Search results for "Electronic correlation"
showing 10 items of 100 documents
Density Functional Theory Calculations On Magnetic Properties Of Actinide Compounds
2011
ABSTRACTWe have performed a detailed analysis of the magnetic (collinear and noncollinear) order and atomic and electron structures of UO2, PuO2 and UN on the basis of density functional theory with the Hubbard electron correlation correction (DFT+U). We have shown that the 3-k magnetic structure of UO2 is stabilized for the Hubbard parameter value of U=4.6 eV (while J=0.5 eV) when Dudarev’s formalism is used. UO2 keeps cubic shape in this structure. Two O atoms nearest to each U atom in direction of its magnetic moment move toward this U atom. Neither UN nor PuO2 shows the energetical preference for the rhombohedral distortion, in contrast to UO2, and, thus, no complex 3-k magnetic structu…
Theoretical study of the electronic spectra ofcis-1,3,5-hexatriene andcis-1,3-butadiene
1994
The electronic spectra forcis-1,3-butadiene andcis-1,3,5-hexatriene have been studied using multiconfiguration second-order perturbation theory (CASPT2) and extended ANO basis sets. The calculations comprise all singlet valence excited states below 8.0 eV, the first 3s, 3p, 3d Rydberg states, and the second 3s state. The four lowest triplet states were also studied. The resulting excitation energies forcis-hexatriene have been used in an assignment of the experimental spectrum, leading to a maximum deviation of 0.13 eV for the vertical transition energies. The calculations place the 11 B 2 state 0.04 eV below the 21 A 1 state. 16 excited states were studied incis-butadiene, using a CASPT2 o…
On the dissociation energy of Cu2 and CuH using a differential correlation approach
1990
The energy contributions involved in the “dissociation-consistent configuration interaction” (DCCI) scheme proposed by Goddard and co-workers plus the dispersion effects associated with the valence MOs adjacent to the bond (DISP) are evaluated for the Cu2 and CuH systems, following the “configuration interaction by perturbation with multiconfigurational zeroth-order wavefunction selected by iterative process” (CIPSI) algorithm. Using a relativistic pseudopotential to represent the neon core of copper, and a flexible basis set for the valence shell, the results obtained with the CIPSI/DCCI (+ DISP) approach shows a good agreement with previous theoretical results employing basis sets of simi…
A theoretical study of the electronic spectrum of thiophene
1993
Abstract The electronic spectrum of thiophene has been studied using multiconfiguration second-order perturbation theory and extended ANO basis sets. The calculations comprise four singlet valence excited states and the 3s3p3rd Rydberg series. The lowest triplet states were included and some n-π* and n-σ* states. The results have been used to assign the experimental spectrum below 8.0 eV, with a maximum deviation of about 0.1 eV for vertical transition energies. The calculations place the 2 1A1 valence state at 5.33 eV, below the 1 1B2 valence state at 5.72 eV, and the most intense valence transitions at 6.69 eV (3 1A1) and 7.32 eV (4 1B2) with oscillator strengths 0.19 and 0.39, respective…
Correction: “On-the-fly” coupled cluster path-integral molecular dynamics: impact of nuclear quantum effects on the protonated water dimer
2015
We present an accelerated ab initio path-integral molecular dynamics technique, where the interatomic forces are calculated “on-the-fly” by accurate coupled cluster electronic structure calculations. In this way not only dynamic electron correlation, but also the harmonic and anharmonic zero-point energy, as well as tunneling effects are explicitly taken into account. This method thus allows for very precise finite temperature quantum molecular dynamics simulations. The predictive power of this novel approach is illustrated on the example of the protonated water dimer, where the impact of nuclear quantum effects on its structure and the 1H magnetic shielding tensor are discussed in detail.
Internally Contracted Multireference Coupled Cluster Calculations with a Spin-Free Dirac-Coulomb Hamiltonian: Application to the Monoxides of Titaniu…
2017
We combine internally contracted multireference coupled cluster theory with a four-component treatment of scalar-relativistic effects based on the spin-free Dirac–Coulomb Hamiltonian. This strategy allows for a rigorous treatment of static and dynamic correlation as well as scalar-relativistic effects, which makes it viable to describe molecules containing heavy transition elements. The use of a spin-free formalism limits the impact of the four-component treatment on the computational cost to the non-rate-determining steps of the calculations. We apply the newly developed method to the lowest singlet and triplet states of the monoxides of titanium, zirconium, and hafnium and show how the in…
The bromine nuclear quadrupole moment revisited
2013
For the bromine atom and the hydrogen bromide molecule, we report results for the electric-field gradient at the bromine nucleus based on quantum-chemical calculations. Highly accurate values are obtained by using coupled-cluster methods for the treatment of electron correlation, by minimising remaining basis-set effects through the use of large atomic-orbital sets, and by taking into account relativistic effects. For hydrogen bromide, zero-point vibrational corrections are considered as well. The obtained results for the bromine electric-field gradients are used to derive values for the Br-79 quadrupole moment: 308.1 and 309.3 mb based on data for the bromine atom and hydrogen bromide, res…
Binding and isomerization energies for the Cu/CN and Cu(I)CN interactions
1993
Abstract Binding and isomerization energies of the CuCN, CuNC, CuCN+, and CuNC+ systems were investigated by means of a multireference CI perturbatively selected, MRCI-PS approach. The inclusion of the main dynamical correlation effects are evaluated. The binding energies for CuCN and CuNC are 4.37 and 4.03 eV, respectively, and those for CuCN+ and CuNC+ are 0.08 and 1.61 eV. Calculated isomerization energies are 7.86 and 35.98 kcal/mol for CuCN and Cu(I)CN isomerizations, respectively.
Dissociation energies within selected configuration interaction and perturbation theory
1993
Abstract Selected configuration interaction (CI) calculations and second-order perturbational theory are used to truncate systematically multireference single and double excitation CI (MRCI) expansions in the calculation of the bond dissociation energies of several systems like the single-bonded LiF molecule or the multiple-bonded N2, NO and O2 diatomic systems. The method is extended to compute the CH bond dissociation energy ofethene C2H4. It is shown how the proposed scheme (perturbation-selected MRCI (MRCI-PS)) is able to reproduce the accuracy of complete MRCI expansions with only a small number of configurations variationally evaluated.
ChemInform Abstract: A Theoretical Determination of the Dissociation Energy of the Nitric Oxide Dimer.
2010
Multi-reference CI methods have been applied to determine the dissociation energy and structure of thecis-N2O2 molecule. The convergence of the theoretical result has been checked with respect to a systematic expansion of the one-electron basis set and the multi-reference CI wave function. The best calculated value, 13.8 kJ/mol, is in agreement with the experimental value, 12.2 kJ/mol. It has been obtained with an extended ANO-type basis set [6s5p3d2f], including the effect of the basis set superposition error (BSSE) in the geometry optimization, and additional effects, such as the electron correlation of core electrons and relativistic corrections, using the average coupled pair functional…