Search results for "Wave function"
showing 10 items of 395 documents
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…
Construction of a General Library for the Rational Design of Nanomagnets and Spin Qubits Based on Mononuclear f-Block Complexes. The Polyoxometalate …
2014
This paper belongs to a series of contributions aiming at establishing a general library that helps in the description of the crystal field (CF) effect of any ligand on the splitting of the J ground states of mononuclear f-element complexes. Here, the effective parameters associated with the oxo ligands (effective charges and metal-ligand distances) are extracted from the study of the magnetic properties of the first two families of single-ion magnets based on lanthanoid polyoxometalates (POMs), formulated as [Ln(W5O18)2](9-) and [Ln(β2-SiW11O39)2](13-) (Ln = Tb, Dy, Ho, Er, Tm, Yb). This effective CF approach provides a good description of the lowest-lying magnetic levels and the associate…
Rational Design of Lanthanoid Single-Ion Magnets: Predictive Power of the Theoretical Models
2016
We report two new single‐ion magnets (SIMs) of a family of oxydiacetate lanthanide complexes with D3 symmetry to test the predictive capabilities of complete active space ab initio methods (CASSCF and CASPT2) and the semiempirical radial effective charge (REC) model. Comparison of the theoretical predictions of the energy levels, wave functions and magnetic properties with detailed spectroscopic and magnetic characterisation is used to critically discuss the limitations of these theoretical approaches. The need for spectroscopic information for a reliable description of the properties of lanthanide SIMs is emphasised. SPINMOL ERC-CoG-647301 DECRESIM MAT2014-56143-R CTQ2014-52758-P CTQ2011-2…
Open-shell doublet character in a hexaazatrinaphthylene trianion complex
2015
Three-electron reduction of hexaazatrinaphthylene (HAN) with a magnesium(I) reagent leads to [(HAN){Mg(nacnac)}3] (1), containing a [HAN]3– ligand with a spin of S = ½. Ab initio calculations reveal that the [HAN]3– ligand in 1 has a groundstate wave function with multiconfigurational properties, and can be described as a triradicaloid species with a small amount of open-shell doublet character. peerReviewed
Relativistic corrections and unitary equivalence in elastic electron deuteron scattering.
1993
The role of unitary equivalence of relativistic corrections in elastic electron deutron scattering is studied, starting from a class of approximately, unitarily equivalent Hamiltonians and using consistent charge density operators. The connection of various formal approaches for deriving the relativistic corrections to wave functions and operators are discussed in detail. For reasons of simplicity, we have chosen a pure one-pion-exchange model and calculated the charge and quadrupole form factors of the deuteron. The numerical results show that the unitary equivalence holds at small momentum transfers, but breaks down rather soon with increasing momentum transfers (\ensuremath{\lesssim}5 ${…
Evolution of a Quantum System: Lifetime of a Determinant
1976
A measure of the ''dependency'' of a many-particle system is defined and its time dependence is evaluated for systems initially described by a single Slater determinant. An uncertainty product between the energy spread of the initial determinant and the lifetime of a system's independence is established. Numerical estimates of some lifetimes are given. They are not so long as to be reassuring for nuclear time-dependent Hartree--Fock calculations. Each separate case ought to be checked. 1 table.
Pressure stability field of Mg-perovskite under deep mantle conditions: A topological approach based on Bader's analysis coupled with catastrophe the…
2019
Abstract The pressure stability field of the Mg-perovskite phase was investigated by characterizing the evolution of the electron arrangement in the crystal. Ab initio calculations of the perovskite structures in the range 0–185 GPa were performed at the HF/DFT (Hartree-Fock/Density Functional Theory) exchange–correlation terms level. The electron densities, calculated throughout the ab-initio wave functions, were analysed by means of the Bader's theory, coupled with Thom's catastrophe theory. To the best of our knowledge the approach is used for the first time. The topological results show the occurrence of two topological anomalies at P~20 GPa and P~110 GPa which delineate the pressure ra…
Spatial carrier distribution in InP/GaAs type II quantum dots and quantum posts
2011
We performed a detailed investigation of the structural and optical properties of multi-layers of InP/GaAs quantum dots, which present a type II interface arrangement. Transmission electronic microscopy analysis has revealed relatively large dots that coalesce forming so-called quantum posts when the GaAs layer between the InP layers is thin. We observed that the structural properties and morphology affect the resulting radiative lifetime of the carriers in our systems. The carrier lifetimes are relatively long, as expected for type II systems, as compared to those observed for single layer InP/GaAs quantum dots. The interface intermixing effect has been pointed out as a limiting factor for…
Diagonalization of large matrices: a new parallel algorithm.
2015
On the basis of a dressed matrices formalism, a new algorithm has been devised for obtaining the lowest eigenvalue and the corresponding eigenvector of large real symmetric matrices. Given an N × N matrix, the proposed algorithm consists in the diagonalization of (N - 1)2 × 2 dressed matrices. Both sequential and parallel versions of the proposed algorithm have been implemented. Tests have been performed on a Hilbert matrix, and the results show that this algorithm is up 340 times faster than the corresponding LAPACK routine for N = 10(4) and about 10% faster than the Davidson method. The parallel MPI version has been tested using up to 512 nodes. The speed-up for a N = 10(6) matrix is fair…