Predicting the frequency dispersion of electronic hyperpolarizabilities on the basis of absorption data and thomas-kuhn sum rules

Successfully predicting the frequency dispersion of electronic hyperpolarizabilities is an unresolved challenge in materials science and electronic structure theory. We show that the generalized Thomas-Kuhn sum rules, combined with linear absorption data and measured hyperpolarizability at one or two frequencies, may be used to predict the entire frequency-dependent electronic hyperpolarizability spectrum. This treatment includes two- and three-level contributions that arise from the lowest two or three excited electronic state manifolds, enabling us to describe the unusual observed frequency dispersion of the dynamic hyperpolarizability in high oscillator strength M-PZn chromophores, where (porphinato)zinc(II) (PZn) and metal(II)polypyridyl (M) units are connected via an ethyne unit that aligns the high oscillator strength transition dipoles of these components in a head-to-tail arrangement. We show that some of these structures can possess very similar linear absorption spectra yet manifest dramatically different frequency dependent hyperpolarizabilities, because of three-level contributions that result from excited state-to excited state transition dipoles among charge polarized states. Importantly, this approach provides a quantitative scheme to use linear optical absorption spectra and very limited individual hyperpolarizability measurements to predict the entire frequency-dependent nonlinear optical response. Copyright © 2010 American Chemical Society.

Cumulative exposure to traumatic events in older adults.

OBJECTIVES: The present study examined the impact of cumulative trauma exposure on current posttraumatic stress disorder (PTSD) symptom severity in a nonclinical sample of adults in their 60s. The predictive utility of cumulative trauma exposure was compared to other known predictors of PTSD, including trauma severity, personality traits, social support, and event centrality. METHOD: Community-dwelling adults (n = 2515) from the crest of the Baby Boom generation completed the Traumatic Life Events Questionnaire, the PTSD Checklist, the NEO Personality Inventory, the Centrality of Event Scale, and rated their current social support. RESULTS: Cumulative trauma exposure predicted greater PTSD symptom severity in hierarchical regression analyses consistent with a dose-response model. Neuroticism and event centrality also emerged as robust predictors of PTSD symptom severity. In contrast, the severity of individuals' single most distressing life event, as measured by self-report ratings of the A1 PTSD diagnostic criterion, did not add explanatory variance to the model. Analyses concerning event categories revealed that cumulative exposure to childhood violence and adulthood physical assaults were most strongly associated with PTSD symptom severity in older adulthood. Moreover, cumulative self-oriented events accounted for a larger percentage of variance in symptom severity compared to events directed at others. CONCLUSION: Our findings suggest that the cumulative impact of exposure to traumatic events throughout the life course contributes significantly to posttraumatic stress in older adulthood above and beyond other known predictors of PTSD.

Cumulative stress in childhood is associated with blunted reward-related brain activity in adulthood.

Early life stress (ELS) is strongly associated with negative outcomes in adulthood, including reduced motivation and increased negative mood. The mechanisms mediating these relations, however, are poorly understood. We examined the relation between exposure to ELS and reward-related brain activity, which is known to predict motivation and mood, at age 26, in a sample followed since kindergarten with annual assessments. Using functional neuroimaging, we assayed individual differences in the activity of the ventral striatum (VS) during the processing of monetary rewards associated with a simple card-guessing task, in a sample of 72 male participants. We examined associations between a cumulative measure of ELS exposure and VS activity in adulthood. We found that greater levels of cumulative stress during childhood and adolescence predicted lower reward-related VS activity in adulthood. Extending this general developmental pattern, we found that exposure to stress early in development (between kindergarten and grade 3) was significantly associated with variability in adult VS activity. Our results provide an important demonstration that cumulative life stress, especially during this childhood period, is associated with blunted reward-related VS activity in adulthood. These differences suggest neurobiological pathways through which a history of ELS may contribute to reduced motivation and increased negative mood.

Cumulative early life adversity predicts longevity in wild baboons.

In humans and other animals, harsh circumstances in early life predict morbidity and mortality in adulthood. Multiple adverse conditions are thought to be especially toxic, but this hypothesis has rarely been tested in a prospective, longitudinal framework, especially in long-lived mammals. Here we use prospective data on 196 wild female baboons to show that cumulative early adversity predicts natural adult lifespan. Females who experience ≥3 sources of early adversity die a median of 10 years earlier than females who experience ≤1 adverse circumstances (median lifespan is 18.5 years). Females who experience the most adversity are also socially isolated in adulthood, suggesting that social processes partially explain the link between early adversity and adult survival. Our results provide powerful evidence for the developmental origins of health and disease and indicate that close ties between early adversity and survival arise even in the absence of health habit and health care-related explanations.

Design of Latent Thermal Energy Storage Systems

This dissertation documents the results of a theoretical and numerical study of time dependent storage of energy by melting a phase change material. The heating is provided along invading lines, which change from single-line invasion to tree-shaped invasion. Chapter 2 identifies the special design feature of distributing energy storage in time-dependent fashion on a territory, when the energy flows by fluid flow from a concentrated source to points (users) distributed equidistantly on the area. The challenge in this chapter is to determine the architecture of distributed energy storage. The chief conclusion is that the finite amount of storage material should be distributed proportionally with the distribution of the flow rate of heating agent arriving on the area. The total time needed by the source stream to ‘invade’ the area is cumulative (the sum of the storage times required at each storage site), and depends on the energy distribution paths and the sequence in which the users are served by the source stream. Chapter 3 shows theoretically that the melting process consists of two phases: “invasion” thermal diffusion along the invading line, which is followed by “consolidation” as heat diffuses perpendicularly to the invading line. This chapter also reports the duration of both phases and the evolution of the melt layer around the invading line during the two-dimensional and three-dimensional invasion. It also shows that the amount of melted material increases in time according to a curve shaped as an S. These theoretical predictions are validated by means of numerical simulations in chapter 4. This chapter also shows that the heat transfer rate density increases (i.e., the S curve becomes steeper) as the complexity and number of degrees of freedom of the structure are increased, in accord with the constructal law. The optimal geometric features of the tree structure are detailed in this chapter. Chapter 5 documents a numerical study of time-dependent melting where the heat transfer is convection dominated, unlike in chapter 3 and 4 where the melting is ruled by pure conduction. In accord with constructal design, the search is for effective heat-flow architectures. The volume-constrained improvement of the designs for heat flow begins with assuming the simplest structure, where a single line serves as heat source. Next, the heat source is endowed with freedom to change its shape as it grows. The objective of the numerical simulations is to discover the geometric features that lead to the fastest melting process. The results show that the heat transfer rate density increases as the complexity and number of degrees of freedom of the structure are increased. Furthermore, the angles between heat invasion lines have a minor effect on the global performance compared to other degrees of freedom: number of branching levels, stem length, and branch lengths. The effect of natural convection in the melt zone is documented.