Gillian Murphy

The range in static stereochemistry of the cation distortion isomers of the [Cu (chelate)2Cl]+ cation, where chelate=bipy, phen or bipyam. The low temperature crystal structure (150 K) of [Cu (bipy)2Cl] [PF6]·H2O and [Cu (phen)2Cl] [BPh4]

Abstract Low temperature crystallography (150 K) has been used to confirm that the two extreme [Cu (chelate)2Cl] [Y] stereochemistries of 3 [Cu (bipy)2Cl] [PF6]·H2O, trigonal bipyramidal and 6 [Cu (phen)2Cl] [BPh4], trigonal bipyramidal distorted square based pyramidal, are genuine and static stereochemistries of the copper (II) ion.

Structural systematics of the [Cu(chelate)3][Y]2 series. An interesting crystallographic structural insight involving vibronic coupling and the Jahn–Teller effect (JTE). The syntheses and low temperature crystal structures of tris(2,2′bipyridyl)copper(II) tetraphenylborate and tris(2,2′bipyridyl)zinc(II) tetraphenylborate

The crystal structures of [Cu(bipy)(3)][BPh(4)](2), 1, and [Zn(bipy)(3)][BPh(4)](2), have been determined at low temperature. 1 and 2 are closely related, but are not isostructural. Both contain a two-dimensional supramolecular construct (SC) involving a sandwich structure. 1 has a six-coordinate CuN(6) chromophore with a regular elongated octahedral stereochemistry and rhombic in-plane bond lengths. The associated tetragonality value, T, of 1 is 0.8868. 2 involves a six-coordinate octahedral chromophore. Differences between 1 and 2 relate to the tendency of copper(II) complexes to undergo a Jahn-Teller (JT) distortion. The zinc(II) cation feels solely the host site strain, whereas the copper(II) cation also involves vibronic JT type coupling. The copper polyhedron geometry is characterized by both phenomena, with the vibronic interaction dominating. Scatter plot analysis involving the tris-chelate copper(II) series suggests that neither pure Q(theta) or Q(epsilon) components or the a(2u) mode operate in isolation over the entire series. All three operate in combination with varying quantifiable contributions, leading to distortion from the regular tetragonal octahedral stereochemistry.

Crystal structures, electronic properties and structural pathways offour [Cu(phen)2Cl][Y] complexes(phen = 1,10-phenanthroline;Y = BF4-·0.5H2O, PF6-,CF3SO3-·H2O orBPh4-)

The crystal structures of [Cu(phen) 2 Cl][BF 4 ]·0.5H 2 O 1 (phen = 1,10-phenanthroline), [Cu(phen) 2 Cl][PF 6 ] 2, [Cu(phen) 2 Cl][CF 3 SO 3 ]·H 2 O 3 and [Cu(phen) 2 Cl][BPh 4 ] 4 have been determined by X-ray crystallography. Three of the complexes, 1–3, involve a CuN 4 Cl chromophore with a square based pyramidal distorted trigonal bipyramidal stereochemistry, while 4 involves a trigonal bipyramidal distorted square based pyramidal stereochemistry. The geometries of the CuN 4 Cl chromophores in 1–4 were compared by scatter-plot analysis with those of four other [Cu(phen) 2 Cl][Y] complexes of known structure. The scatter plots of the eight cation distortion isomers of the [Cu(phen) 2 Cl][Y] complex suggest that all the complexes involve a -A + B route distortion of the CuN 4 Cl chromophore, -A (ca. 60%) and +B (ca. 40%), The observation of linear and parallel correlations are alternatively interpreted as a direct observation of vibronic coupling of a mixture of the symmetric, ν sym , C 2 mode and the asymmetric, ν asym , non-C 2 mode of vibration of the CuN 4 Cl chromophore. This emphasises the need to determine the structure of more than one complex in a series of cation distortion isomers, in which the limits of the range of stereochemistries are indicated by the measurement of the electronic reflectance spectra.

Perceptual Load Affects Eyewitness Accuracy and Susceptibility to Leading Questions.

Load Theory (Lavie, 1995, 2005) states that the level of perceptual load in a task (i.e., the amount of information involved in processing task-relevant stimuli) determines the efficiency of selective attention. There is evidence that perceptual load affects distractor processing, with increased inattentional blindness under high load. Given that high load can result in individuals failing to report seeing obvious objects, it is conceivable that load may also impair memory for the scene. The current study is the first to assess the effect of perceptual load on eyewitness memory. Across three experiments (two video-based and one in a driving simulator), the effect of perceptual load on eyewitness memory was assessed. The results showed that eyewitnesses were less accurate under high load, in particular for peripheral details. For example, memory for the central character in the video was not affected by load but memory for a witness who passed by the window at the edge of the scene was significantly worse under high load. High load memories were also more open to suggestion, showing increased susceptibility to leading questions. High visual perceptual load also affected recall for auditory information, illustrating a possible cross-modal perceptual load effect on memory accuracy. These results have implications for eyewitness memory researchers and forensic professionals.

Crystal structures, electronic properties and structural pathways of two[Cu(phen)2(OH2)][Y]2 complexes(phen = 1,10-phenanthroline,Y = CF3SO3- or ClO4-)

The crystal structures of [Cu(phen) 2 (OH 2 )][CF 3 SO 3 ] 2 1 and [Cu(phen) 2 (OH 2 )][ClO 4 ] 2 2 (phen = 1,10-phenanthroline) have been determined by diffractometer data collection. The CuN 4 O chromophores in both complexes 1 and 2 lie on a crystallographic two-fold axis, with a square pyramidal distorted trigonal bipyramidal stereochemistry, an elongation along the Cu–O direction, Cu–O 2.066(3) and 2.245(4) A, and an increase in the N(4)–Cu–N(2) α 3 angle to 123.4(1) and 136.0(1)°, respectively. This suggests that the stereochemistry of 1 is best described as near regular trigonal bipyramidal, RTB, and that of 2 as square based pyramidal distorted trigonal bipyramidal, SBPDTB. The structures of 1 and 2 were compared by scatter-plot analysis, with other [Cu(chelate ligand) 2 (OH 2 )][Y] 2 complexes involving two-fold axes of symmetry. This shows that the spread of the data points is not random, is relatively large and suggests the presence of vibronic coupling to account for the distortion from the RTB CuN 4 O chromophore, along the C 2 dominated +A and -A route distortions. A continuous linear structural pathway is suggested, determined by the coupled ν sym str and ν sym bend modes of vibration, involving a progression of 40–50 modes, spanning an angular distortion range of 91–140°, which correlate with electronic and ESR spectral data.

The role of prenatal, obstetric, and post-partum factors in the parenting stress of mothers and fathers of 9-month old infants

Abstract Introduction: The aim of this paper was to examine the role of perinatal, obstetric and post partum factors on maternal and paternal stress. It will present the first examination of the role of prenatal, obstetric, post-partum, and demographic variables in parenting stress for mothers and fathers at 9 months. Methods: Data from 6821 parental dyads of 9-month-old infants were extracted from the Growing Up in Ireland National Longitudinal Study of Children. Participants completed the Parental Stress Scale, the Dyadic Adjustment Scale, the Quality of Attachment Sub-scale from the Maternal and Paternal Postnatal Attachment Scales, and a single item health status question from the Short Form 12 Health Survey. Information on prenatal care, pregnancy complications, obstetric outcomes, infant health, and participant demographics were also collected. Separate hierarchical linear regressions were conducted for mothers and fathers Results: Mothers reported higher levels of parenting stress than fathers (p < 0.001). Maternal parenting stress was predicted by attachment, own health status, average sleep, occupation, household income, and having a very rapid labor. Paternal parenting stress was predicted by attachment and own health status. Discussion: A range of perinatal factors was associated with an increased risk of higher parenting stress at 9 months post-partum and the roles of these factors differ between mothers and fathers. These findings are important for predicting and reducing risk of parenting stress in both genders.

High perceptual load causes inattentional blindness and deafness in drivers

ABSTRACT Perceptual load theory of attention predicts that the level of perceptual load in a primary task affects the processing of additional stimuli. Given the lack of ecologically valid evidence for the model, the current study assessed the effect of perceptual load on driver awareness during simulated driving tasks. The results showed that perceptual load dramatically affected driver awareness for visual and auditory stimuli, even those that were driving relevant and safety critical (e.g. pedestrians or the sound of a car horn). The results support load theory and suggest that perceptual load may be an important factor in driver safety.

Visual feature vs. conjunction searches as a robust manipulation of perceptual load

ABSTRACT It has previously been suggested that Lavie’s Perceptual Load Theory can be assessed using feature vs. conjunction search tasks. In this study we manipulated load using a novel paradigm which retains the key features of both classic Load Theory and Feature Integration Theory paradigms. This new paradigm has the advantage of an inbuilt manipulation check which is necessary for future research to translate Load Theory to applied contexts. Across five experiments, we demonstrate the robust nature of this paradigm, which functions with extended display times, large, complex stimuli and when conditions are intermixed on a trial-by-trial basis. We also rule out dilution as a possible cause of these results. The results of all five experiments provide evidence that the feature vs. conjunction search dichotomy is an effective means of imposing low and high perceptual load while controlling for working memory load.

Load Theory Behind the Wheel; Perceptual and Cognitive Load Effects

Perceptual Load Theory has been proposed as a resolution to the longstanding early versus late selection debate in cognitive psychology. There is much evidence in support of Load Theory but very few applied studies, despite the potential for the model to shed light on everyday attention and distraction. Using a driving simulator, the effect of perceptual and cognitive load on drivers’ visual search was assessed. The findings were largely in line with Load Theory, with reduced distractor processing under high perceptual load, but increased distractor processing under high cognitive load. The effect of load on driving behaviour was also analysed, with significant differences in driving behaviour under perceptual and cognitive load. In addition, the effect of perceptual load on drivers’ levels of awareness was investigated. High perceptual load significantly increased inattentional blindness and deafness, for stimuli that were both relevant and irrelevant to driving. High perceptual load also increased RTs to hazards. The current study helps to advance Load Theory by illustrating its usefulness outside of traditional paradigms. There are also applied implications for driver safety and roadway design, as the current study suggests that perceptual and cognitive load are important factors in driver attention. La théorie de la charge perceptuelle a été proposée comme une solution à l’éternel débat entre la sélection précoce et la sélection tardive en psychologie cognitive. Plusieurs preuves viennent appuyer la théorie de la charge, mais très peu d’études appliquées ont été réalisées, malgré le potentiel de ce modèle à faire la lumière sur l’attention et la distraction de tous les jours. Au moyen d’un simulateur de conduite automobile, l’effet des charges perceptuelle et cognitive sur la recherche visuelle du conducteur a été évalué. Les conclusions étaient en grande partie alignées avec la théorie de la charge, affichant un traitement réduit des éléments de distraction sous une charge perceptuelle élevée et un traitement accru des éléments de distraction sous une charge cognitive élevée. L’effet de charge sur le comportement au volant a également été analysé, affichant des différences significatives au niveau du comportement au volant selon que ce dernier était soumis à une charge perceptuelle ou cognitive. De plus, l’effet de la charge perceptuelle sur les niveaux de conscience des conducteurs a été étudié. Les charges perceptuelles élevées ont considérablement augmenté la surdité et la cécité d’inattention en réponse à des stimuli pertinents et non pertinents à la conduite automobile. La charge perceptuelle augmentait aussi les temps de réaction par rapport aux dangers. La présente étude contribue à faire progresser la théorie de la charge en démontrant son utilité en dehors de paradigmes traditionnels. Cette théorie a aussi des implications en matière de sécurité des conducteurs et de conception des routes, étant donné que la présente étude actuelle suggère que les charges perceptuelle et cognitive jouent un rôle important sur l’attention du conducteur.