and Mathematics grades (adjusted R2 = .225). There was a discussion and recommendations for policies and research. The results support the need to consider noncognitive factors and the consideration of communication skills in the education of juvenile delinquents

Consistent schemes for non-adiabatic dynamics derived from partial linearized density matrix propagation

Powerful approximate methods for propagating the density matrix of complex systems that are conveniently described in terms of electronic subsystem states and nuclear degrees of freedom have recently been developed that involve linearizing the density matrix propagator in the difference between the forward and backward paths of the nuclear degrees of freedom while keeping the interference effects between the different forward and backward paths of the electronic subsystem described in terms of the mapping Hamiltonian formalism and semi-classical mechanics. Here we demonstrate that different approaches to developing the linearized approximation to the density matrix propagator can yield a mean-field like approximate propagator in which the nuclear variables evolve classically subject to Ehrenfest-like forces that involve an average over quantum subsystem states, and by adopting an alternative approach to linearizing we obtain an algorithm that involves classical like nuclear dynamics influenced by a quantum subsystem state dependent force reminiscent of trajectory surface hopping methods. We show how these different short time approximations can be implemented iteratively to achieve accurate, stable long time propagation and explore their implementation in different representations. The merits of the different approximate quantum dynamics methods that are thus consistently derived from the density matrix propagator starting point and different partial linearization approximations are explored in various model system studies of multi-state scattering problems and dissipative non-adiabatic relaxation in condensed phase environments that demonstrate the capabilities of these different types of approximations for treating non-adiabatic electronic relaxation, bifurcation of nuclear distributions, and the passage from nonequilibrium coherent dynamics at short times to long time thermal equilibration in the presence of a model dissipative environment

Computer simulations of localized small polarons in amorphous polyethylene

We use a simple mean field scheme to compute the polarization energy of an excess electron in amorphous polyethylene that allows us to study dynamical properties. Nonadiabatic simulations of an excess electron in amorphous polyethylene at room temperature show the spontaneous formation of localized small polaron states in which the electron is confined in a spherically shaped region with a typical dimension of 5 Å. We compute the self-trapping energy to be −0.06±0.03 eV, with a lifetime on the time scale of a few tens of picoseconds

Electronic states for excess electrons in polyethylene compared to long-chain alkanes

Versión Post-Print del autorWe use a pseudopotential model to calculate the electronic states available to an excess electron in crystalline and amorphous regions of model polyethlyene as well as the molecular crystal of the linear alkane C27H56. It is shown that alkane crystals of whatever chain length are not representative of crystalline polyethylene (PE) although they are often considered to be so. We discuss the implications for electron transport in PE.This work was supported by EPSRC through Grants GR/R18222 and GR/M9442

Electronic transport in disordered n-alkanes: From fluid methane to amorphous polyethylene

We use a fast Fourier transform block Lanczos diagonalization algorithm to study the electronic states of excess electrons in fluid alkanes (methane, ethane, and propane) and in a molecular model of amorphous polyethylene (PE) relevant to studies of space charge in insulating polymers. We obtain a new pseudopotential for electron–PE interactions by fitting to the electronic properties of fluid alkanes and use this to obtain new results for electron transport in amorphous PE. From our simulations, while the electronic states in fluid methane are extended throughout the whole sample, in amorphous PE there is a transition between localized and delocalized states slightly above the vacuum level (∼+0.06 eV). The localized states in our amorphous PE model extend to −0.33 eV below this level. Using the Kubo–Greenwood equation we compute the zero-field electron mobility in pure amorphous PE to be μ≈2×10−3 cm2/V s. Our results highlight the importance of electron transport through extended states in amorphous regions to an understanding of electron transport in PE.EPSRC through Grants No.GR/R18222 and No. GR/M9442

A Comparison of Fathers' and Mothers' Talk to Toddlers in Low-income Families

The purpose of this study was to provide descriptive information about low-income fathers’ and mothers’ talk to toddlers and to re-examine the bridge hypothesis (Gleason, 1975) in light of current changes in family structure and childcare responsibilities. Thirty-three father–child and mother–child dyads were videotaped during semi-structured free play at home. Fathers’ and mothers’ talk to children did not differ in amount, diversity of vocabulary, or linguistic complexity as measured by mean length of utterance. However, fathers produced more wh-questions and explicit clarification requests, thus presenting more conversational challenges to children. Resident fathers employed more direct forms of prohibitives. Results suggest the need for closer examination of factors related to child-directed speech in varying family configurations

A bacteriophage tubulin harnesses dynamic instability to center DNA in infected cells.

Dynamic instability, polarity, and spatiotemporal organization are hallmarks of the microtubule cytoskeleton that allow formation of complex structures such as the eukaryotic spindle. No similar structure has been identified in prokaryotes. The bacteriophage-encoded tubulin PhuZ is required to position DNA at mid-cell, without which infectivity is compromised. Here, we show that PhuZ filaments, like microtubules, stochastically switch from growing in a distinctly polar manner to catastrophic depolymerization (dynamic instability) both in vitro and in vivo. One end of each PhuZ filament is stably anchored near the cell pole to form a spindle-like array that orients the growing ends toward the phage nucleoid so as to position it near mid-cell. Our results demonstrate how a bacteriophage can harness the properties of a tubulin-like cytoskeleton for efficient propagation. This represents the first identification of a prokaryotic tubulin with the dynamic instability of microtubules and the ability to form a simplified bipolar spindle