Search results for "Ab initio quantum chemistry methods"
showing 10 items of 468 documents
Ab initio quantum-chemical computations of the electronic states in HgBr2 and IBr: Molecules of interest on the Earth’s atmosphere
2016
The electronic states of atmospheric relevant molecules IBr and HgBr are reported, within the UV-Vis spectrum range (170nm≤λphoton≤600 nm) by means of the complete-active-space self-consistent field/multi-state complete-active-space second-order perturbation theory/spin-orbit restricted-active-space state-interaction (CASSCF/MS-CASPT2/SO-RASSI) quantum-chemical approach and atomic-natural-orbital relativistic-correlation-consistent (ANO-RCC) basis sets. Several analyses of the methodology were carried out in order to reach converged results and therefore to establish a highly accurate level of theory. Good agreement is found with the experimental data with errors not higher than around 0.1 …
Quadrupole moments of radium isotopes from the 7p 2 P 3/2 hyperfine structure in Ra II
1988
The hyperfine structure and isotope shift of221–226Ra and212,214Ra have been measured in the ionic (Ra II) transition 7s 2 S 1/2–7p 2 P 3/2 (λ=381.4 nm). The method of on-line collinear fast-beam laser spectroscopy has been applied using frequency-doubling of cw dye laser radiation in an external ring cavity. The magnetic hyperfine fields are compared with semi-empirical and ab initio calculations. The analysis of the quadrupole splitting by the same method yields the following, improved values of spectroscopic quadrupole moments:Q s (221Ra)=1.978(7)b,Q s (223Ra)=1.254(3)b and the reanalyzed valuesQ s (209Ra)=0.40(2)b,Q s (211Ra)=0.48(2)b,Q s (227Ra)=1.58(3)b,Q s (229Ra)=3.09(4)b with an ad…
Transition probability ratios for selected multiplets of C I, N I, and O I, and comparisons with recent calculations
2000
With a wall-stabilized high-current arc, we have measured the transition probabilities of several multiplet pairs of C I, N I, and O I. Pairs have been selected for which two recent ab initio calculations have produced widely different results. All chosen multiplets are among the prominent, strong features of their respective spectra, and the pairing is in each case done for multiplets that hardly differ in their excitation energies. Our results do not favor either of the calculations, but are consistent with an earlier experiment.
Ab-Initio Studies of Electronic and Spectroscopic Properties of MgO, ZnO and CdO
2008
We present ab-initio calculations of excited-state properties within single-particle and two-particle approaches in comparison with corresponding experimental results. For the theoretical treatment of the electronic structure, we compute eigenvalues and eigenfunctions by using a spatially nonlocal exchange-correlation potential. From this starting point, quasiparticle energies within the fully frequency-dependent G(0)W(0) approximation are obtained. By solving the Bethe-Salpeter equation, we evaluate optical properties, including the electron-hole attraction and the local-field effects. The results are compared with experimental spectra from soft X-ray emission, as well as from X-ray photoe…
Ab InitioCalculations and High-Resolution Spectroscopy of the Bending Pentad of SiH2D2in the 10–16 μm Region
1998
Abstract The SiH 2 D 2 asymmetric top has nine vibrational modes, five of them forming a pentad strongly perturbed by Coriolis interactions. High-level ab initio calculations of SiH 2 D 2 have been performed which yield numerous spectroscopic parameters related to the harmonic and anharmonic force fields. The bending pentad comprising ν 4 (A 1 ), ν 7 (B 1 ), ν 5 (A 2 ), ν 9 (B 2 ), and ν 3 (A 1 ) has been studied by high-resolution Fourier transform spectroscopy; the region 600–1050 cm −1 has been investigated with a resolution of ca. 4 × 10 −3 cm −1 . Raman BOXCARS spectroscopy has been used for the infrared inactive ν 5 band. The Raman apparatus function was 0.0054 cm −1 . Assignments of …
Examining the N=28 shell closure through high-precision mass measurements of Ar46–48
2020
The strength of the $N=28$ magic number in neutron-rich argon isotopes is examined through high-precision mass measurements of $^{46\text{--}48}\mathrm{Ar}$, performed with the ISOLTRAP mass spectrometer at ISOLDE/CERN. The new mass values are up to 90 times more precise than previous measurements. While they suggest the persistence of the $N=28$ shell closure for argon, we show that this conclusion has to be nuanced in light of the wealth of spectroscopic data and theoretical investigations performed with the SDPF-U phenomenological shell model interaction. Our results are also compared with ab initio calculations using the valence space in-medium similarity renormalization group and the s…
Theoretical study of the electron structure of superheavy elements with an open 6d shell: Sg, Bh, Hs, and Mt
2019
We use recently developed efficient versions of the configuration interaction method to perform {\em ab initio} calculations of the spectra of superheavy elements seaborgium (Sg, $Z=106$), bohrium (Bh, $Z=107$), hassium (Hs, $Z=108$) and meitnerium (Mt, $Z=109$). We calculate energy levels, ionization potentials, isotope shifts and electric dipole transition amplitudes. Comparison with lighter analogs reveals significant differences caused by strong relativistic effects in superheavy elements. Very large spin-orbit interaction distinguishes subshells containing orbitals with a definite total electron angular momentum $j$. This effect replaces Hund's rule holding for lighter elements.
Accurate ab initio density fitting for multiconfigurational self-consistent field methods
2008
Using Cholesky decomposition and density fitting to approximate the electron repulsion integrals, an implementation of the complete active space self-consistent field (CASSCF) method suitable for large-scale applications is presented. Sample calculations on benzene, diaquo-tetra- μ -acetato-dicopper(II), and diuraniumendofullerene demonstrate that the Cholesky and density fitting approximations allow larger basis sets and larger systems to be treated at the CASSCF level of theory with controllable accuracy. While strict error control is an inherent property of the Cholesky approximation, errors arising from the density fitting approach are managed by using a recently proposed class of auxi…
Finite-temperature correlations in the trapped Bose-Einstein gas
2001
There is a large literature (cf. eg. [1, 2]) which, under conditions of translational invariance, has used functional integral methods to calculate, ab initio, the equilibrium finite temperature 2-point correlation functions (Green ’s functions) \[\left\langle {\hat \psi (r,\tau ){{\hat \psi }^\dag }(r',\tau ')} \right\rangle \] \(G\left( {r,r'} \right) \equiv \left\langle {\psi \left( {r,\tau } \right){{{\hat{\psi }}}^{\dag }}\left( {r',\tau '} \right)} \right\rangle \) for a Bose gas in each of d=3, d=2, d=1 space dimensions: (…) means thermal average and τ, τ′ are ‘thermal times’ for which 0<τ,<τ′β and β−1=k B T, T the temperature. These functional integral methods [1, 2] solve the many-…
Comment on "High-pressure phases of group-II difluorides: Polymorphism and superionicity"
2018
Nelson et al. [Phys. Rev. B 95, 054118 (2017)] recently have reported first-principles calculations on the behaviour of group-II difluorides (BeF$_{2}$, MgF$_{2}$, and CaF$_{2}$) under high-pressure and low- and high-temperature conditions. The calculations were based on ab initio random structure searching and the quasi-harmonic approximation (QHA). Here, we point out that, despite the of inestimable value of such calculations at high-pressure and low-temperature conditions, the high-$P$ high-$T$ phase diagram proposed by Nelson et al. for CaF$_{2}$ neither is in qualitative agreement with the results of previous ab initio molecular dynamics simulations nor with the existing corps of exper…