Enhanced Lifetime Of Excitons In Nonepitaxial Au/cds Core/shell Nanocrystals

The ability of metal nanoparticles to capture light through plasmon excitations offers an opportunity for enhancing the optical absorption of plasmon-coupled semiconductor materials via energy transfer. This process, however, requires that the semiconductor component is electrically insulated to prevent a backward charge flow into metal and interfacial states, which causes a premature dissociation of excitons. Here we demonstrate that such an energy exchange can be achieved on the nanoscale by using nonepitaxial Au/CdS core/shell nanocomposites. These materials are fabricated via a multistep cation exchange reaction, which decouples metal and semiconductor phases leading to fewer interfacial defects. Ultrafast transient absorption measurements confirm that the lifetime of excitons in the CdS shell (tau approximate to 300 ps) is much longer than lifetimes of excitons in conventional, reduction-grown Au/CdS heteronanostructures. As a result, the energy of metal nanoparticles can be efficiently utilized by the semiconductor component without undergoing significant nonradiative energy losses, an important property for catalytic or photovoltaic applications. The reduced rate of exciton dissociation in the CdS domain of Au/CdS nanocomposites was attributed to the nonepitaxial nature of Au/CdS interfaces associated with low defect density and a high potential barrier of the interstitial phase

Ab initio studies of structures and properties of small potassium clusters

We have studied the structure and properties of potassium clusters containing even number of atoms ranging from 2 to 20 at the ab initio level. The geometry optimization calculations are performed using all-electron density functional theory with gradient corrected exchange-correlation functional. Using these optimized geometries we investigate the evolution of binding energy, ionization potential, and static polarizability with the increasing size of the clusters. The polarizabilities are calculated by employing Moller-Plesset perturbation theory and time dependent density functional theory. The polarizabilities of dimer and tetramer are also calculated by employing large basis set coupled cluster theory with single and double excitations and perturbative triple excitations. The time dependent density functional theory calculations of polarizabilities are carried out with two different exchange-correlation potentials: (i) an asymptotically correct model potential and (ii) within the local density approximation. A systematic comparison with the other available theoretical and experimental data for various properties of small potassium clusters mentioned above has been performed. These comparisons reveal that both the binding energy and the ionization potential obtained with gradient corrected potential match quite well with the already published data. Similarly, the polarizabilities obtained with Moller-Plesset perturbation theory and with model potential are quite close to each other and also close to experimental data.Comment: 33 pages including 10 figure

Dynamics of purple sulfur bacteria in saline meromictic Lake Shira (Khakasia, Siberia) for the period 2007-2013

Текст статьи не публикуется в открытом доступе в соответствии с политикой журнала.According to the results of seasonal monitoring, in 2007–2013 purple sulfur bacteria morphologically similar to Thiocapsa sp. Shira_1 (AJ633676 in EMBL/GenBank) predominated in the anoxygenic phototrophic community of the water column of the meromictic Lake Shira (Khakassia, Siberia). No pronounced seasonal periodicity in the total cell number in the water column was revealed during the period of observation. In some years cell number during the period when the lake was covered with ice was reliably higher than in summer. The absence of seasonal periodicity was probably due to the low amplitude of seasonal variations in temperature and illumination in the redox zone, resulting from its relatively deep location (12– 16 m). The year-to-year dynamics was characterized by a reliable decrease of the total cell number in 2009– 2010 and maxima in 2007 and 2011–2012. Canonical correlation analysis revealed that water temperature in the redox zone was the best predictor of the PSB abundance in Lake Shira. Water temperature, in turn, depended on the depth of mixing of the water column. Intense mixing in 2009–2011 was probably responsible for decreased PSB abundance in the lake. On the other hand, the absence of deep winter mixing, resulting in stable conditions in the chemocline, favored the preservation of relatively high PSB biomass. Prediction of circulation depth, which depends mainly on the weather conditions and dynamics of the water level, is required for prediction of PSB abundance in Lake Shira. These results may be useful for paleolimnological reconstructions of the history of the lake based on the remnants of purple sulfur bacteria in bottom sediments

Dynamics of purple sulfur bacteria in saline meromictic Lake Shira (Khakasia, Siberia) for the period 2007-2013

Текст статьи не публикуется в открытом доступе в соответствии с политикой журнала.According to the results of seasonal monitoring, in 2007–2013 purple sulfur bacteria morphologically similar to Thiocapsa sp. Shira_1 (AJ633676 in EMBL/GenBank) predominated in the anoxygenic phototrophic community of the water column of the meromictic Lake Shira (Khakassia, Siberia). No pronounced seasonal periodicity in the total cell number in the water column was revealed during the period of observation. In some years cell number during the period when the lake was covered with ice was reliably higher than in summer. The absence of seasonal periodicity was probably due to the low amplitude of seasonal variations in temperature and illumination in the redox zone, resulting from its relatively deep location (12– 16 m). The year-to-year dynamics was characterized by a reliable decrease of the total cell number in 2009– 2010 and maxima in 2007 and 2011–2012. Canonical correlation analysis revealed that water temperature in the redox zone was the best predictor of the PSB abundance in Lake Shira. Water temperature, in turn, depended on the depth of mixing of the water column. Intense mixing in 2009–2011 was probably responsible for decreased PSB abundance in the lake. On the other hand, the absence of deep winter mixing, resulting in stable conditions in the chemocline, favored the preservation of relatively high PSB biomass. Prediction of circulation depth, which depends mainly on the weather conditions and dynamics of the water level, is required for prediction of PSB abundance in Lake Shira. These results may be useful for paleolimnological reconstructions of the history of the lake based on the remnants of purple sulfur bacteria in bottom sediments

Photodissociation of Bromobenzene in Solution.

The photodissociation of bromobenzene in solution was investigated with ultrafast transient absorption spectroscopy following excitation at 266 nm. Ab initio calculations of lower singlet and triplet states were performed in order to guide the interpretations. The main feature of the kinetics measured between 300 and 930 nm in acetonitrile is a 9±1 ps decay, which we mainly assign to predissociation. Similar decays were observed in hexane, dichloromethane and tetrachloromethane at 400 and 800 nm. Other features in acetonitrile, such as complicated short-time dynamics between 420 and 620 nm and a long-lived component, might indicate the involvement of lower triplet states

Disturbance of meromixis in saline Lake Shira (Siberia, Russia): possible reasons and ecosystem response

Saline Lake Shira (Southern Siberia, Russia) was meromictic through the observation period 2002-2015. During the under-ice periods of 2015 and 2016, complete mixing of the water column was recorded for the first time, and hydrogen sulphide temporarily disappeared from the water column of the lake; i.e. in those years the lake turned to holomixis. In the summer of 2015, a sharp increase in chlorophyll a, organic carbon, zooplankton, and phytoflagellates was observed in the lake, which was probably due to the release of nutrients from the monimolimnion. Purple sulfur bacteria completely disappeared from the lake after the first mixing in 2015, and did not reappear despite the restoration of meromixis in 2017. Thus, it was demonstrated that purple sulfur bacteria are sensitive to the weakening of the stratification of Lake Shira. Based on the data of the seasonal monitoring of temperature and salinity profiles over the period 2002-2017, it was presumed that the main cause of deep mixing in 2015 was the weakening of the salinity gradient due to strong wind impact and early ice retreat in the spring of 2014. In addition, it was shown that in previous years a significant contribution to the maintenance of meromixis was made by an additional influx of fresh water, which caused a rise in the lake level in the period 2002-2007. Thus, we identified a relationship between the stratification regime of the lake and the change in its level, which provides valuable information both for the forecast of water quality and for reconstruction of the Holocene climate humidity in this region of Southern Siberia from the sediment cores of Lake Shira

Disturbance of meromixis in saline Lake Shira (Siberia, Russia): possible reasons and ecosystem response

Saline Lake Shira (Southern Siberia, Russia) was meromictic through the observation period 2002-2015. During the under-ice periods of 2015 and 2016, complete mixing of the water column was recorded for the first time, and hydrogen sulphide temporarily disappeared from the water column of the lake; i.e. in those years the lake turned to holomixis. In the summer of 2015, a sharp increase in chlorophyll a, organic carbon, zooplankton, and phytoflagellates was observed in the lake, which was probably due to the release of nutrients from the monimolimnion. Purple sulfur bacteria completely disappeared from the lake after the first mixing in 2015, and did not reappear despite the restoration of meromixis in 2017. Thus, it was demonstrated that purple sulfur bacteria are sensitive to the weakening of the stratification of Lake Shira. Based on the data of the seasonal monitoring of temperature and salinity profiles over the period 2002-2017, it was presumed that the main cause of deep mixing in 2015 was the weakening of the salinity gradient due to strong wind impact and early ice retreat in the spring of 2014. In addition, it was shown that in previous years a significant contribution to the maintenance of meromixis was made by an additional influx of fresh water, which caused a rise in the lake level in the period 2002-2007. Thus, we identified a relationship between the stratification regime of the lake and the change in its level, which provides valuable information both for the forecast of water quality and for reconstruction of the Holocene climate humidity in this region of Southern Siberia from the sediment cores of Lake Shira