Search results for "Electronic correlation"
showing 10 items of 100 documents
Accurate Nonlinear Optical Properties for Small Molecules
2006
During the last decade it became possible to calculate by quantum chemical ab initio methods not only static but also frequency-dependent properties with high accuracy. Today, the most important tools for such calculations are coupled cluster response methods in combination with systematic hierarchies of correlation consistent basis sets. Coupled cluster response methods combine a computationally efficient treatment of electron correlation with a qualitatively correct pole structure and frequency dispersion of the response functions. Both are improved systematically within a hierarchy of coupled cluster models. The present contribution reviews recent advances in the highly accurate calculat…
Quantum Monte-Carlo calculation of correlation functions of undistorted, cis-distorted and trans-distorted polyacene
2003
Abstract We have studied polyacene within the Hubbard model to explore the effect of electrons correlations on the bond–bond correlation as well as spin–spin correlation functions. We employ the determinantal quantum Monte-Carlo to resolve the microscopic Hamiltonian of this system which involves a nearest-neighbor electron hopping matrix element t , an on-site Coulomb repulsion U . The objective of this study is to understand the effect of electron–electron (e–e) correlations on the structural instability in polyacene. We find strong similarities between polyacene and polyacetylene. The system shows no tendency to destroy the imposed bond-alternation pattern. The spin–spin correlations sho…
High-accuracy extrapolated ab initio thermochemistry. II. Minor improvements to the protocol and a vital simplification
2006
The recently developed high-accuracy extrapolated ab initio thermochemistry method for theoretical thermochemistry, which is intimately related to other high-precision protocols such as the Weizmann-3 and focal-point approaches, is revisited. Some minor improvements in theoretical rigor are introduced which do not lead to any significant additional computational overhead, but are shown to have a negligible overall effect on the accuracy. In addition, the method is extended to completely treat electron correlation effects up to pentuple excitations. The use of an approximate treatment of quadruple and pentuple excitations is suggested; the former as a pragmatic approximation for standard cas…
Relativistic coupled-cluster calculations on XeF6: Delicate interplay between electron-correlation and basis-set effects
2015
A systematic relativistic coupled-cluster study is reported on the harmonic vibrational frequencies of the O(h), C(3v), and C(2v) conformers of XeF6, with scalar-relativistic effects efficiently treated using the spin-free exact two-component theory in its one-electron variant (SFX2C-1e). Atomic natural orbital type basis sets recontracted for the SFX2C-1e scheme have been shown to provide rapid basis-set convergence for the vibrational frequencies. SFX2C-1e as well as complementary pseudopotential based computations consistently predicts that both O(h) and C(3v) structures are local minima on the potential energy surface, while the C(2v) structure is a transition state. Qualitative disagre…
Calculations of Perovskite Surface Relaxation
2000
AbstractThe (100) and (110) surface relaxations are calculated for SrTiO3 and BaTiO3 perovskite thin films by means of a semi-empirical shell model (SM) for different surface terminations. Our SM results for the (100) surface structure are in good agreement with our present ab initio Hartree-Fock calculations with electron correlation corrections, previous ab initio pseudopotential calculationsand LEED experiments. The surface energy for the Ba-, Sr-, TiO- terminated (110) surfaces is found much larger than that for the (100) one. In contrast, the surface energy for the asymmetric O-termination, where outermost O atoms are strongly on-plane displaced, is the lowest for all (110) termination…
Why benchmark-quality computations are needed to reproduce 1-adamantyl cation NMR chemical shifts accurately.
2011
While the experimental (1)H NMR chemical shiftsof the 1-adamantyl cation can be computed within reasonably small error bounds, the usual Hartree-Fock and density functional quantum-chemical computations, as well as those based on rather elaborate second-order Møller-Plesset perturbation theory, fail to reproduce its experimental (13)C NMR chemical shifts satisfactorily. This also is true even if the NMR shielding calculations treat electron correlation adequately by the coupled-cluster singles and doubles model augmented by a perturbative correction for triple excitations (i.e., at the CCSD(T) level) with quadruple-ζ basis sets. We demonstrate that good agreement can be achieved if highly a…
Theoretical study of YbOH173 to search for the nuclear magnetic quadrupole moment
2019
A $CP$-violating interaction of the nuclear magnetic quadrupole moment (MQM) with electrons in the ytterbium monohydroxide molecule $^{173}\mathrm{YbOH}$ is considered. Both the MQM of the $^{173}\mathrm{Yb}$ nucleus and the molecular interaction constant ${W}_{M}$ are estimated. Electron correlation effects are taken into account within the relativistic Fock-space coupled-cluster method. Results are interpreted in terms of the strength constants of $CP$-violating nuclear forces, neutron dipole moment (EDM), QCD vacuum angle $\ensuremath{\theta}$, quark EDMs, and chromo-EDMs.
Electron correlation in metal clusters, quantum dots and quantum rings
2009
This short review presents a few case studies of finite electron systems for which strong correlations play a dominant role. In simple metal clusters, the valence electrons determine stability and shape of the clusters. The ionic skeleton of alkali metals is soft, and cluster geometries are often solely determined by electron correlations. In quantum dots and rings, the electrons may be confined by an external electrostatic potential, formed by a gated heterostructure. In the low density limit, the electrons may form so-called Wigner molecules, for which the many-body quantum spectra reveal the classical vibration modes. High rotational states increase the tendency for the electrons to loca…
Ab initiomodeling of surface structure forSrTiO3perovskite crystals
2001
We present and discuss the results of calculations of ${\mathrm{SrTiO}}_{3}$ (100) surface relaxation and rumpling with two different terminations (SrO and ${\mathrm{TiO}}_{2}).$ These are based on ab initio Hartree-Fock method with electron correlation corrections and density functional theory calculations with different exchange-correlation functionals, including hybrid exchange techniques. Both approaches use the localized Gaussian-type basis set. All methods agree well on surface energies and on atomic displacements, as well as on considerable increase of covalency effects nearby the surface. More detailed experiments on surface rumpling and relaxation are necessary for further testing …
The first-principles treatment of the electron-correlation and spin-orbital effects in uranium mononitride nuclear fuels.
2012
The DFT+U calculations were employed in a detailed study of the strong electron correlation effects in a promising nuclear fuel-uranium mononitride (UN). A simple method for solving the multiple minima problem in DFT+U simulations and insure obtaining the correct ground state is suggested and applied. The crucial role of spin-orbit interactions in reproduction of the U atom total magnetic moment is demonstrated. Basic material properties (the lattice constants, the spin- and total magnetic moments on U atoms, the magnetic ordering, and the density of states) were calculated varying the Hubbard U-parameter. By varying the tetragonal unit cell distortion, the meta-stable states have been care…