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The order-emerging stage of crystallization in solution of pentacene and its derivatives was investigated using molecular dynamics simulations. Spontaneous formation of the layered herringbone moti...

Recent studies using video-based eye tracking have presented accumulating evidence that postsaccadic oscillation defined in reference to the pupil center (PSOp) is larger than that to the iris center (PSOi). This indicates that the relative motion of the pupil reflects the viscoelasticity of the tissue of the iris. It is known that the pupil size controlled by the sphincter/dilator pupillae muscles reflects many aspects of cognition. A hypothesis derived from this fact is that cognitive tasks affect the properties of PSOp due to the change in the state of these muscles. To test this hypothesis, we conducted pro- and antisaccade tasks for human participants and adopted the recent physical model of PSO to evaluate the dynamic properties of PSOp/PSOi. The results showed the dependence of the elasticity coefficient of the PSOp on the antisaccade task, but this effect was not significant for the PSOi. This suggests that cognitive tasks such as antisaccade tasks affect elasticity of the muscle of the iris. We found that the trial-by-trial fluctuation in the presaccade absolute pupil size correlated with the elasticity coefficient of PSOp. We also found the task dependence of the viscosity coefficient and overshoot amount of PSOi, which probably reflects the dynamics of the entire eyeball movement. The difference in task dependence between PSOp and PSOi indicates that the separate measures of these two can be means to distinguish factors related to the oculomotor neural system from those related to the physiological states of the iris tissue. NEW & NOTEWORTHY The state of the eyeball varies dynamically moment by moment depending on underlying neural/cognitive processing. Combining simultaneous measurements of pupil-centric and iris-centric movements and a recent physical model of postsaccadic oscillation (PSO), we show that the pupil-centric PSO is sensitive to the type of saccade task, suggesting that the physical state of the iris muscles reflects the underlying cognitive processes.

The structures and dynamics of quinuclidinium perrhenate, which is the first example of a plastic/ferroelectric crystal, were investigated by molecular dynamics simulation. Our simulation results s...

The formation of oleylamine-stabilized colloidal silver nanoparticles (Ag-NPs), which are the most promising metal NP inks for printed electronics, was modeled and simulated to investigate the shel...

Despite the prevalent use of alerting sounds in alarms and human–machine interface systems and the long-hypothesized role of the auditory system as the brain's “early warning system,” we have only a rudimentary understanding of what determines auditory salience—the automatic attraction of attention by sound—and which brain mechanisms underlie this process. A major roadblock has been the lack of a robust, objective means of quantifying sound-driven attentional capture. Here we demonstrate that: (1) a reliable salience scale can be obtained from crowd-sourcing (N= 911), (2) acoustic roughness appears to be a driving feature behind this scaling, consistent with previous reports implicating roughness in the perceptual distinctiveness of sounds, and (3) crowd-sourced auditory salience correlates with objective autonomic measures. Specifically, we show that a salience ranking obtained from online raters correlated robustly with the superior colliculus-mediated ocular freezing response, microsaccadic inhibition (MSI), measured in naive, passively listening human participants (of either sex). More salient sounds evoked earlier and larger MSI, consistent with a faster orienting response. These results are consistent with the hypothesis that MSI reflects a general reorienting response that is evoked by potentially behaviorally important events regardless of their modality.SIGNIFICANCE STATEMENTMicrosaccades are small, rapid, fixational eye movements that are measurable with sensitive eye-tracking equipment. We reveal a novel, robust link between microsaccade dynamics and the subjective salience of brief sounds (salience rankings obtained from a large number of participants in an online experiment): Within 300 ms of sound onset, the eyes of naive, passively listening participants demonstrate different microsaccade patterns as a function of the sound's crowd-sourced salience. These results position the superior colliculus (hypothesized to underlie microsaccade generation) as an important brain area to investigate in the context of a putative multimodal salience hub. They also demonstrate an objective means for quantifying auditory salience.

The molecular packing and electronic transport characteristics of mesogenic phthalocyanines having alkyl side chains at non-peripheral sites, 1,4,8,11,15,18,22,25-octaalkylphthalocyanine and its fa...

The monolayer crystal phase structure of the organic semiconductor 7-decyl-2-phenyl[1]benzothieno[3,2-b][1]benzothiophene was theoretically investigated. On the basis of a transition model from the...

Herein, we report the rational design of practical small-molecule organic semiconductors based on a π-electron skeleton of benzothieno[3,2-b]naphtho[2,3-b]thiophene (BTNT) whose layered herringbone (LHB) packing is intentionally modulated by the designated asymmetric substitutions with the phenyl group and normal alkyl chains. The thermal stability of the hybrid BTNT core is high enough, as it lies between those of dinaphtho[2,3-b:2′,3′-f]thieno[3,2-b]thiophene (DNTT) and benzothieno[3,2-b]benzothiophene (BTBT), although the solvent solubility for the substituted BTNT at ordinary 2,8-substituting positions by the alkyl chain and phenyl group remains extremely low. We show in the BTBT and BTNT derivatives that the tuning of the substituting position works to slightly bend the rodlike organic semiconductor molecules and thus to decrease the cohesive energy of the crystals with retention of the bilayer-type herringbone (b-LHB) packing for the asymmetric rodlike molecules. This modification eventually leads t...

Recent reports have demonstrated that printing processes are more suitable for producing high-performance organic thin-film transistors (OTFTs) than vacuum processes, although the formation mechanism of solution-based films is not yet understood. Here, we use molecular dynamics simulations to show that prototypical solution-processable organic semiconductors (OSCs) form a temporal lyotropic liquid-crystalline (LLC) molecular layer at the air–liquid interface of the semiconductor solution, which subsequently serves as a versatile precursor to the growth of a single-crystalline film. The molecules exhibit spontaneous alignments of the molecular long axes to form a molecular layer that is parallel to the air–liquid interface, whereas alignment with the short axes is not observed and the molecules move diffusively within the layer. The onset of short-axis orientational and positional ordering was observed in the later stage of film growth. Our findings provide evidence that unique way of film growth occurs vi...

The direction of π-stacking in a polymer thin film is crucially important in applications of semiconducting polymers. Two π-stacking configurations, “edge-on” and “face-on”, are most important in applications of semiconducting polymers. However, the molecular-level mechanism of how these configurations are selected is not clear. In this study, we perform molecular dynamics (MD) simulations to study the π-stacking orientations in solution thin films of the donor–acceptor (D–A) semiconducting polymer PNTz4T. Our simulation results showed that the PNTz4T polymers spontaneously π-stacked in an edge-on configuration near the air–PNTz4T/DCB solution interface. Our simulations using a model substrate surface showed that the PNTz4T alignment near the substrate surface was dependent on the substrate interaction strength, i.e., the orientation changed from edge-on to face-on with increasing substrate interaction strength. These results imply that the edge-on and face-on configurations are simply selected by the interaction energetics. We also investigated the effects of blending a fullerene derivative, PC61BM, on the π-stacking orientation of PNTz4T via MD simulations.

Here we discuss requirements for high performance and solution processable organic semiconductors, by presenting a systematic investigation of 7-alkyl-2-phenyl[1]benzothieno[3,2-b][1]benzothiophenes (Ph-BTBT-C n ’s). We found that the solubility and thermal properties of Ph-BTBT-C n ’s depend systematically on the substituted alkyl-chain length n. The observed features are well understood in terms of the change of molecular packing motif with n: The compounds with n ≤ 4 do not form independent alkyl chain layers, whereas those with n ≥ 5 form isolated alkyl chain layers. The latter compounds afford a series of isomorphous bilayer-type crystal structures that form two-dimensional carrier transport layers within the crystals. We also show that the Ph-BTBT-C10 afford high performance single-crystalline field-effect transistors the mobility of which reaches as high as 15.9 cm2/Vs. These results demonstrate a crucial role of the substituted alkyl chain length for obtaining high performance organic semiconductors and field-effect transistors.

The origin of the negative temperature dependence of carrier mobility in a crystal phase of 1,4,8,11,15,18,22,25-octahexylphthalocyanine was studied by utilizing a charge transport simulation based on Marcus theory and density functional theory. In order to understand the unique negative temperature dependence of carrier mobility, the theoretical calculation was carried out by taking the thermal expansion of the lattice parameters into consideration. The calculated hole mobility exhibited the similar temperature dependence as the experimental results. In the electron mobility calculation, the negative temperature dependence could be simulated by considering the degeneracy of lowest unoccupied molecular orbitals as well as the thermal expansion.

The monolayer crystal phase structure of the organic semiconductor 7-decyl-2-phenyl[1]benzothieno[3,2-b][1]benzothiophene was reinvestigated. A smaller two- or three-step bilayer-monolayer transition model than the previous transition model was newly proposed. The carrier mobilities of the resultant two monolayer crystal structure models were theoretically compared. The results show that the antiparallel monolayer crystal model that can be transformed with only two steps (without any rotation) from the bilayer structure is more probable than the nanosegregated model.

© 2019 American Physical Society. ©2019 American Physical Society. To reveal the relationship between microstructural disorder and charge localization dynamics in a van-der-Waals-bonded molecular semiconductor, the electrical properties of field-effect transistors with zone-cast pentacene films were characterized by using in situ micro-Raman spectroscopy to monitor the films' intermolecular and intramolecular vibrations. Transformations from a high-temperature phase with reduced molecular vibration along the long axis that were induced by electron localization in pentacene molecules at the channel interface and transformations from a low-temperature phase with increased molecular vibration that were induced by the electron delocalization were clearly observed under gate-bias stress, photoexcitation, and thermal annealing. Multilayer molecular dynamics simulations revealed that electrons should be localized in each pentacene molecule to stabilize the low-temperature phase and that the intramolecular Raman peak corresponds to the amount of out-of-plane molecular displacement that is most influential to charge localization and mobility reduction induced by fluctuating transfer integrals. We propose a unified picture to describe the relationship between out-of-plane structural disorder and charge localization dynamics in pentacene polymorphs.

There are indications that the pupillary dilation response (PDR) reflects surprising moments in an auditory sequence such as the appearance of a deviant noise against repetitively presented pure tones (Liao, Yoneya, Kidani, Kashino, & Furukawa, 2016), and salient and loud sounds that are evaluated by human participants subjectively (Liao, Kidani, Yoneya, Kashino, & Furukawa, 2016). In the current study, we further examined whether the reflection of PDR in auditory surprise can be accumulated and revealed in complex and yet structured auditory stimuli, i.e., music, and when the surprise is defined subjectively. Participants listened to 15 excerpts of music while their pupillary responses were recorded. In the surprise-rating session, participants rated how surprising an instance in the excerpt was, i.e., rich in variation versus monotonous, while they listened to it. In the passive-listening session, they listened to the same 15 excerpts again but were not involved in any task. The pupil diameter data obtained from both sessions were time-aligned to the rating data obtained from the surprise-rating session. Results showed that in both sessions, mean pupil diameter was larger at moments rated more surprising than unsurprising. The result suggests that the PDR reflects surprise in music automatically.

Human listeners exhibit marked sensitivity to familiar music, perhaps most readily revealed by popular “name that tune” games, in which listeners often succeed in recognizing a familiar song based on extremely brief presentation. In this work, we used electroencephalography (EEG) and pupillometry to reveal the temporal signatures of the brain processes that allow differentiation between a familiar, well liked, and unfamiliar piece of music. In contrast to previous work, which has quantified gradual changes in pupil diameter (the so-called “pupil dilation response”), here we focus on the occurrence of pupil dilation events. This approach is substantially more sensitive in the temporal domain and allowed us to tap early activity with the putative salience network. Participants (N = 10) passively listened to snippets (750 ms) of a familiar, personally relevant and, an acoustically matched, unfamiliar song, presented in random order. A group of control participants (N = 12), who were unfamiliar with all of the songs, was also tested. We reveal a rapid differentiation between snippets from familiar and unfamiliar songs: Pupil responses showed greater dilation rate to familiar music from 100–300 ms post-stimulus-onset, consistent with a faster activation of the autonomic salience network. Brain responses measured with EEG showed a later differentiation between familiar and unfamiliar music from 350 ms post onset. Remarkably, the cluster pattern identified in the EEG response is very similar to that commonly found in the classic old/new memory retrieval paradigms, suggesting that the recognition of brief, randomly presented, music snippets, draws on similar processes.