Search results for "correlation"
showing 10 items of 2282 documents
Regional Susceptibility in VCD Spectra to Dynamic Molecular Motions
2018
Experimental and theoretical studies of the vibrational circular dichroism (VCD) spectrum of 3-methyl-1-(methyldiphenlsilyl)-1-phenylbutan-1-ol, whose absolute configuration is key to elucidating the Brook rearrangement of tertiary benzylic α-hydroxylsilanes, are presented. It is found that the entire OH-bending region in this spectrum—a region that provides important marker bands—cannot be reproduced at all by standard theoretical approaches even though other regions are well described. Using a novel approach to disentangle contributions to the rotational strength of these bands, internal coordinates are identified that critically influence the appearance of this part of the spectrum. We s…
Vibrational dephasing of νs (OH) in 2,4-dichlorophenol
1990
Abstract A quantitative analysis of the infrared bandshape of ν s (OH) in intramolecularly hydrogen-bonded 2,4-dichlorophenol in a series of solvents is presented. A distinct dependence of bandshape indices and relaxation parameters on the polarity of solvent has been found. The band shifts to lower wavenumbers, broadens and becomes more intense with increasing solvent polarity; correspondingly, the correlation function decays faster and the correlation time diminishes. The results are compared with those for previously studied systems. Factors influencing the bandshape are discussed.
Stratigraphical ranges of tegulated inoceramid bivalves in the type area of the Maastrichtian Stage (Belgium, the Netherlands)
2018
Abstract Recently collected material, in fine- to medium-grained biocalcarenites and in coeval flint nodules, of the tegulated inoceramid taxa Spyridoceramus tegulatus (von Hagenow, 1842) and Tenuipteria argentea (Conrad, 1858) from various members of the Gulpen Formation and the overlying Maastricht Formation allows their stratigraphical ranges to be refined. It is concluded that the ranges correspond closely to those in east-central Poland (Vistula [Wisla] River valley region), where S. tegulatus occurs in the lower Maastrichtian and lower upper Maastrichtian ( Endocostea typica , Trochoceramus radiosus and ‘ Inoceramus ’ ianjonaensis inoceramid zones, or Belemnella occidentalis and Belem…
Kinetic and thermodynamic stability of the group 13 trihydrides.
2009
The kinetic and thermodynamic stabilities of the group 13 hydrides EH(3) (E = B, Al, Ga, In, Tl, E113) are investigated by relativistic density functional and wave function based theories. The unimolecular decomposition of EH(3) --EH + H(2) becomes energetically more favorable going down the Group 13 elements, with the H(2)-abstraction of InH(3), TlH(3), and (E113)H(3) (E113: element with nuclear charge 113) being exothermic. In accordance with the Hammond-Leffler postulate, the activation barrier for the dissociation process decreases accordingly going down the group 13 elements in the periodic table shifting to an early transition state, with activation energies ranging from 88.4 kcal/mol…
Nature of Bonding in Group 13 Dimetallenes: a Delicate Balance between Singlet Diradical Character and Closed Shell Interactions
2010
The nature of metal-metal bonding in group 13 dimetallenes REER (E = Al, Ga, In, Tl; R = H, Me, (t)Bu, Ph) was investigated by use of quantum chemical methods that include HF, second order Møller-Plesset perturbation theory (MP2), coupled cluster (CCSD(T)), complete active space with (CASPT2) and without (CAS) second order perturbation theory, and two density functionals, namely, B3LYP and M06-2X. The results show that the metal-metal interaction in group 13 dimetallenes stems almost exclusively from static and dynamic electron correlation effects: both dialuminenes and digallenes have an important singlet diradical component in their wave function, whereas the bonding in the heavier diinde…
The equilibrium structure of propadienylidene
1999
Abstract A coupled-cluster study of the equilibrium geometry of propadienylidene (C3H2) is presented. Deviations between a recently reported experimental re structure and those computed at the CCSD(T)/cc-pVQZ and CCSD(T)/cc-pCVQZ levels are larger than expected. A closer analysis reveals that this discrepancy is due to inaccuracies in the cubic force field that was used to correct the measured rotational constants for vibrational effects. A satisfactory agreement between theory and experiment is obtained if the vibrational effects on the rotational constants are computed from harmonic and cubic force fields determined at either the CCSD(T)/cc-pVTZ and CCSD(T)/cc-pCVTZ levels. Revised values…
Effects of Electron Correlation inside Disordered Crystals
2022
S.P.K. acknowledges support by the National Academy of Sciences of Ukraine (Project No.0116U002067). Calculations were performed using Latvian Super Cluster (LASC), located in the Center of Excellence at Institute of Solid State Physics, the University of Latvia, which is supported by European Union Horizon 2020 Framework Programme H2020-WIDESPREAD-01-2016-2017-Teaming. Phase two under Grant Agreement No. 739508, project CAMART2.
Controlling the cohesion of cement paste
2005
The main source of cohesion in cement paste is the nanoparticles of calcium silicate hydrate (C-S-H), which are formed upon the dissolution of the original tricalcium silicate (C(3)S). The interaction between highly charged C-S-H particles in the presence of divalent calcium counterions is strongly attractive because of ion-ion correlations and a negligible entropic repulsion. Traditional double-layer theory based on the Poisson-Boltzmann equation becomes qualitatively incorrect in these systems. Monte Carlo (MC) simulations in the framework of the primitive model of electrolyte solution is then an alternative, where ion-ion correlations are properly included. In addition to divalent calciu…
Domestic vs. International correlations of interest rate maturities
2010
The association between long and short interest rates is traditionally envisaged from a purely domestic perspective, where it is believed an empirical regularity. Hence, the weakening of this relationship in the first half of the 2000s has represented a conundrum, calling for a reassessment of the term structure and the conduct of monetary policy. Some commentators have called for investigations into the international dimension of this puzzle. Hence, in this paper we employ recent advances in panel data econometrics to investigate the co-movement of interest rate maturities both at the domestic and international levels for a sample of industrial countries. Specifically, we use the Ng (2006)…
Timescale-dependent stock market comovement: BRICs vs. developed markets
2014
This paper examines the differences in the asset return comovement of the BRIC countries (Brazil, Russia, India and China), the other developed economies in their regions (Canada, Hong Kong and Australia) and the major industrialized economies (the U.K., Germany and Japan) with respect to the U.S. for different return periods. The novelty of the paper is that the stock return indices are decomposed to several timescales using wavelet analysis and that the results are further used as inputs for the dynamic conditional correlation (DCC) framework, which is used as a measure of comovement. The results propose that the level of stock market comovement depends on regional aspects, the level of d…