On the optical properties of Ag^{+15} ion-beam irradiated TiO_{2} and SnO_{2} thin films

The effects of 200-MeV Ag^{+15} ion irradiation on the optical properties of TiO_{2} and SnO_{2} thin films prepared by using the RF magnetron sputtering technique were investigated. These films were characterized by using UV-vis spectroscopy, and with increasing irradiation fluence, the transmittance for the TiO_{2} films was observed to increase systematically while that for SnO_{2} was observed to decrease. Absorption spectra of the irradiated samples showed minor changes in the indirect bandgap from 3.44 to 3.59 eV with increasing irradiation fluence for TiO_{2} while significant changes in the direct bandgap from 3.92 to 3.6 eV were observed for SnO_{2}. The observed modifications in the optical properties of both the TiO_{2} and the SnO_{2} systems with irradiation can be attributed to controlled structural disorder/defects in the system.Comment: 6 pages, ICAMD-201

Quasiparticle interfacial level alignment of highly hybridized frontier levels: H2_2O on TiO2_2(110)

Knowledge of the frontier levels' alignment prior to photo-irradiation is necessary to achieve a complete quantitative description of H$_2$O photocatalysis on TiO$_2$(110). Although H$_2$O on rutile TiO$_2$(110) has been thoroughly studied both experimentally and theoretically, a quantitative value for the energy of the highest H$_2$O occupied levels is still lacking. For experiment, this is due to the H$_2$O levels being obscured by hybridization with TiO$_2$(110) levels in the difference spectra obtained via ultraviolet photoemission spectroscopy (UPS). For theory, this is due to inherent difficulties in properly describing many-body effects at the H$_2$O-TiO$_2$(110) interface. Using the projected density of states (DOS) from state-of-the-art quasiparticle (QP) $G_0W_0$, we disentangle the adsorbate and surface contributions to the complex UPS spectra of H$_2$O on TiO$_2$(110). We perform this separation as a function of H$_2$O coverage and dissociation on stoichiometric and reduced surfaces. Due to hybridization with the TiO$_2$(110) surface, the H$_2$O 3a$_1$ and 1b$_1$ levels are broadened into several peaks between 5 and 1 eV below the TiO$_2$(110) valence band maximum (VBM). These peaks have both intermolecular and interfacial bonding and antibonding character. We find the highest occupied levels of H$_2$O adsorbed intact and dissociated on stoichiometric TiO$_2$(110) are 1.1 and 0.9 eV below the VBM. We also find a similar energy of 1.1 eV for the highest occupied levels of H$_2$O when adsorbed dissociatively on a bridging O vacancy of the reduced surface. In both cases, these energies are significantly higher (by 0.6 to 2.6 eV) than those estimated from UPS difference spectra, which are inconclusive in this energy region. Finally, we apply self-consistent QP$GW$ (scQP$GW$1) to obtain the ionization potential of the H$_2$O-TiO$_2$(110) interface.Comment: 12 pages, 12 figures, 1 tabl

A density functional theory study of sulphur dioxide adsorption on rutile TiO2 (110)

We have performed density functional theory calculations to investigate SO2 adsorption on both ideal and defective TiO2(110) surfaces. In agreement with experiments, we identify SO2-, SO3- and SO4-like adsorption complexes. We also find that adsorption on the defective surface leads to very strong bonding between the molecule and the surface. More importantly, we show that upon adsorption on the defective surface the S hybridization changes from the sp(2) in the isolated molecule to the sp(3) type. We demonstrate that the change is responsible for the formation of stable SO4-like species at high temperature

Exothermic water dissociation on the rutile TiO2(110) surface

There has been a long-running debate among theorists and experimentalists on the precise nature of water adsorption at the TiO2(110) surface. Some experimentalists argue that dissociative adsorption occurs only at defect sites (O vacancies) and therefore at low coverages. Although there is no doubt that vacancies are strongly reactive, until now there has been no firm understanding of adsorption on a perfect surface with which to contrast behavior. Here we report extensive and very detailed calculations that demonstrate that dissociation of a molecule is exothermic. Experimental findings are rationalized by the existence of a metastable molecular state separated from the dissociated state by a substantial barrier. We show that the barrier varies in height with coverage and with the presence of neighboring adsorbates, and we detail mechanisms for both phenomena. Finally, we reassess photoelectron spectroscopy results, showing their consistency with our predictions

Towards a first-principles picture of the oxide-water interface

We apply first-principles molecular dynamics and static calculations in the study of several layers of water adsorbed at an oxide surface. Our aim is to bridge the gap between the well-explored monolayer and the complex, little-understood oxide-water interface by probing this middle ground where there is still contact with vacuum surface experiments. By examining coverages up to three monolayers on rutile TiO2(110) we emerge with three major conclusions. First, there is a trend with increasing coverage for water near the surface to become more molecular in nature, viz. the coordination of H to O for all near-surface molecules tends to lower values as the coverage increases. This means the hydroniumlike and other partially dissociated structures predicted up to 1.5 monolayers become less favorable as the coverage increases. Second, the templating influence of the surface disrupts the structure of the second and third layers at 3 ML coverage. Third, we can make a very satisfactory interpretation of experimental results (HREELS and TPD) gaining some new insights in the process. The assignment of TPD peaks to layer-by-layer desorption is shown to be open to question, as some second-layer molecules may contribute to the same peak as do those in the third layer. (C) 2003 American Institute of Physics

A density functional theory study of the coadsorption of water and oxygen on TiO2(110)

The behavior of adsorbed water on oxides is of fundamental interest in many areas. Despite considerable attention received recently, our understanding of water chemistry is still short of needs and expectations, particularly on the topic of the coadsorption of water and other species. In this study we carry out density functional theory calculations to investigate the coadsorption of water and oxygen on the TiO2(110) surface. We show that oxygen exerts profound influences on the water adsorption, altering the mechanism of water dissociation. On the one hand, the possible dissociation route along [-110] is prohibited due to the weakening of the H bond between water and the lattice bridging oxygen in the presence of the coadsorbed oxygen, and on the other hand the coadsorbed oxygen induces dissociation along [001]. These results lead to a consistent interpretation of experiments. Furthermore, several possible final states and the related formation mechanisms are discussed in detail

Multilayer water adsorption on rutile TiO2(110): A first-principles study

The adsorption of water on the TiO2(110) surface has become the model process in efforts to understand metal oxide-aqueous solution interfaces. Considerable progress has been made in understanding low-coverage situations where first-principle calculations have been employed to good effect. However, current theory is less well developed for coverage above one monolayer. Here we present results of calculations on the adsorption process in forming the second water layer, that is, the adsorption of water on the fully hydrated surface. We show that there are many competitive adsorption sites owing to the numerous hydrogen-bonding possibilities. The presence of the second layer water molecules facilitates proton transfer among the adsorbates within chainlike configurations, and we present some illustration of these processes. We show how the adsorption energetics computed here along with recent calculations on defective surface and low-coverage adsorption may be used to provide a satisfactory interpretation of the temperature programmed desorption data for this system. Finally, we compute the vibrational spectrum for H and compare with the high-resolution electron-energy-loss spectroscopy measurements. (C) 2003 American Institute of Physics

Vegetation EVI changes and response to natural factors and human activities based on geographically and temporally weighted regression

The research on vegetation changes plays a crucial role in the assessment of ecosystem health, monitoring environmental changes, providing early warnings for natural disasters, and supporting decision-making for sustainable development. However, understanding the nonstationary characteristics of drivers affecting vegetation change remains challenging. This study used Enhanced Vegetation Index (EVI) data obtained through Google Earth Engine (GEE), Theil-Sen, and Mann-Kendall methods to analyze the spatial-temporal patterns and trends of vegetation changes in Sichuan, western China from 2000 to 2020. The Geographical and Temporal Weighted Regression (GTWR) method was applied to deal with spatial and temporal nonstationarity simultaneously. Results showed that vegetation cover in Sichuan was good overall, with medium and high vegetation covering more than 78% of the area. About 72.75% of the area showed an increasing trend in vegetation cover, and areas with extremely significant and significant EVI growth (p < 0.01 and 0.01 ≤ p < 0.05) accounted for 23.94% of the total area. The areas with significant increases in vegetation EVI were mainly distributed in northeast, east, southeast, central, and southwest in Sichuan, while the areas with significant decreases were mainly distributed in the central Sichuan plain urban agglomeration and western Sichuan plateau. GTWR addressed the nonstationary effect of the temporal dimension on the drivers of natural and human activities, with a fitted R2 of 0.846. The study identified climate, terrain, and human activities as the primary driving factors behind vegetation EVI fluctuations. Annual average temperature and precipitation, human activities, and slope had a positive impact on vegetation EVI changes, while solar radiation and aspect had a negative inhibitory effect. The effects of climate, terrain, and human activities on EVI changes exhibited significant spatial heterogeneity and clustering, resulting in either positive promotion or negative inhibition. This study provides an additional methodology to solve the nonstationary problem of vegetation change trends and their response mechanisms. The revealed changes in vegetation EVI and the spatiotemporal heterogeneity characteristics of their driving factors are important for fragile ecosystems to adapt to and mitigate the effects of natural changes and human activities. Revealing the variations in vegetation EVI and their underlying drivers can showcase diverse characteristics across regions and time periods, the presence of spatiotemporal heterogeneity holds great significance in comprehending the adaptive strategies employed by fragile ecosystems to mitigate the effects of natural fluctuations and human-induced activities