Search results for "Valence"
showing 10 items of 2732 documents
Calibration of Cholesky Auxiliary Basis Sets for Multiconfigurational Perturbation Theory Calculations of Excitation Energies
2010
The accuracy of auxiliary basis sets derived from Cholesky decomposition of two-electron integrals is assessed for excitation energies calculated at the state-average complete active space self-consistent field (CASSCF) and multiconfigurational second order perturbation theory (CASPT2) levels of theory using segmented as well as generally contracted atomic orbital basis sets. Based on 196 valence excitations in 26 organic molecules and 72 Rydberg excitations in 3 organic molecules, the results show that Cholesky auxiliary basis sets can be used without compromising the accuracy of the multiconfigurational methods. Specifically, with a decomposition threshold of 10(-4) au, the mean error due…
Metal valence states inEu0.7NbO3,EuNbO3,andEu2Nb5O9by TB-LMTO-ASA band-structure calculations and resonant photoemission spectroscopy
1998
The electronic structures of ${\mathrm{Eu}}_{2}{\mathrm{Nb}}_{5}{\mathrm{O}}_{9},$ ${\mathrm{EuNbO}}_{3},$ and ${\mathrm{Eu}}_{0.7}{\mathrm{NbO}}_{3}$ have been investigated by photoemission and total-yield spectroscopy with synchrotron radiation, and in the case of ${\mathrm{Eu}}_{2}{\mathrm{Nb}}_{5}{\mathrm{O}}_{9}$ by tight-binding linear muffin-tin orbital (LMTO) band-structure calculations. A central question for reduced europium niobates is that of the valence of Eu and Nb. Both europium and niobium atoms can appear in different valence states so that various electronic configurations in the title compounds are possible. For this reason, the valence band was studied by the resonant Eu…
Pseudospin Symmetry and Microscopic Origin of Shape Coexistence in the Ni78 Region: A Hint from Lifetime Measurements
2018
Lifetime measurements of excited states of the light N = 52 isotones 88 Kr , 86 Se , and 84 Ge have been performed, using the recoil distance Doppler shift method and VAMOS and AGATA spectrometers for particle identification and gamma spectroscopy, respectively. The reduced electric quadrupole transition probabilities B ( E 2 ; 2 + → 0 + ) and B ( E 2 ; 4 + → 2 + ) were obtained for the first time for the hard-to-reach 84 Ge . While the B ( E 2 ; 2 + → 0 + ) values of 88 Kr , 86 Se saturate the maximum quadrupole collectivity offered by the natural valence ( 3 s , 2 d , 1 g 7 / 2 , 1 h 11 / 2 ) space of an inert 78 Ni core, the value obtained for 84 Ge largely exceeds it, suggesting that sh…
Hyperfine structure constants of the CaII states 4s 2 S 1/2 and 4p 2 P 1/2, 3/2 and the nuclear quadrupole moment of43Ca
1991
The hyperfine structure splittings of the 4s 2 S 1/2 → 4p 2 P 1/2, 3/2 transitions in43CaII have been measured by fast ion beam collinear laser spectroscopy. The resonant laser interaction was observed using non-optical detection based on optical ground state depopulation pumping, state selective neutralization and charge state separated particle counting. The extracted magnetic dipole hyperfine structure constants for43CaA(2 S 1/2)=−805(2) MHz,A(2 P 1/2)=−145.5(1.0) MHz andA(2 P 3/2)=−31.9(0.2) MHz are in excellent agreement with relativistic many body perturbation theory predictions available for this alkali-like ion. The combined results are used to evaluate the semi-empirical analysis m…
Valence change ReRAMs (VCM) - Experiments and modelling: General discussion
2019
Valence change ReRAMs (VCM) - Experiments and modelling: General discussion
Multiconfigurational perturbation theory (CASPT2) applied to the study of the low-lying singlet and triplet excited states of cyclopropene
1996
The electronic spectrum of cyclopropene has been studied using multiconfigurational second-order perturbation theory (CASPT2) with extended ANO-type basis sets. The calculation comprises two valence states and the 3s, 3p, 3d members of the Rydberg series converging to the π and σ ionization limits. A total of twenty singlet and twenty triplet excited states have been analyzed. The results confirm the valence nature of the lowest energy singlet-singlet band and yield a conclusive assignment: the first dipole-allowed transition in cyclcopropene is due to absorption to a (σ → π*) state. The (π → π*) (V) state is interleaved among a number of Rydberg states in the most intense band of the syste…
Shell structure in mixed3He−4Hedroplets
2004
Due to the immiscibility of ${}^{3}\mathrm{He}$ into ${}^{4}\mathrm{He}$ at very low temperatures, mixed helium droplets consist of a core of ${}^{4}\mathrm{He}$ atoms coated by a ${}^{3}\mathrm{He}$ layer whose thickness depends on the number of atoms of each isotope. When these numbers are such that the centrifugal kinetic energy of the ${}^{3}\mathrm{He}$ atoms is small and can be considered as a perturbation to the mean-field energy, a novel shell structure arises, with magic numbers different from these of pure ${}^{3}\mathrm{He}$ droplets. If the outermost shell is not completely filled, the valence atoms align their spins up to the maximum value allowed by the Pauli principle.
Electrically switchable magnetic exchange in the vibronic model of linear mixed valence triferrocenium complex
2018
In this article, we report our development of a vibronic model for the electric-field control of antiferromagnetic superexchange in the mixed-valence (MV) triferrocenium complex FeIII-FeII-FeIII proposed as a possible candidate for the molecular implementation of a quantum logic gate. Along with the electronic interactions, such as electron transfer between the iron ions in different oxidation degrees and Coulomb repulsion of the extra holes, the proposed model of the triferrocenium complex also takes into account the vibronic coupling as an inherent ingredient of the problem of mixed valency. The latter is described by the conventional Piepho-Krauzs-Shatz (PKS) model adapted to the linear …
Quantum chemical simulations of hole self-trapping in semi-ionic crystals
1994
A novel formalism is presented for reliable calculations of the energetics of hole self-trapping in semi-ionic solids with mixed valence bands. Unlike previous model-Hamiltonian-type approaches, it is based on self-consistent quantum chemical INDO simulations of the atomistic and electronic structure of a self-trapped hole, making no a priori assumptions about a particular form of its localization (if any). This formalism is applied to the problem of hole self-trapping in corundum crystals (a -A1203). The hole self-trapping is found to be energetically favorable in the form of a diatomic 02 molecule with strong covalent bonding quite similar to the self-trapped hole (VK-center) in alkali ha…
Isovector spin-multipole strength distributions in double- β -decay triplets
2017
In this work the energetics and strength distributions of isovector spin-dipole and spin-quadrupole transitions from the ground states of the pairs ($^{76}\mathrm{Ge}, ^{76}\mathrm{Se}$), ($^{82}\mathrm{Se}, ^{82}\mathrm{Kr}$), ($^{96}\mathrm{Zr}, ^{96}\mathrm{Mo}$), ($^{100}\mathrm{Mo}, ^{100}\mathrm{Ru}$), ($^{116}\mathrm{Cd}, ^{116}\mathrm{Sn}$), ($^{128}\mathrm{Te}, ^{128}\mathrm{Xe}$), ($^{130}\mathrm{Te}, ^{130}\mathrm{Xe}$), and ($^{136}\mathrm{Xe}, ^{136}\mathrm{Ba}$), of double-$\ensuremath{\beta}$-decay initial and final nuclei, to the ${J}^{\ensuremath{\pi}}={0}^{\ensuremath{-}},{1}^{\ensuremath{-}},{2}^{\ensuremath{-}},{1}^{+},{2}^{+}$, and ${3}^{+}$ excited states of the interm…