Manipulating the reliability of target-color information modulates value-driven attentional capture.

Previously rewarded stimuli slow response times (RTs) during visual search, despite being physically non-salient and no longer task-relevant or rewarding. Such value-driven attentional capture (VDAC) has been measured in a training-test paradigm. In the training phase, the search target is rendered in one of two colors (one predicting high reward and the other low reward). In this study, we modified this traditional training phase to include pre-cues that signaled reliable or unreliable information about the trial-to-trial color of the training phase search target. Reliable pre-cues indicated the upcoming target color with certainty, whereas unreliable pre-cues indicated the target was equally likely to be one of two distinct colors. Thus reliable and unreliable pre-cues provided certain and uncertain information, respectively, about the magnitude of the upcoming reward. We then tested for VDAC in a traditional test phase. We found that unreliably pre-cued distractors slowed RTs and drew more initial eye movements during search for the test-phase target, relative to reliably pre-cued distractors, thus providing novel evidence for an influence of information reliability on attentional capture. That said, our experimental manipulation also eliminated value-dependency (i.e., slowed RTs when a high-reward-predicting distractor was present relative to a low-reward-predicting distractor) for both kinds of distractors. Taken together, these results suggest that target-color uncertainty, rather than reward magnitude, played a critical role in modulating the allocation of value-driven attention in this study.

Cumulative lifetime stressor exposure assessed by the STRAIN predicts economic ambiguity aversion.

Uncertainty is inherent in most decisions humans make. Economists distinguish between two types of decision-making under non-certain conditions: those involving risk (i.e., known outcome probabilities) and those that involve ambiguity (i.e., unknown outcome probabilities). Prior research has identified individual differences that explain risk preferences, but little is known about factors associated with ambiguity aversion. Here, we hypothesized that cumulative exposure to major psychosocial stressors over the lifespan might be one factor that predicts individuals' ambiguity aversion. Across two studies (Study 1: n = 58, Mage = 25.7; Study 2: n = 188, Mage = 39.81), we used a comprehensive lifetime stressor exposure inventory (i.e., the Stress and Adversity Inventory for Adults, or STRAIN) and a standard economic approach to quantify risk and ambiguity preferences. Greater lifetime stressor exposure as measured by the STRAIN, particularly in early life, was associated with higher aversion to ambiguity but not risk preferences.

Perceptual Fading of a Stabilized Cortical Image: Replication in the Undergraduate Classroom.

Prolonged exposure to a stimulus causes desensitization of cortical neurons and results in perceptual changes. One example of this phenomenon is contrast adaptation, in which perceived differences between light and dark regions of a stimulus decrease. Blakemore, Muncey, and Ridley reported evidence for the "perceptual fading of a stabilized cortical image" in a 1971 Nature paper. Our goal was to replicate their second experiment, in which adaptation was measured across many contrasts, and develop an active learning exercise for undergraduate students. The experiment was coded using an open-source python package and psychophysical data were collected from two observers. On each trial, a sinusoidally modulated luminance grating appeared above fixation, and the task of the observer was to adjust the contrast of a grating below fixation until the two appeared identical. Between trials in the adaptation condition, a high contrast grating was presented in the top location; no such grating appeared between trials in the control condition. Contrast matches showed a clear reduction during the adaptation condition, thus demonstrating perceptual fading and a successful replication of Blakemore et al. (1971) We then simplified the approach and modified the code to create a single, seamless experience for use in the classroom. With instructions and theoretical background provided in a one-page handout, students can perform the experiment on themselves and view their results in an automatically generated figure. This exercise, a primary example of active learning, will help students gain a first-hand understanding of the perceptual effects of adaptation.

Higher cost of finance exacerbates a climate investment trap in developing economies.

Finance is vital for the green energy transition, but access to low cost finance is uneven as the cost of capital differs substantially between regions. This study shows how modelled decarbonisation pathways for developing economies are disproportionately impacted by different weighted average cost of capital (WACC) assumptions. For example, representing regionally-specific WACC values indicates 35% lower green electricity production in Africa for a cost-optimal 2 °C pathway than when regional considerations are ignored. Moreover, policy interventions lowering WACC values for low-carbon and high-carbon technologies by 2050 would allow Africa to reach net-zero emissions approximately 10 years earlier than when the cost of capital reduction is not considered. A climate investment trap arises for developing economies when climate-related investments remain chronically insufficient. Current finance frameworks present barriers to these finance flows and radical changes are needed so that capital is more equitably distributed.

Sudden onsets reflexively drive spatial attention, but those that predict reward do more.

The sudden appearance of an unexpected object elicits the automatic allocation of spatial attention. Even without eye movements, effortless, but transient, improvements in perception occur at the onset location. Much is known about the consequences of such exogenously elicited shifts of covert attention, but most research has used stimuli that carry very little, if any, additional information. In everyday life, attention is captured by sudden onsets that, due to past experience, alert us to more than just their appearance. An abundance of recent work has shed light on the interaction of associative learning and attention, leading to refinements in current models of attentional control; in this study, we tested two hypotheses concerning the efficacy of meaning-imbued onsets, specifically those that predict reward, to drive the reflexive allocation of covert spatial attention and to improve task performance more generally. First, spatially uninformative, abrupt-onset cues that are predictive of reward may elicit the involuntary allocation of attention more effectively than nonreward-predictive onsets; second, the presence of peripheral cues that are predictive of reward, regardless of validity, may impact global attentional processes in a spatially nonspecific manner. We paired monetary reward with one of two luminance-defined, abrupt-onset cues and measured each cue's ability to modulate performance in a visual task. Replicating research with nonmeaning-imbued stimuli, both kinds of abrupt onsets reflexively improved visual perception at attended, relative to unattended, locations. However, when features of the onset predicted the availability of monetary reward, enhancements in perception become less constrained, spreading rapidly to other task-relevant locations.

Investigating the role of exogenous cueing on selection history formation.

An abundance of recent empirical data suggest that repeatedly allocating visual attention to task-relevant and/or reward-predicting features in the visual world engenders an attentional bias for these frequently attended stimuli, even when they become task irrelevant and no longer predict reward. In short, attentional selection in the past hinders voluntary control of attention in the present. But do such enduring attentional biases rely on a history of voluntary, goal-directed attentional selection, or can they be generated through involuntary, effortless attentional allocation? An abrupt visual onset triggers such a reflexive allocation of covert spatial attention to its location in the visual field, automatically modulating numerous aspects of visual perception. In this Registered Report, we asked whether a selection history that has been reflexively and involuntarily derived (i.e., through abrupt-onset cueing) also interferes with goal-directed attentional control, even in the complete absence of exogenous cues. To build spatially distinct histories of exogenous selection, we presented abrupt-onset cues twice as often at one of two task locations, and as expected, these cues reflexively modulated visual processing: task accuracy increased, and response times (RTs) decreased, when the cue appeared near the target's location, relative to that of the distractor. Upon removal of these cues, however, we found no evidence that exogenous selection history modulated task performance: task accuracy and RTs at the previously most-cued and previously least-cued sides were statistically indistinguishable. Thus, unlike voluntarily directed attention, involuntary attentional allocation may not be sufficient to engender historically contingent selection biases.

Assessing the role of accuracy-based feedback in value-driven attentional capture.

Despite being physically nonsalient and task-irrelevant, objects rendered in a color that once signaled monetary reward reflexively capture attention during visual search, a phenomenon known as value-driven attentional capture (VDAC). However, it remains a subject of empirical controversy whether learned reward associations are necessary to driving subsequent attentional capture: VDAC-like effects have been observed when accuracy-based feedback alone was used during the VDAC training phase, resulting in attentional capture by objects that were never associated with monetary reward; perplexingly, the presence of these VDAC-like effects in the literature conflicts with those of a number of control studies in which no such capture has been observed, leaving the issue currently unresolved. In this Registered Report, we present new empirical evidence of attentional capture by unrewarded former targets following limited accuracy-based training. We proposed to replicate these results in an independent sample and to test an empirically derived hypothesis concerning a methodological difference between the studies that have shown VDAC-like effects with accuracy-based feedback and those that have not. In short, we found no evidence that this methodological difference accounts for the inconsistencies in the literature, but our replication efforts were overwhelmingly successful, thus reinvigorating debate about the role that selection history may play in value-driven attentional capture.

A method of extracting speed-dependent vector correlations from 2 + 1 REMPI ion images.

We present analytical expressions for extracting Dixon's bipolar moments in the semi-classical limit from experimental anisotropy parameters of sliced or reconstructed non-sliced images. The current method focuses on images generated by 2 + 1 REMPI (Resonance Enhanced Multi-photon Ionization) and is a necessary extension of our previously published 1 + 1 REMPI equations. Two approaches for applying the new equations, direct inversion and forward convolution, are presented. As demonstration of the new method, bipolar moments were extracted from images of carbonyl sulfide (OCS) photodissociation at 230 nm and NO2 photodissociation at 355 nm, and the results are consistent with previous publications.

Unravelling the mechanisms of vibrational relaxation in solution.

We present a systematic study of the mode-specific vibrational relaxation of NO2 in six weakly-interacting solvents (perfluorohexane, perfluoromethylcyclohexane, perfluorodecalin, carbon tetrachloride, chloroform, and d-chloroform), chosen to elucidate the dominant energy transfer mechanisms in the solution phase. Broadband transient vibrational absorption spectroscopy has allowed us to extract quantum state-resolved relaxation dynamics of the two distinct NO2 fragments produced from the 340 nm photolysis of N2O4 → NO2(X) + NO2(A) and their separate paths to thermal equilibrium. Distinct relaxation pathways are observed for the NO2 bending and stretching modes, even at energies as high as 7000 cm-1 above the potential minimum. Vibrational energy transfer is governed by different interaction mechanisms in the various solvent environments, and proceeds with timescales ranging from 20-1100 ps. NO2 relaxation rates in the perfluorocarbon solvents are identical despite differences in acceptor mode state densities, infrared absorption cross sections, and local solvent structure. Vibrational energy is shown to be transferred to non-vibrational solvent degrees of freedom (V-T) through impulsive collisions with the perfluorocarbon molecules. Conversely, NO2 relaxation in chlorinated solvents is reliant on vibrational resonances (V-V) while V-T energy transfer is inefficient and thermal excitation of the surrounding solvent molecules inhibits faster vibrational relaxation through direct complexation. Intramolecular vibrational redistribution allows the symmetric stretch of NO2 to act as a gateway for antisymmetric stretch energy to exit the molecule. This study establishes an unprecedented level of detail for the cooling dynamics of a solvated small molecule, and provides a benchmark system for future theoretical studies of vibrational relaxation processes in solution.

Neuroanatomy accounts for age-related changes in risk preferences.

Many decisions involve uncertainty, or 'risk', regarding potential outcomes, and substantial empirical evidence has demonstrated that human aging is associated with diminished tolerance for risky rewards. Grey matter volume in a region of right posterior parietal cortex (rPPC) is predictive of preferences for risky rewards in young adults, with less grey matter volume indicating decreased tolerance for risk. That grey matter loss in parietal regions is a part of healthy aging suggests that diminished rPPC grey matter volume may have a role in modulating risk preferences in older adults. Here we report evidence for this hypothesis and show that age-related declines in rPPC grey matter volume better account for age-related changes in risk preferences than does age per se. These results provide a basis for understanding the neural mechanisms that mediate risky choice and a glimpse into the neurodevelopmental dynamics that impact decision-making in an aging population.

Translational, rotational and vibrational relaxation dynamics of a solute molecule in a non-interacting solvent.

Spectroscopically observing the translational and rotational motion of solute molecules in liquid solutions is typically impeded by their interactions with the solvent, which conceal spectral detail through linewidth broadening. Here we show that unique insights into solute dynamics can be made with perfluorinated solvents, which interact weakly with solutes and provide a simplified liquid environment that helps to bridge the gap in our understanding of gas- and liquid-phase dynamics. Specifically, we show that in such solvents, the translational and rotational cooling of an energetic CN radical can be observed directly using ultrafast transient absorption spectroscopy. We observe that translational-energy dissipation within these liquids can be modelled through a series of classic collisions, whereas classically simulated rotational-energy dissipation is shown to be distinctly faster than experimentally measured. We also observe the onset of rotational hindering from nearby solvent molecules, which arises as the average rotational energy of the solute falls below the effective barrier to rotation induced by the solvent.

Reaction Dynamics of CN Radicals in Acetonitrile Solutions.

The bimolecular reactions that follow 267 nm ultraviolet photolysis of ICN in acetonitrile solution have been studied using transient absorption spectroscopy on the picosecond time scale. Time-resolved electronic absorption spectroscopy (TEAS) in the ultraviolet and visible spectral regions observes rapid production and loss (with a decay time constant of 0.6 ± 0.1 ps) of the photolytically generated free CN radicals. Some of these radicals convert to a solvated form which decays with a lifetime of 8.5 ± 2.1 ps. Time-resolved vibrational absorption spectroscopy (TVAS) reveals that the free and solvated CN-radicals undergo geminate recombination with I atoms to make ICN and INC, H atom abstraction reactions, and addition reactions to solvent molecules to make C3H3N2 radical species. These radical products have a characteristic absorption band at 2036 cm(-1) that shifts to 2010 cm(-1) when ICN is photolyzed in CD3CN. The HCN yield is low, suggesting the addition pathway competes effectively with H atom abstraction from CH3CN, but the delayed growth of the C3H3N2 radical band is best described by reaction of solvated CN radicals through an unobserved intermediate species. Addition of methanol or tetrahydrofuran as a cosolute promotes H atom abstraction reactions that produce vibrationally hot HCN. The combination of TEAS and TVAS measurements shows that the rate-limiting process for production of ground-state HCN is vibrational cooling, the rate of which is accelerated by the presence of methanol or tetrahydrofuran.

Recombination, Solvation and Reaction of CN Radicals Following Ultraviolet Photolysis of ICN in Organic Solvents.

The fates of CN radicals produced by ultraviolet (UV) photolysis of ICN in various organic solvents have been examined by transient electronic and vibrational absorption spectroscopy (TEAS and TVAS). Near-UV and visible bands in the TEAS measurement enable direct observation of the CN radicals and their complexes with the solvent molecules. Complementary TVAS measurements probe the products of CN-radical reactions. Geminate recombination to form ICN and INC is a minor pathway on the 150 fs -1300 ps time scales of our experiments in the chosen organic solvents; nonetheless, large infrared transition dipole moments permit direct observation of INC that is vibrationally excited in the C≡N stretching mode. The time constants for INC vibrational cooling range from 30 ps in tetrahydrofuran (THF) to 1400 ps in more weakly interacting solvents such as chloroform. The major channel for CN removal in the organic solvents is reaction with solvent molecules, as revealed by depletion of solvent absorption bands and growth of product bands in the TVA spectra. HCN is a reaction product of hydrogen atom abstraction in most of the photoexcited solutions, and forms with vibrational excitation in both the C-H and C≡N stretching modes. The vibrational cooling rate of the C≡N stretch in HCN depends on the solvent, and follows the same trend as the cooling rate of the C≡N stretch in INC. However, in acetonitrile solution an additional reaction pathway produces C3H3N2(•) radicals, which release HCN on a much longer time scale.

Ultraviolet Absorption Induces Hydrogen-Atom Transfer in G⋠C Watson-Crick DNA Base Pairs in Solution.

Ultrafast deactivation pathways bestow photostability on nucleobases and hence preserve the structural integrity of DNA following absorption of ultraviolet (UV) radiation. One controversial recovery mechanism proposed to account for this photostability involves electron-driven proton transfer (EDPT) in Watson-Crick base pairs. The first direct observation is reported of the EDPT process after UV excitation of individual guanine-cytosine (G⋅C) Watson-Crick base pairs by ultrafast time-resolved UV/visible and mid-infrared spectroscopy. The formation of an intermediate biradical species (G[-H]⋅C[+H]) with a lifetime of 2.9 ps was tracked. The majority of these biradicals return to the original G⋅C Watson-Crick pairs, but up to 10% of the initially excited molecules instead form a stable photoproduct G*⋅C* that has undergone double hydrogen-atom transfer. The observation of these sequential EDPT mechanisms across intermolecular hydrogen bonds confirms an important and long debated pathway for the deactivation of photoexcited base pairs, with possible implications for the UV photochemistry of DNA.

Interactions between voluntary and involuntary attention modulate the quality and temporal dynamics of visual processing.

Successfully navigating a dynamic environment requires the efficient distribution of finite neural resources. Voluntary (endogenous) covert spatial attention selectively allocates those processing resources to goal-relevant locations in the visual scene in the absence of eye movements. However, the allocation of spatial attention is not always voluntary; abrupt onsets in the visual periphery automatically enhance processing of nearby stimuli (exogenous attention). In dynamic environments, exogenous events and internal goals likely compete to determine the distribution of attention, but how such competition is resolved is not well understood. To investigate how exogenous events interact with the concurrent allocation of voluntary attention, we used a speed-accuracy trade-off (SAT) procedure. SAT conjointly measures the rate of information accrual and asymptotic discriminability, allowing us to measure how attentional interactions unfold over time during stimulus processing. We found that both types of attention sped information accrual and improved discriminability. However, focusing endogenous attention at the target location reduced the effects of exogenous cues on the rate of information accrual and rendered negligible their effects on asymptotic discriminability. We verified the robustness of these findings in four additional experiments that targeted specific, critical response delays. In conclusion, the speed and quality of visual processing depend conjointly on internally and externally driven attentional states, but it is possible to voluntarily diminish distraction by irrelevant events in the periphery.

Tracking a Paternò-Büchi reaction in real time using transient electronic and vibrational spectroscopies.

A detailed mechanistic investigation of the early stages of the Paternò-Büchi reaction following 267 nm excitation of benzaldehyde in cyclohexene has been completed using ultrafast, broadband transient UV-visible and IR absorption spectroscopies. Absorption due to electronically excited triplet state benzaldehyde decays on a 80 ps time scale via reaction with cyclohexene. The growth and subsequent decay of the biradical intermediate produced following C-O bond formation is followed by transient vibrational spectroscopy. The biradical decays by ring closure to an oxetane or by dissociating, reforming the ground state reactants. Detailed kinetic analysis allowed derivation of quantum yields and rate constants for these competing biradical decay processes, ϕ(oxetane) = 0.53, ϕ(diss) = 0.47, koxetane = 0.27 ± 0.09 ns(-1) and k(diss) = 0.24 ± 0.09 ns(-1). This study provides a striking illustration of the ways in which contemporary ultrafast transient absorption spectroscopy methods can be used to dissect the mechanism and kinetics of a classic photoreaction.

On the participation of photoinduced N-H bond fission in aqueous adenine at 266 and 220 nm: a combined ultrafast transient electronic and vibrational absorption spectroscopy study.

A combination of ultrafast transient electronic absorption spectroscopy (TEAS) and transient vibrational absorption spectroscopy (TVAS) is used to investigate whether photoinduced N­H bond fission, mediated by a dissociative 1πσ(*) state, is active in aqueous adenine (Ade) at 266 and 220 nm. In order to isolate UV/visible and IR spectral signatures of the adeninyl radical (Ade[-H]), formed as a result of N­H bond fission, TEAS and TVAS are performed on Ade in D2O under basic conditions (pD = 12.5), which forms Ade[-H](-) anions via deprotonation at the N7 or N9 sites of Ade's 7H and 9H tautomers. At 220 nm we observe one-photon detachment of an electron from Ade[-H](-), which generates solvated electrons (eaq(-)) together with Ade[-H] radicals, with clear signatures in both TEAS and TVAS. Additional wavelength dependent TEAS measurements between 240­260 nm identify a threshold of 4.9 ± 0.1 eV (∼250 nm) for this photodetachment process in D2O. Analogous TEAS experiments on aqueous Ade at pD = 7.4 generate a similar photoproduct signal together with eaq(-) after excitation at 266 and 220 nm. These eaq(-) are born from ionization of Ade, together with Ade(+) cations, which are indistinguishable from Ade[-H] radicals in TEAS. Ade(+) and Ade[-H] are found to have different signatures in TVAS and we verify that the pD = 7.4 photoproduct signal observed in TEAS following 220 nm excitation is solely due to Ade(+) cations. Based on these observations, we conclude that: (i) N­H bond fission in aqueous Ade is inactive at wavelengths ≥220 nm; and (ii) if such a channel exists in aqueous solution, its threshold is strongly blue-shifted relative to the onset of the same process in gas phase 9H-Ade (≤233 nm). In addition, we extract excited state lifetimes and vibrational cooling dynamics for 9H-Ade and Ade[-H](-). In both cases, excited state lifetimes of <500 fs are identified, while vibrational cooling occurs within a time frame of 4­5 ps. In contrast, 7H-Ade is confirmed to have a longer excited state lifetime of ∼5­10 ps through both TEAS and TVAS.

Transient UV pump-IR probe investigation of heterocyclic ring-opening dynamics in the solution phase: the role played by nσ* states in the photoinduced reactions of thiophenone and furanone.

The heterocyclic ring-opening dynamics of thiophenone and furanone dissolved in CH3CN have been probed by ultrafast transient infrared spectroscopy. Following irradiation at 267 nm (thiophenone) or 225 nm (furanone), prompt (τ < 1 ps) ring-opening is confirmed by the appearance of a characteristic antisymmetric ketene stretching feature around 2150 cm(-1). The ring-opened product molecules are formed highly vibrationally excited, and cool subsequently on a ∼6.7 ps timescale. By monitoring the recovery of the parent (S0) bleach, it is found that ∼60% of the initially photoexcited thiophenone molecules reform the parent molecule, in stark contrast with the case in furanone where there is less than 10% parent bleach recovery. Complementary ab initio calculations of potential energy cuts along the S-C([double bond, length as m-dash]O) and O-C([double bond, length as m-dash]O) ring-opening coordinate reveals insights into the reaction mechanism, and the important role played by dissociative (n/π)σ* states in the UV-induced photochemistry of such heterocyclic systems.