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Results for “effective core potentials”

Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

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At least 19 records
All sourcesNASA NTRSDOE OSTI
NASA NTRS2022

The reliability of the small-core Lanthanide effective core potentials

The reliability of the small-core Lanthanide effective core potentials (ECP) is tested using MF and MF(3), for M=Eu, Gd, Tb, and Yb and the atomic excitation energies for Pr, Nd, Eu, Gd, Tb, Dy, Ho, Er, Tm, and Yb. In some case the ECP and all-electron (AE) results are in good agreement, while in others there are significant difference. The difference are much larger when the segmented basis set is used in conjunction with the ECP than when the atomic natural orbital (ANO) basis set is used. The study of the atoms suggests that problems for lanthanide containing molecules are associated with poor atomic excitation energies in the ECP treatment and even using the ANO basis set does not completely solve the problem. We note that the problem appears to be more severe for density functional approaches than for traditional correlation methods. We suggest that additional studies and new effective core potentials may be required for the Lanthanide atoms.

effective core potentials, atomic excitation, atom↗
DOE OSTI2022

A new generation of effective core potentials from correlated and spin–orbit calculations: Selected heavy elements

We introduce new correlation consistent effective core potentials (ccECPs) for the elements I, Te, Bi, Ag, Au, Pd, Ir, Mo, and W with 4d, 5d, 6s, and 6p valence spaces. These ccECPs are given as a sum of spin-orbit averaged relativistic effective potential (AREP) and effective spin–orbit (SO) terms. The construction involves several steps with increasing refinements from more simple to fully correlated methods. The optimizations are carried out with objective functions that include weighted many-body atomic spectra, norm-conservation criteria, and SO splittings. Transferability tests involve molecular binding curves of corresponding hydride and oxide dimers. The constructed ccECPs are systematically better and in a few cases on par with previous effective core potential (ECP) tables on all tested criteria and provide a significant increase in accuracy for valence-only calculations with these elements. Our study confirms the importance of the AREP part in determining the overall quality of the ECP even in the presence of sizable spin–orbit effects. The subsequent quantum Monte Carlo calculations point out the importance of accurate trial wave functions that, in some cases (mid-series transition elements), require treatment well beyond a single-reference.

Wang, Guangming (ORCID:0000000231327925)↗
NASA NTRS1978

Effective core potentials for the cadmium and mercury atoms

Ab initio effective core potentials have been obtained for the cadmium and mercury atoms by the methods of Kahn et al. (1976). Both two and twelve valence electron representations of Cd and Hg were tested for various atom state-configurations by comparison with all-electron calculations. The generated potentials were used to obtain the equilibrium bond distances and molecular binding energies for the dichloride and dimethyl compounds of both atoms from single and optimum-double configuration self-consistent field calculations.

Basch, H.↗
NASA NTRS1987

Effective core potential parameters for first- and second-row atoms

An improved effective core potential (ECP) technique is described and used to give ECP parameters for the atoms of the first two rows of the periodic table. A given basis set is parametrized which allows for a direct comparison with all-electron calculations. Extensive test calculations on first- and second-row molecules using the ECP have been performed, giving excellent agreement with the all-electron results at the SCF, CASSCF, and CI levels of treatment. Correlating and diffuse functions may be added without modifying the ECP parameters. The present ECP descriptions result in CPU time reductions of the order of 50 percent in addition to reduced disk storage.

Pettersson, Lars G. M.↗
DOE OSTI2024

A new generation of effective core potentials: Selected lanthanides and heavy elements

Here, we construct correlation-consistent effective core potentials (ccECPs) for a selected set of heavy atoms and ƒ-elements that are of significant current interest in materials and chemical applications, including Y, Zr, Nb, Rh, Ta, Re, Pt, Gd, and Tb. As is customary, ccECPs consist of spin orbit averaged relativistic effective potential (AREP) and effective spin-orbit (SO) terms. For the AREP part, our constructions are carried out within a relativistic coupled-cluster framework while also taking into account objective function one-particle characteristics for improved convergence in optimizations. The transferability is adjusted using binding curves of hydride and oxide molecules. We address the difficulties encountered with ƒ-elements, such as the presence of large cores and multiple near-degeneracies of excited levels. For these elements, we construct ccECPs with core valence partitioning that includes 4ƒ-subshell in the valence space. The developed ccECPs achieve an excellent balance between accuracy, size of the valence space, and transferability and are also suitable to be used in plane wave codes with reasonable energy cutoffs.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS1986

Accurate Effective Core Potential for Germanium. Application to the Singlet-Triplet Splitting in GeH2

An accurate effective core potential (ECP), including frozen 3s, 3p orbitals and a single-zeta contracted 3d orbital, has been developed for germanium. The ECP with associated valence basis set reproduces the corresponding all-electron results for the atomic excitations and the geometry and excitation energies of GeH2. At the SCF, CAS SCF and CI levels the maximum difference from the all-electron results is 0.5 kcal/mol in the (sup 1)A(sub 1) - (sup 3)B(sub 1) excitation energy. Finally, the ECP description is used with an extended valence basis set and large-scale CAS SCF and multi-reference CI wavefunctions to compute the singlet-triplet separation; the final CI result including the Davidson correction is 22.5 kcal/mol.

Pettersson, Lars G. M.↗
DOE OSTI2022

Correlation consistent effective core potentials for late 3 d transition metals adapted for plane wave calculations

We construct a new modification of correlation consistent effective core potentials (ccECPs) for late 3d elements Cr–Zn with Ne-core that are adapted for efficiency and low energy cut-offs in plane wave calculations. The decrease in accuracy is rather minor, so that the constructions are in the same overall accuracy class as the original ccECPs. The resulting new constructions work with energy cut-offs at or below ≈400 Ry and, thus, make calculations of large systems with transition metals feasible for plane wave codes. We also provide the basic benchmarks for atomic spectra and molecular tests of this modified option that we denote as ccECP-soft.

Chemistry↗
NASA NTRS1979

Ab initio studies of the electronic structure of UF6, UF6/+/, and UF6/-/ using relativistic effective core potentials

The paper presents ab initio calculations performed on the electronic states of UF6, UF6(+), and UF6(-) using a relativistic effective core potential (ECP) for uranium and a nonrelativistic ECP for fluorine. In most of the calculations 56 valence electrons are treated explicitly using a contracted (3s 3p 2d 2f/2s2p) Gaussian basis. It is noted that various ECP's were explored, but all yield an overall charge density of U(+2.4)/F(-0.4)/6. In addition, the bonding in the ground state of UF6 is discussed. SCF and CI calculations on UF6(+) are compared with the experimental photoelectron spectrum and with previous scattered wave calculations. Further, the role of spin-orbit coupling in the states of UF6(+) and UF6(-) is covered. Finally, it is concluded that the calculated electron affinity of UF6 (7.1 eV) is considerably larger than in current experimental estimates, but the relative energies of the states of UF6(-) are in agreement (0.1-0.2 eV) with those of the experiment.

Hay, P. J.↗
DOE OSTI2021

A quantum Monte Carlo study of systems with effective core potentials and node nonlinearities

In this report we study beryllium dihydride (BeH2) and acetylene (C2H2) molecules using real-space diffusion Monte Carlo (DMC) method. The molecules serve as perhaps the simplest prototypes that illustrate the difficulties with biases in the fixed-node DMC calculations that might appear with the use of effective core potentials (ECPs) or other nonlocal operators. This is especially relevant for the recently introduced correlation consistent ECPs (ccECPs) for 2s2p elements. Corresponding ccECPs exhibit deeper potential functions due to higher fidelity to all-electron counterparts, which could lead to larger local energy fluctuations. We point out that the difficulties stem from issues that are straightforward to address by upgrades of basis sets, use of T-moves for nonlocal terms, inclusion of a few configurations into the trial function and similar. The resulting accuracy corresponds to the ccECP target (chemical accuracy) and it is in consistent agreement with independent correlated calculations. Further possibilities for upgrading the reliability of the DMC algorithm and considerations for better adapted and more robust Jastrow factors are discussed as well.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS1991

All-electron molecular Dirac-Hartree-Fock calculations: Properties of the group IV monoxides GeO, SnO and PbO

Dirac-Hartree-Fock calculations have been carried out on the ground states of the group IV monoxides GeO, SnO and PbO. Geometries, dipole moments and infrared data are presented. For comparison, nonrelativistic, first-order perturbation and relativistic effective core potential calculations have also been carried out. Where appropriate the results are compared with the experimental data and previous calculations. Spin-orbit effects are of great importance for PbO, where first-order perturbation theory including only the mass-velocity and Darwin terms is inadequate to predict the relativistic corrections to the properties. The relativistic effective core potential results show a larger deviation from the all-electron values than for the hydrides, and confirm the conclusions drawn on the basis of the hydride calculations.

Dyall, Kenneth G.↗
NASA NTRS1993

All-electron molecular Dirac-Hartree-Fock calculations - Properties of the group IV monoxides GeO, SnO, and PbO

Dirac-Hartree-Fock calculations have been carried out on the ground states of the group IV monoxides GeO, SnO and PbO. Geometries, dipole moments and infrared data are presented. For comparison, nonrelativistic, first-order perturbation and relativistic effective core potential calculations have also been carried out. Where appropriate the results are compared with the experimental data and previous calculations. Spin-orbit effects are of great importance for PbO, where first-order perturbation theory including only the mass-velocity and Darwin terms is inadequate to predict the relativistic corrections to the properties. The relativistic effective core potential results show a larger deviation from the all-electron values than for the hydrides, and confirm the conclusions drawn on the basis of the hydride calculations.

Dyall, Kenneth G.↗
NASA NTRS1999

Bond Dissociation Energies of the Tungsten Fluorides and Their Singly-Charged Ions: A Density Functional Survey

The dissociation of WF6 and the related singly-charged cations and anions into the lower fluorides and fluorine atoms has been investigated theoretically using density functional theory (B3LYP) and relativistic effective core potentials, with estimates of spin-orbit effects included using a simple model. The inclusion of spin-orbit is essential for a correct description of the thermochemistry. The total atomization energy of the neutral and anionic WF6 is reproduced to within 25 kcal/mol, but comparison of individual bond dissociation energies with available experimental data shows discrepancies of up to 10 kcal/mol. The results are nevertheless useful to help resolve discrepancies in experimental data and provide estimates of missing data.

Dyall, Kenneth G.↗
DOE OSTI2022

Ab initio calculations in atoms, molecules, and solids, treating spin–orbit coupling and electron interaction on an equal footing

We incorporate explicit, non-perturbative treatment of spin–orbit coupling into ab initio auxiliary-field quantum Monte Carlo (AFQMC) calculations. The approach allows a general computational framework for molecular and bulk systems in which material specificity, electron correlation, and spin–orbit coupling effects can be captured accurately and on an equal footing, with favorable computational scaling vs system size. We adopt relativistic effective-core potentials that have been obtained by fitting to fully relativistic data and that have demonstrated a high degree of reliability and transferability in molecular systems. This results in a two-component spin-coupled Hamiltonian, which is then treated by generalizing the ab initio AFQMC approach. We demonstrate the method by computing the electron affinity in Pb, the bond dissociation energy in Br 2 and I 2 , and solid Bi.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS1982

Ab initio calculation of the X 1 Sigma + state of CsH

Stevens et al. (1981) considered CsH as a two electron problem, but simulated the Cs core electrons by an empirical pseudopotential following the work by Bardsley (1970). These potentials, since they are derived empirically, include the relativistic effects and the atomic core-valence interactions. However, molecular core-core interactions are not accounted for. Stevens et al. obtained an R(e) value which is too small. This result was attributed to uncorrected core (proton)-core interactions in the molecule. The present investigation is concerned with a resolution of the discrepancies between the results of earlier studies. The X 1 Sigma + ground state of CsH is recalculated. The calculation employs a nine valence electron relativistic effective core potential (RECP) for Cs. The bonding in CsH is found to involve a Cs(6s)-H(1s) bond but with a significant ionic (Cs+H-) component.

Laskowski, B. C.↗