Chemical Modification of Polaronic States in Anatase TiO2(101)

Two polymorphs of TiO2, anatase and rutile, are employed in photocatalytic applications. It is broadly accepted that anatase is the more catalytically active and subsequently finds wider commercial use. In this work, we focus on the Ti3+ polaronic states of anatase TiO2(101), which lie at ∼1.0 eV binding energy and are known to increase catalytic performance. Using UV-photoemission and two-photon photoemission spectroscopies, we demonstrate the capability to tune the excited state resonance of polarons by controlling the chemical environment. Anatase TiO2(101) contains subsurface polarons which undergo sub-band-gap photoexcitation to states ∼2.0 eV above the Fermi level. Formic acid adsorption dramatically influences the polaronic states, increasing the binding energy by ∼0.3 eV. Moreover, the photoexcitation oscillator strength changes significantly, resonating with states ∼3.0 eV above the Fermi level. We show that this behavior is likely due to the surface migration of subsurface oxygen vacancies

Is retention of the acetabular component at revision surgery a long-term solution?

BACKGROUND: Acetabular retention in revision total hip arthroplasty (THA) may be advantageous, yet long-term survival data is limited. Thus, we investigated long-term survivorship of retained acetabular components in revision THA with analysis of rerevision rate, instability risk, and clinical outcomes. METHODS: We reviewed 98 hips with polyethylene wear and/or osteolysis that were revised with retained acetabular components. Acetabular inclination and anteversion were measured from prerevision radiographs. A retrospective chart review was performed, collecting outcomes of interest including Harris hip score, instability events, and rerevision surgery. Kaplan-Meier analysis was used to calculate the risk of revision over time. Predictors of survival including acetabular component position were analyzed by multiple logistic regression. RESULTS: Average follow-up was 13 years (range, 5-24). Survivorship rates at 5, 10, 15, and 20 years were 89.7%, 81.6%, 70.8%, and 63.8%, respectively. There was improvement in average Harris hip score (61 to 76, CONCLUSIONS: Retention of a well-fixed acetabular component in revision THA provides acceptable long-term outcomes with a 15-year survivorship of 71%. Instability and aseptic loosening were the most common reasons for rerevision. Surgeons may consider retaining the acetabular component at revision surgery if the implant is well-fixed and well-positioned

Photoexcitation of bulk polarons in rutile TiO₂

The excitation of surface-localized polaronic states has recently been discussed as an additional photocatalytic channel to band gap excitation for rutile Ti O 2 . A contribution from photoexcitation of bulk polarons could, in principle, provide a greater contribution because of their higher number and their protection from oxidation. However, determining such a contribution to the photoyield is challenging and has not been achieved thus far. Here we use two photon photoemission spectroscopy measurements to separate bulk and surface polaron photoexcitation. We find that bulk polarons are less bound by 0.2 eV compared with polarons at the surface, consistent with our results of hybrid density functional theory calculations. Because the excited state is also shifted to higher energy, bulk polarons have the same photoexcitation resonance energy as at the surface (3.6 eV) with a threshold at 3.1 eV. This is degenerate with the band gap, suggesting that bulk polarons could also provide an additional contribution to the photoyield

Zero Threshold for Water Adsorption on MAPbBr3

Hybrid organic-inorganic perovskites (HOIPs) have shown great promise in a wide range of optoelectronic applications. However, this performance is inhibited by the sensitivity of HOIPs to various environmental factors, particularly high levels of relative humidity. This study uses X-ray photoelectron spectroscopy (XPS) to determine that there is essentially no threshold to water adsorption on the in situ cleaved MAPbBr3 (001) single crystal surface. Using scanning tunneling microscopy (STM), it shows that the initial surface restructuring upon exposure to water vapor occurs in isolated regions, which grow in area with increasing exposure, providing insight into the initial degradation mechanism of HOIPs. The electronic structure evolution of the surface was also monitored via ultraviolet photoemission spectroscopy (UPS), evidencing an increased bandgap state density following water vapor exposure, which is attributed to surface defect formation due to lattice swelling. This study will help to inform the surface engineering and designs of future perovskite-based optoelectronic devices

An overview of ISCAT 2000

The Investigation of Sulfur Chemistry in the Antarctic Troposphere (ISCAT) took place over the timer period of 15 November to 31 December in the year 2000. The study location was the Amundsen Scott Station in Antarctica. ISCAT 2000 defines the second phase of a program designed to explore tropospheric chemistry in Antarctica. As in 1998, the 2000 ISCAT study revealed a strong oxidizing environment at South Pole (SP). During the 2000 investigation, however, the suite of measurements was greatly expanded. These new measurements established the recycling of reactive nitrogen as a critical component of this unique environment. This paper first presents the historical background leading up to the ISCAT 2000 observations; then it focuses on providing a summary of the year 2000 results and contrasts these with those recorded during 1998. Important developments made during the 2000 study included the recording of SP data for several species being emitted from the snowpack. These included NO, H 2O2 and CH2O. In this context, eddy-diffusion flux measurements provided the first quantitative estimates of the SP NO and NOx snow-to-atmosphere fluxes. This study also revealed that HNO 3 and HO2NO2 were major sink species for HOx and NOx radicals. And, it identified the critical factors responsible for SP NO levels exceeding those at other polar sites by nearly an order of magnitude. Finally, it reports on the levels of gas phase sulfur species and provides evidence indicating that the absence of DMS at SP is most likely due to its greatly shorten chemical lifetime in the near vicinity of the plateau. It is proposed that this is due to the influence of NO on the distribution of OH in the lower free troposphere over a region that extends well beyond the plateau itself. Details related to each of the above findings plus others can be found in the 11 accompanying Special Issue papers. © 2004 Elsevier Ltd. All rights reserved

Polaron-adsorbate coupling at the TiO2(110)-carboxylate interface

Understanding how adsorbates influence polaron behavior is of fundamental importance in describing the catalytic properties of TiO2. Carboxylic acids adsorb readily at TiO2 surfaces, yet their influence on polaronic states is unknown. Using UV photoemission spectroscopy (UPS), two-photon photoemission spectroscopy (2PPE), and density functional theory (DFT) we show that dissociative adsorption of formic and acetic acids has profound, yet different, effects on the surface density, crystal field, and photoexcitation of polarons in rutile TiO2(110). We also show that these variations are governed by the contrasting electrostatic properties of the acids, which impacts the extent of polaron−adsorbate coupling. The density of polarons in the surface region increases more in formate-terminated TiO2(110) relative to acetate. Consequently, increased coupling gives rise to new photoexcitation channels via states 3.83 eV above the Fermi level. The onset of this process is 3.45 eV, likely adding to the catalytic photoyield

Contributions of nitrogen deposition and forest regrowth to terrestrial carbon uptake

<p>Abstract</p> <p>Background</p> <p>The amount of reactive nitrogen deposited on land has doubled globally and become at least five-times higher in Europe, Eastern United States, and South East Asia since 1860 mostly because of increases in fertilizer production and fossil fuel burning. Because vegetation growth in the Northern Hemisphere is typically nitrogen-limited, increased nitrogen deposition could have an attenuating effect on rising atmospheric CO₂by stimulating the vegetation productivity and accumulation of carbon in biomass.</p> <p>Results</p> <p>This study shows that elevated nitrogen deposition would not significantly enhance land carbon uptake unless we consider its effects on re-growing forests. Our results suggest that nitrogen enriched land ecosystems sequestered 0.62–2.33 PgC in the 1980s and 0.75–2.21 PgC in the 1990s depending on the proportion and age of re-growing forests. During these two decades land ecosystems are estimated to have absorbed 13–41% of carbon emitted by fossil fuel burning.</p> <p>Conclusion</p> <p>Although land ecosystems and especially forests with lifted nitrogen limitations have the potential to decelerate the rise of CO₂concentrations in the atmosphere, the effect is only significant over a limited period of time. The carbon uptake associated with forest re-growth and amplified by high nitrogen deposition will decrease as soon as the forests reach maturity. Therefore, assessments relying on carbon stored on land from enhanced atmospheric nitrogen deposition to balance fossil fuel emissions may be inaccurate.</p

An Ethnohistorical Perspective on Cheyenne Demography

Administrative censuses of the Southern Cheyenne Indians from 1880,1891, and 1900 permit family reconstitution, identification of residence groups, and comparisons of fertility between monogamous and polygynous women, when the records are approached by ethnohistori cal methods. This approach includes an awareness of the aboriginal adoption practices, kinship system, and naming practices. It is argued that the biases and distortions of administrative records can be effectively corrected to add to our store of information on band and tribal societies.Yeshttps://us.sagepub.com/en-us/nam/manuscript-submission-guideline

Error-driven retrieval in agreement attraction rarely leads to misinterpretation

Previous work on agreement computation in sentence comprehension motivates a model in which the parser predicts the verb’s number and engages in retrieval of the agreement controller only when it detects a mismatch between the prediction and the bottom-up input. It is the error-driven second stage of this process that is prone to similarity-based interference and can result in the illusory licensing of a subject–verb number agreement violation in the presence of a structurally irrelevant noun matching the number marking on the verb (‘The bed by the lamps were…’), giving rise to an effect known as ‘agreement attraction’. Here we ask to what extent the error-driven retrieval process underlying the illusory licensing alters the structural and thematic representation of the sentence. We use a novel dual-task paradigm that combines self-paced reading with a speeded forced choice task to investigate whether agreement attraction leads comprehenders to erroneously interpret the attractor as the thematic subject, which would indicate structural reanalysis. Participants read sentence fragments (‘The bed by the lamp/lamps was/were undoubtedly quite’) and completed the sentences by choosing between two adjectives (‘comfortable’/’bright’) which were either compatible with the subject’s head noun or with the attractor. We found the expected agreement attraction profile in the self-paced reading data but the interpretive error occurs on only a small subset of attraction trials, suggesting that in agreement attraction agreement checking rarely matches the thematic relation. We propose that illusory licensing of an agreement violation often reflects a low-level rechecking process that is only concerned with number and does not have an impact on the structural representation of the sentence. Interestingly, this suggests that error-driven repair processes can result in a globally inconsistent final sentence representation with a persistent mismatch between the subject and the verb

Attraction effects in honorific agreement in Korean

Previous studies have suggested that sentence processing is mediated by content-addressable direct retrieval processes (McElree, 2000; McElree, Foraker, & Dyer, 2003). However, the memory retrieval processes may differ as a function of the type of dependency. For example, while many studies have reported facilitatory intrusion effects associated with a structurally illicit antecedent during the processing of subject-verb number or person agreement and negative polarity items (Dillon, Mishler, Sloggett, & Phillips, 2013; Pearlmutter, Garnsey & Bock, 1999; Xiang, Dillon, & Phillips, 2009), studies investigating reflexives have not found consistent evidence of intrusion effects (Parker & Lago, & Phillips, 2015; Sturt & Kwon, 2015; cf. Nicol & Swinney, 1989; Sturt, 2003). Similarly, the memory retrieval processes could be also sensitive to cross-linguistic differences (cf. Lago, Shalom, Sigman, Lau & Phillips, 2015). We report one self-paced reading experiment and one eye-tracking experiment that examine the processing of subject-verb honorific agreement, a dependency that is different from those that have been studied to date, in Korean, a typologically different language from those previously studied. The overall results suggest that the retrieval processes underlying the processing of subject-verb honorific agreement in Korean are susceptible to facilitatory intrusion effects from a structurally illicit but feature-matching subject, with a pattern that is similar to subject-verb agreement in English. In addition, the attraction effect was not limited to the ungrammatical sentences but was also found in grammatical sentences. The clear attraction effect in the grammatical sentences suggest that the attraction effect does not solely arise as the result of an error-driven process (cf. Wagers, Lau & Phillips, 2009), but is likely also to result from general mechanisms of retrieval processes of activating of potential items in memory (Vasishth, Brüssow, Lewis, & Drenhaus, 2008)