Search results for " Correlation"
showing 10 items of 1380 documents
Comparative theoretical study of the Ag–MgO (100) and (110) interfaces
1999
We have calculated the atomic and electronic structures of Ag–MgO(100) and (110) interfaces using a periodic (slab) model and an ab initio Hartree–Fock approach with a posteriori electron correlation corrections. The electronic structure information includes interatomic bond populations, effective charges, and multipole moments of ions. This information is analyzed in conjunction with the interface binding energy and the equilibrium distances for both interfaces for various coverages. There are significant differences between partly covered surfaces and surfaces with several layers of metal, and these can be understood in terms of electrostatics and the electron density changes. For complet…
Spin-orbit ZORA and four-component Dirac-Coulomb estimation of relativistic corrections to isotropic nuclear shieldings and chemical shifts of noble …
2015
Hartree-Fock and density functional theory with the hybrid B3LYP and general gradient KT2 exchange-correlation functionals were used for nonrelativistic and relativistic nuclear magnetic shielding calculations of helium, neon, argon, krypton, and xenon dimers and free atoms. Relativistic corrections were calculated with the scalar and spin-orbit zeroth-order regular approximation Hamiltonian in combination with the large Slater-type basis set QZ4P as well as with the four-component Dirac-Coulomb Hamiltonian using Dyall's acv4z basis sets. The relativistic corrections to the nuclear magnetic shieldings and chemical shifts are combined with nonrelativistic coupled cluster singles and doubles …
High excitations in coupled-cluster series: vibrational energy levels of ammonia
2004
The ammonia molecule containing large amplitude inversion motion is a revealing system in examining high-order correlation effects on potential energy surfaces. Correlation contributions to the equilibrium and saddle point geometries, inversion barrier height and vibrational energy levels, including inversion splittings, have been investigated. A six-dimensional Taylor-type series expansion of the Born–Oppenheimer potential energy surface, which is scaled to different levels of theory, is used to determine vibrational energy levels and inversion splittings variationally. The electronic energies are calculated by coupled-cluster methods, combining explicitly correlated R12 theory (which incl…
Dynamic Polarizability and Higher-Order Electric Properties of Fluorene, Carbazole, and Dibenzofuran
2019
Static electric properties, from the dipole moment to the second-hyperpolarizability tensor γ, of the 3-membered, isoelectronic ring molecules, fluorene (FL), carbazole (CR), and dibenzofuran (DBF), have been calculated at various levels of approximation. The electron correlation effects have been included at the coupled-cluster (CC) level, using CCSD and CC2 versions of the method. DFT calculations with the CAM-B3LYP functional have also been performed, and the results are compared to the CC values. The electric property-tailored Pol basis set and its more compact Z3Pol version have been employed in all static calculations. Differences between dipole polarizability values computed at the P…
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 …
Spectral alignment of multi-temporal cross-sensor images with automated kernel canonical correlation analysis
2015
In this paper we present an approach to perform relative spectral alignment between optical cross-sensor acquisitions. The proposed method aims at projecting the images from two different and possibly disjoint input spaces into a common latent space, in which standard change detection algorithms can be applied. The system relies on the regularized kernel canonical correlation analysis transformation (kCCA), which can accommodate nonlinear dependencies between pixels by means of kernel functions. To learn the projections, the method employs a subset of samples belonging to the unchanged areas or to uninteresting radiometric differences. Since the availability of ground truth information to p…
Sr/Ca and Mg/Ca ratios of ontogenetically old, long-lived bivalve shells (Arctica islandica) and their function as paleotemperature proxies
2011
International audience; The Sr/Ca and Mg/Ca ratios of many biogenic skeletons provide useful paleotemperature estimates. As yet however, it has remained largely impossible to obtain such information from bivalve shells. In the present study, metal-to-calcium values in the hinge plate (aragonite, outer shell layer) of four ontogenetically old (85 to 374 year-old) specimens of the long-lived bivalve, Arctica islandica, were measured on a LA-ICP-MS. The shells were collected alive in 1868, 1986 and 2003 from three different localities around Iceland. With increasing ontogenetic age and decreasing growth rate, a distinct trend toward increasing Sr/Ca (max. 5.17 mmol/mol) and Mg/Ca values (max. …
Warm season precipitation signal in δ 2 H values of wood lignin methoxyl groups from high elevation larch trees in Switzerland
2017
RATIONALE In this study, we tested stable hydrogen isotope ratios of wood lignin methoxyl groups (δ 2Hmethoxyl values) as a palaeoclimate proxy in dendrochronology. This is a quite new method in the field of dendrochronology and the sample preparation is much simpler than the methods used before to measure δ2H values from wood. METHODS We measured δ 2Hmethoxyl values in high elevation larch trees (Larix decidua Mill.) from Simplon Valley (southern Switzerland). Thirty-seven larch trees were sampled and five individuals analysed for their δ 2Hmethoxyl values at annual (1971-2009) and pentadal resolution (1746-2009). The δ 2Hmethoxyl values were measured as CH3I released upon treatment of the…
Carbon-isotope records of the Early Jurassic (Toarcian) Oceanix Anixic Event from the Valdorbia (Umbria-Marche Apennines) and Monte Mangart (Julian A…
2009
The Toarcian oceanic anoxic event (ca 183 Ma) coincides with a global perturbation marked by enhanced organic carbon burial and a general decrease in calcium carbonate production, probably triggered by changes in the composition of marine plankton and elevated carbon dioxide levels in the atmosphere. This study is based on high-resolution sampling of two stratigraphic successions, located in Valdorbia (Umbria-Marche Apennines) and Monte Mangart (Julian Alps), Italy, which represent expressions of the Toarcian oceanic anoxic event in deep-water pelagic sediments. These successions are characterized by the occurrence of black shales showing relatively low total organic carbon concentrations (…