Search results for "coupled"
showing 10 items of 742 documents
Calculation of electronic g-tensors using coupled cluster theory.
2009
A scheme for the calculation of the electronic g-tensor at the coupled cluster (CC) level is presented. The reported implementation employs an effective one-electron spin-orbit operator, allows the inclusion of arbitrary excitations in the cluster operator, and offers various options concerning the treatment of orbital relaxation and choice of reference determinants. In addition, the use of gauge-including atomic orbitals (GIAOs) is possible to overcome the gauge origin problem. Benchmark calculations for the NH ((3)Sigma(-)) radical reveal the importance of electron correlation effects for the accurate prediction of the g-shift as well as the slow basis set convergence of such calculations…
Bond Dissociation Energies for Diatomic Molecules Containing 3d Transition Metals: Benchmark Scalar-Relativistic Coupled-Cluster Calculations for 20 …
2017
Benchmark scalar-relativistic coupled-cluster calculations for dissociation energies of the 20 diatomic molecules containing 3d transition metals in the 3dMLBE20 database ( J. Chem. Theory Comput. 2015 , 11 , 2036 ) are reported. Electron correlation and basis set effects are systematically studied. The agreement between theory and experiment is in general satisfactory. For a subset of 16 molecules, the standard deviation between computational and experimental values is 9 kJ/mol with the maximum deviation being 15 kJ/mol. The discrepancies between theory and experiment remain substantial (more than 20 kJ/mol) for VH, CrH, CoH, and FeH. To explore the source of the latter discrepancies, the …
Approximate treatment of higher excitations in coupled-cluster theory. II. Extension to general single-determinant reference functions and improved a…
2008
The theory and implementation of approximate coupled-cluster (CC), in particular approximate CC singles, doubles, triples, and quadruples methods, are discussed for general single-determinant reference functions. While the extension of iterative approximate models to the non-Hartree-Fock case is straightforward, the generalization of perturbative approaches is not trivial. In contrast to the corresponding perturbative triples methods, there are additional terms required for non-Hartree-Fock reference functions, and there are several possibilities to derive approximations to these terms. As it turns out impossible to develop an approach that is consistent with the canonical Hartree-Fock-base…
Cycloaddition of Strained Cyclic Alkenes and Ortho-Quinones : A Distortion/Interaction Analysis
2020
The chemistry of strained unsaturated cyclic compounds has experienced remarkable growth in recent years via the development of metal–free click reactions. Among these reactions, the cycloaddition of cyclopropenes and their analogues to ortho-quinones has been established as a highly promising click reaction. The present work investigates the mechanism involved in the cycloaddition of strained dienes to ortho-quinones and structural factors that would influence this reaction. For this purpose, we use B97D density functional theory calculations throughout, and for relevant cases, we use spin component–scaled MP2 calculations and single–point domain-based local pair natural orbital coupled cl…
2D Hydro-Mechanical-Chemical Modeling of (De)hydration Reactions in Deforming Heterogeneous Rock: The Periclase-Brucite Model Reaction
2020
Deformation at tectonic plate boundaries involves coupling between rock deformation, fluid flow, and metamorphic reactions, but quantifying this coupling is still elusive. We present a new two-dimensional hydro-mechanical-chemical numerical model and investigate the coupling between heterogeneous rock deformation and metamorphic (de)hydration reactions. We consider linear viscous compressible and power-law viscous shear deformation. Fluid flow follows Darcy's law with a Kozeny-Carman type permeability. We consider a closed isothermal system and the reversible (de)hydration reaction: periclase and water yields brucite. Fluid pressure within a circular or elliptical inclusion is initially bel…
Chemical and mineralogical analyses on stones from Sagunto Castle (Spain)
2019
Abstract For the first time, an archaeometric study was carried out on the carbonate rock ashlars of the Sagunto Castle. The studied site is one of the most important and best preserved Spanish archaeological and architectural monuments, characterized by different construction phases from the Roman period to Modern Ages. Forty samples collected from thirteen different structures of Sagunto Castle and two quarries, located in the Sagunto's hill were used for comparative purposes. The samples were analyzed by X-ray diffraction, X-ray fluorescence and inductively coupled plasma mass spectrometry to determine their mineralogical and elemental composition. The obtained data show similar chemical…
Mn/Ca in shells of Arctica islandica (Baltic Sea) – A potential proxy for ocean hypoxia?
2021
Oxygen depletion threatens an increasing number of shallow water environments, specifically habitats below the seasonal halocline in coastal settings of the Baltic Sea. To understand the natural variations of dissolved oxygen levels on seasonal and inter-annual time-scales prior to the instrumental era, high-resolution archives are urgently required. The present study evaluates the potential use of Mn/Ca values in shells of the bivalve, Arctica islandica to infer concentrations of past dissolved oxygen concentrations. This study is based on laser ablation – inductively coupled plasma – mass spectrometry (LA-ICP-MS) data of six contemporaneous specimens and demonstrates that background varia…
Green methodology for quality control of elemental content of infant milk powder
2019
Abstract A green methodology for the direct determination of elemental content in infant milk powder samples from 0 to 3 years was developed. A portable energy dispersive X-ray fluorescence (ED-XRF) tool has been used as a direct method for the quantification of five essential elements (Ca, K, Fe, Cu and Zn). For analysis pellets from 0.8 g of each sample weight were made and analyzed. Due to the high dependence of the ED-XRF signal with the sample matrix, external calibrations using cocoa powder diluted with glucose were performed. Infant milk samples were diluted with lactose and the signals were interpolated in the external calibrations. Concentrations obtained by ED-XRF were compared wi…
Two-Dimensional Numerical Modelling of a Moored Floating Body under Sloping Seabed Conditions
2020
A coupled floating body-mooring line model is developed by combining a boundary element model for a two-dimensional floating body and a catenary mooring line model. The boundary element model is formulated in the time domain by a continuous Rankine source, and a reflection potential is introduced to account for the wave reflection due to sloping seabed. This newly developed model is validated by comparisons against available data. Then, dynamic response analyses are performed for the moored body in various seabed conditions. Compared with a flat seabed, a sloping seabed causes unsymmetrical mooring line configuration and generates noticeable effects in the motion responses of the floating b…
II) Wood pellets for home heating can be considered environmentally friendly fuels? Heavy metals determination by inductively coupled plasma-optical …
2016
Abstract The aim of the present study was to determine the concentrations of twelve potentially hazardous elements in wood pellet ashes obtained by the combustion of 13 pellet brands for sale in Italy, the impact of adding the ashes to soils and health risk of operator due to dust exposure. Samples were analysed by Inductively Coupled Plasma Optical Emission Spectrometry. The concentrations of heavy metals in ashes from stoves ranged from 0.41 to 7.2 mg kg − 1 for As, from 1.3 to 12 mg kg − 1 for Sb, from 1.8 to 12 mg kg − 1 for Zn, from 0.23 to 0.8 mg kg − 1 for Pb, from 0.18 to 2.8 mg kg − 1 for Ni, from 0.09 to 1.0 mg kg − 1 for Cd, from 0.46 to 3.4 mg kg − 1 for Cr, from 0.94 to 2.7 mg …