CCSD(T) Study of CD3-O-CD3 and CH3-O-CD3 Far-Infrared Spectra

From a vibrationally corrected 3D potential energy surface determined with highly correlated ab initio calculations (CCSD(T)), the lowest vibrational energies of two dimethyl-ether isotopologues, 12CH3–16O–12CD3 (DME-d3) and 12CD3–16O–12CD3 (DME-d6), are computed variationally. The levels that can be populated at very low temperatures correspond to the COC-bending and the two methyl torsional modes. Molecular symmetry groups are used for the classification of levels and torsional splittings. DME-d6 belongs to the G36 group, as the most abundant isotopologue 12CH3–16O–12CH3 (DME-h6), while DME-d3 is a G18 species. Previous assignments of experimental Raman and far-infrared spectra are discussed from an effective Hamiltonian obtained after refining the ab initio parameters. Because a good agreement between calculated and experimental transition frequencies is reached, new assignments are proposed for various combination bands corresponding to the two deuterated isotopologues and for the 020 → 030 transition of DME-d6. Vibrationally corrected potential energy barriers, structural parameters, and anharmonic spectroscopic parameters are provided. For the 3N – 9 neglected vibrational modes, harmonic and anharmonic fundamental frequencies are obtained using second-order perturbation theory by means of CCSD and MP2 force fields. Fermi resonances between the COC-bending and the torsional modes modify DME-d3 intensities and the band positions of the torsional overtones

Analysing the impact of climate change on hydrological ecosystem services in laguna del sauce (Uruguay) using the swat model and remote sensing data

Assessing how climate change will affect hydrological ecosystem services (HES) provision is necessary for long-term planning and requires local comprehensive climate information. In this study, we used SWAT to evaluate the impacts on four HES, natural hazard protection, erosion control regulation and water supply and flow regulation for the Laguna del Sauce catchment in Uruguay. We used downscaled CMIP-5 global climate models for Representative Concentration Pathways (RCP) 2.6, 4.5 and 8.5 projections. We calibrated and validated our SWAT model for the periods 2005 2009 and 2010 2013 based on remote sensed ET data. Monthly NSE and R2 values for calibration and validation were 0.74, 0.64 and 0.79, 0.84, respectively. Our results suggest that climate change will likely negatively affect the water resources of the Laguna del Sauce catchment, especially in the RCP 8.5 scenario. In all RCP scenarios, the catchment is likely to experience a wetting trend, higher temperatures, seasonality shifts and an increase in extreme precipitation events, particularly in frequency and magnitude. This will likely affect water quality provision through runoff and sediment yield inputs, reducing the erosion control HES and likely aggravating eutrophication. Although the amount of water will increase, changes to the hydrological cycle might jeopardize the stability of freshwater supplies and HES on which many people in the south-eastern region of Uruguay depend. Despite streamflow monitoring capacities need to be enhanced to reduce the uncertainty of model results, our findings provide valuable insights for water resources planning in the study area. Hence, water management and monitoring capacities need to be enhanced to reduce the potential negative climate change impacts on HES. The methodological approach presented here, based on satellite ET data can be replicated and adapted to any other place in the world since we employed open-access software and remote sensing data for all the phases of hydrological modelling and HES provision assessment. © 2021 by the authors. Licensee MDPI, Basel, Switzerland.This work has received funding from the European Union’s Horizon 2020 research and innovation programme within the framework of the project SMARTLAGOON under grant agreement No. 101017861. This study was also supported by the State Research Agency of Spain through the excellence certification María de Maeztu (Ref. MDM-2017-0714). Celina Aznarez was supported by the Doctoral INPhINIT–INCOMING program, fellowship code (LCF/BQ/DI20/11780004), from “la Caixa” Foundation (ID 100010434). Javier Senent-Aparicio was supported by the training grant (21201/EE/19) awarded by the Séneca Foundation in the framework of the Jimenez de la Espada Mobility, Cooperation and Internationalization Program. Adrián López-Ballesteros was supported by the Spanish Ministerio de Educación, Cultura y Deporte with an FPU grant (FPU17/00923). Juan Pablo Pacheco was supported by the Sino-Danish Center–Aarhus University, the University of the Chinese Academy of Sciences and the University of the Republic, Uruguay. This work has received funding from the European Union?s Horizon 2020 research and innovation programme within the framework of the project SMARTLAGOON under grant agreement No. 101017861. This study was also supported by the State Research Agency of Spain through the excellence certification Mar?a de Maeztu (Ref. MDM-2017-0714). Celina Aznarez was supported by the Doctoral INPhINIT?INCOMING program, fellowship code (LCF/BQ/DI20/11780004), from ?la Caixa? Foundation (ID 100010434). Javier Senent-Aparicio was supported by the training grant (21201/EE/19) awarded by the S?neca Foundation in the framework of the Jimenez de la Espada Mobility, Cooperation and Internationalization Program. Adri?n L?pez-Ballesteros was supported by the Spanish Ministerio de Educaci?n, Cultura y Deporte with an FPU grant (FPU17/00923). Juan Pablo Pacheco was supported by the Sino-Danish Center?Aarhus University, the University of the Chinese Academy of Sciences and the University of the Republic, Uruguay. The authors acknowledge Paper Check Proofreading and Editing Services for proofreading the manuscript

An analysis of the methyl rotation dynamics in the S0 (X̃ 1A1) and T1 (ã 3A2) states of thioacetone, (CH3)2 CS and (CD 3)2 CS from pyrolysis jet spectra

Jet-cooled, laser-induced phosphorescence excitation spectra (LIP) of thioacetone (CH3)2CS/(CD3)2 CS have been recorded over the region 16 800-18 500 cm-1 using the pyrolysis jet spectroscopic technique. The responsible electronic transition, T 1 ←-S0, ã 3 A ″ ← X̃ 1A1, results from an n → π* electron promotion and gives rise to a pattern of vibronic bands that were attributed to activity of the methyl torsion and the sulphur out-of-plane wagging modes. The intensities of the torsional and wagging progressions in the excitation spectra were interpreted in terms of a C2υ-Cs molecular distortion of the triplet molecule from its singlet ground state equilibrium structure. A complete unrestricted Hartree-Fock (UHF) ab initio molecular orbital (MO) structural optimization of the T1 state predicted that the sulphur was displaced by 27.36° from the molecular plane and the methyl groups were rotated by 10.93° in clockwise-counterclockwise directions. Restricted Hartree-Fock (RHF) calculations were used to generate the F(θ1,θ2) potential surface governing methyl rotation for the S0 state. This was incorporated into a two-dimensional Hamiltonian, symmetrized for the G36 point group and solved variationally for the torsional frequencies. The calculated frequencies of 159.97/118.94 for the ν17 (b1) mode of S0 (CH3)2CS/(CD3)2 CS were found to agree with the experimental values, 153.2/114.7 cm-1. © 1991 American Institute of Physics.The authors are grateful to the Natural Sciences and Engineering Research Council of Canada for financial support of this work. D. J. C. acknowledges the support of the National Science Foundation through Grant No. CHE-8914403.Peer Reviewe

Numerical Simulation of the Flow Inside a Scroll Compressor Equipped with Intermediate Discharge Valves

This paper presents the results of CFD simulations of the compression process of a scroll compressor. The compressor geometry accounts for the final scroll gas pockets, two Intermediate Discharge Valves (IDVs), the central discharge zone and the upper shell. The numerical model uses a real gas equation of state to determine gas properties during the compression process and accounts for the motion of the orbiting scroll and IDVs using a mesh smoothing and remeshing algorithm. The IDVs are represented as a spring mass system with their movement controlled via the pressure difference around the valve. Appropriate pressure based boundary conditions are used at entry to the third gas pocket and at the exit of the upper shell. An initial analysis of the results has shown that it is possible to achieve time accurate results of the pressure field throughout the flow domain and also determine the impact of the IDVs on scroll performance. The results will also enable a more thorough analysis of the fluid flow and compression process inside the scroll in order to improve its performance

Laboratory and tentative interstellar detection of trans-methyl formate using the publicly available Green Bank Telescope PRIMOS survey

The rotational spectrum of the higher-energy trans conformational isomer of methyl formate has been assigned for the first time using several pulsed-jet Fourier transform microwave spectrometers in the 6-60 GHz frequency range. This species has also been sought toward the Sagittarius B2(N) molecular cloud using the publicly available PRIMOS survey from the Green Bank Telescope. We detect seven absorption features in the survey that coincide with laboratory transitions of trans-methyl formate, from which we derive a column density of 3.1 (+2.6, -1.2) \times 10^13 cm-2 and a rotational temperature of 7.6 \pm 1.5 K. This excitation temperature is significantly lower than that of the more stable cis conformer in the same source but is consistent with that of other complex molecular species recently detected in Sgr B2(N). The difference in the rotational temperatures of the two conformers suggests that they have different spatial distributions in this source. As the abundance of trans-methyl formate is far higher than would be expected if the cis and trans conformers are in thermodynamic equilibrium, processes that could preferentially form trans-methyl formate in this region are discussed. We also discuss measurements that could be performed to make this detection more certain. This manuscript demonstrates how publicly available broadband radio astronomical surveys of chemically rich molecular clouds can be used in conjunction with laboratory rotational spectroscopy to search for new molecules in the interstellar medium.Comment: 40 pages, 7 figures, 4 tables; accepted for publication in Ap

Natural and sail-displaced doubly-symmetric Lagrange point orbits for polar coverage

This paper proposes the use of doubly-symmetric, eight-shaped orbits in the circular restricted three-body problem for continuous coverage of the high-latitude regions of the Earth. These orbits, for a range of amplitudes, spend a large fraction of their period above either pole of the Earth. It is shown that they complement Sun-synchronous polar and highly eccentric Molniya orbits, and present a possible alternative to low thrust pole-sitter orbits. Both natural and solar-sail displaced orbits are considered. Continuation methods are described and used to generate families of these orbits. Starting from ballistic orbits, other families are created either by increasing the sail lightness number, varying the period or changing the sail attitude. Some representative orbits are then chosen to demonstrate the visibility of high-latitude regions throughout the year. A stability analysis is also performed, revealing that the orbits are unstable: it is found that for particular orbits, a solar sail can reduce their instability. A preliminary design of a linear quadratic regulator is presented as a solution to stabilize the system by using the solar sail only. Finally, invariant manifolds are exploited to identify orbits that present the opportunity of a ballistic transfer directly from low Earth orbit

The Moderating Role of Intellectual Humility in the Adoption of ICT: A Study Across Life-Span

Literature has shown age-related differences in the adoption process. In this way, it is very important to encourage the adoption of ICT by the elderly, in order to maintain their independence in daily life. However, some specific cognitive variables were not considered in theoretical models until a decade ago. One of the emerging fields in this area is the science of learnable intelligence, which investigates the role of thinking dispositions. The variable which we have focused on is intellectual humility. For this propose, a sample of 306 participants from 18 to 87 years was selected. Age was selected as a predictor variable. Intellectual humility was tested as a moderator between aging and ICT adoption, more precisely computer and mobile devices. The model fitted the theoretical proposal. However, the subscale known as Independence of the intellect and ego was the only one to fulfill all the requirements for the moderational analysis. The findings suggest a moderational effect that might enhance the ICT adoption. These results are of interest in the field of personal development and training purposes in life-span