This study proposes the determination of the electronic delocalization contribution to the Anomeric Effect (EDCAE, Delta Delta E(deloc), eq 3) as a computational alternative in the evaluation of the excess of the axial preference shown by an electronegative substituent located at alpha position to the annular heteroatom of a heterocyclic compound (anomeric position) in both the presence and the absence of electronic delocalization retaining the same molecular geometry. The determination of the EDCAE is computationally accessible through the application of the natural bond orbital analysis (NBO). This type of analysis allows the comparison of hypothetical molecules lacking electronic delocalization (Lewis molecules, in which the electrons are strictly located in bonds and lone pairs) with the fully delocalized molecules retaining the same geometry and the evaluation of the anomeric effect in terms of eq 3. The role of the Lewis molecules is the same as the cyclohexane used experimentally to evaluate the anomeric effect. The advantage of doing this is that Lewis molecules are stereoelectronically inert. Applying this methology to cyclic and acyclic molecules at B3LYP/6-31G(d,p) and HF/6-31G(d,p)//B3LYP/6-31G(d,p) levels of theory, we found that the anomeric effect shown by Cl in 1,3-dioxane; F, Cl, SMe, PH(3), and CO(2)Me groups in 1,3-dithiane is of stereoelectronic nature while the preference of F, OMe, and NH(2) in 1,3-dioxane and the P(O)Me(2) group in 1,3-dithiane is not. Furthermore, this methodology shows that anomeric effects without stereoelectronic origin can modify the molecular geometry in agreement with the geometric pattern required by the double-bond no-bond model, as recently proposed by Perrin.

No abstract

No abstract

Key Points.• We validate a method to convert from sub-mm opacity to PWV.• Tipper data was successfully calibrated and correlate to high degree with data from independent sources.• Found a PWV ratio between Cerro Chajnantor and Chajnantor Plateau of 0.68.In this work, we present results from a long-term precipitable water vapor (PWV) study in the Chajnantor area, in northern Chile. Data from several instruments located at relevant sites for sub-millimeter and mid-infrared astronomy were processed to obtain relations between the atmospheric conditions among the sites. The data used for this study can be considered the richest dataset to date, because of the geographical sampling of the region, including sites at different altitudes, a time span from 2005 to 2014, and the different techniques and instruments used for the measurements. We validate a method to convert atmospheric opacity from 350 µm tipper radiometers to PWV. An average of 0.68 PWV ratio between Cerro Chajnantor and Llano of Chajnantor was found.

No abstract

No abstract

Context. Interest in the use of the Chajnantor area for millimeter and submillimeter astronomy is increasing because of its excellent atmospheric conditions. Knowing the general site annual variability in precipitable water vapor (PWV) can contribute to the planning of new observatories in the area. Aims. We seek to create a 20-year atmospheric database (1997−2017) for the Chajnantor area in northern Chile using a single common physical unit, PWV. We plan to extract weather relations between the Chajnantor Plateau and the summit of Cerro Chajnantor to evaluate potential sensitivity improvements for telescopes fielded in the higher site. We aim to validate the use of submillimeter tippers to be used at other sites and use the PWV database to detect a potential signature for local climate change over 20 years. Methods. We revised our method to convert from submillimeter tipper opacity to PWV. We now include the ground temperature as an input parameter to the conversion scheme and, therefore, achieve a higher conversion accuracy. Reults. We found a decrease in the measured PWV at the summit of Cerro Chajnantor with respect to the plateau of 28%. In addition, we found a PWV difference of 1.9% with only 27 m of altitude difference between two sites in the Chajnantor Plateau: the Atacama Pathfinder Experiment and the Cosmic Background Imager near the Atacama Large Millimeter Array center. This difference is possibly due to local topographic conditions that favor the discrepancy in PWV. The scale height for the plateau was extracted from the measurements of the plateau and the Cerro Chajnantor summit, giving a value of 1537 m. Considering the results obtained in this work from the long-term study, we do not see evidence of PWV trends in the 20-year period of the analysis that would suggest climate change in such a timescale.

No abstract