On the Vertical and Adiabatic Excitation Energies of the 21A(g), State of trans-1,3-butadiene

The excitation energy to the 21Ag state of trans-1,3-butadiene is examined using a variety of ab initio electronic structure techniques. While analogous states have been shown to be the lowest singlet excited states for all longer polyenes, for butadiene the position of the 21Ag state relative to the HOMO → LUMO excitation (11Bu) has been difficult to establish theoretically. We employ a variety of methods (CASSCF, CASPT2, MRSDCI, QDVPT) to examine both the vertical and adiabatic excitation energies for this state. At the ground-state geometry, the vertical excitation energies obtained by CASPT2 and Davidson-corrected MRSDCI for the 21Ag state differ by approximately 0.15 eV, but all of the methods predict that the 21Ag state has a lower 0−0 excitation energy than the 11Bu state. Possible reasons for the discrepancies between the various methods for the vertical excitation energy are discussed

Translation and articulation in biological motion perception

Recent models of biological motion processing focus on the articulational aspect of human walking investigated by point-light figures walking in place. However, in real human walking, the change in the position of the limbs relative to each other (referred to as articulation) results in a change of body location in space over time (referred to as translation). In order to examine the role of this translational component on the perception of biological motion we designed three psychophysical experiments of facing (leftward/rightward) and articulation discrimination (forward/backward and leftward/rightward) of a point-light walker viewed from the side, varying translation direction (relative to articulation direction), the amount of local image motion, and trial duration. In a further set of a forward/backward and a leftward/rightward articulation task, we additionally tested the influence of translational speed, including catch trials without articulation. We found a perceptual bias in translation direction in all three discrimination tasks. In the case of facing discrimination the bias was limited to short stimulus presentation. Our results suggest an interaction of articulation analysis with the processing of translational motion leading to best articulation discrimination when translational direction and speed match articulation. Moreover, we conclude that the global motion of the center-of-mass of the dot pattern is more relevant to processing of translation than the local motion of the dots. Our findings highlight that translation is a relevant cue that should be integrated in models of human motion detection

Multistate Effects in Calculations of the Electronic Coupling Element for Electron Transfer Using the Generalized Mulliken−Hush Method

A simple diagnostic is developed for the purpose of determining when a third state must be considered to calculate the electronic coupling element for a given pair of diabatic states within the context of the generalized Mulliken−Hush approach (Chem. Phys. Lett. 1996, 275, 15−19). The diagnostic is formulated on the basis of Löwdin partitioning theory. In addition, an effective 2-state GMH expression is derived for the coupling as it is modified by the presence of the third state. Results are presented for (i) a model system involving charge transfer from ethylene to methaniminium cation, (ii) a pair of donor−acceptor-substituted acridinium ions, and (iii) (dimethylamino)benzonitrile, and the diagnostic is shown to be a useful indicator of the importance of multistate effects. The effective 2-state GMH expression is also shown to yield excellent agreement with the exact 3-state GMH results in most cases. For cases involving more than three interacting states a similar diagnostic is presented and several approximations to the full n-state GMH result are explored

A Theoretical Investigation of Charge Transfer in Several Substituted Acridinium Ions

We present calculations for various properties of the ground and excited states of several arylamine-substituted acridinium ion systems that have been studied experimentally. Using ab initio and semiempirical quantum mechanical methods together with the generalized Mulliken−Hush (GMH) model, we examine the excitation energies, dipole moment shifts, and electronic coupling elements for the vertical charge shift (CSh) processes in these systems. We also examine solvent effects on these properties using a dielectric continuum reaction field model. The results are in generally good agreement with available experimental results and indicate that there is strong electronic coupling in these systems over a wide range of torsional angles. Nevetheless, the initial and final cationic states remain reasonably well-localized over this range, and thus TICT state formation is unlikely in these systems. Finally, a version of the GMH model based on Koopmans\u27 Theorem is developed and found to yield coupling elements generally within a factor of 2 of the many-electron GMH for a sample acridinium system, but with overestimated adiabatic and diabatic dipole moment differences

The role of spatial and temporal information in biological motion perception

Point-light biological motion stimuli provide spatio-temporal information about the structure of the human body in motion. Manipulation of the spatial structure of point-light stimuli reduces the ability of human observers to perceive biological motion. A recent study has reported that interference with the spatial structure of pointlight walkers also reduces the evoked eventrelated potentials over the occipitotemporal cortex, but that interference with the temporal structure of the stimuli evoked event-related potentials similar to normal biological motion stimuli. We systematically investigated the influence of spatial and temporal manipulation on 2 common discrimination tasks and compared it with predictions of a neurocomputational model previously proposed. This model first analyzes the spatial structure of the stimulus independently of the temporal information to derive body posture and subsequently analyzes the temporal sequence of body postures to derive movement direction. Similar to the model predictions, the psychophysical results show that human observers need only intact spatial configuration of the stimulus to discriminate the facing direction of a point-light walker. In contrast, movement direction discrimination needs a fully intact spatiotemporal pattern of the stimulus. The activation levels in the model predict the observed eventrelated potentials for the spatial and temporal manipulations

The Peri-Saccadic Perception of Objects and Space

Eye movements affect object localization and object recognition. Around saccade onset, briefly flashed stimuli appear compressed towards the saccade target, receptive fields dynamically change position, and the recognition of objects near the saccade target is improved. These effects have been attributed to different mechanisms. We provide a unifying account of peri-saccadic perception explaining all three phenomena by a quantitative computational approach simulating cortical cell responses on the population level. Contrary to the common view of spatial attention as a spotlight, our model suggests that oculomotor feedback alters the receptive field structure in multiple visual areas at an intermediate level of the cortical hierarchy to dynamically recruit cells for processing a relevant part of the visual field. The compression of visual space occurs at the expense of this locally enhanced processing capacity

Curie Temperature Enhancement and Cation Ordering in Titanomagnetites: Evidence From Magnetic Properties, XMCD, and Mössbauer Spectroscopy

Previous work has documented time‐ and temperature‐dependent variations in the Curie temperature (Tc) of natural titanomagnetites, independent of any changes in sample composition. To better understand the atomic‐scale processes responsible for these variations, we have generated a set of synthetic titanomagnetites with a range of Ti, Mg, and Al substitution; a subset of samples was additionally oxidized at low temperature (150 °C). Samples were annealed at temperatures between 325 and 400 °C for up to 1,000 hr and characterized in terms of magnetic properties; Fe valence and site occupancy were constrained by X‐ray magnetic circular dichroism (XMCD) and Mössbauer spectroscopy. Annealing results in large (up to ~100 °C) changes in Tc, but Mössbauer, XMCD, and saturation magnetization data all demonstrate that intersite reordering of Fe2+/Fe3+ does not play a role in the observed Tc changes. Rather, the data are consistent with vacancy‐enhanced nanoscale chemical clustering within the octahedral sublattice. This clustering may be a precursor to chemical unmixing at temperatures below the titanomagnetite binary solvus. Additionally, the data strongly support a model where cation vacancies are predominantly situated on octahedral sites, Mg substitution is largely accommodated on octahedral sites, and Al substitution is split between the two sites