Relativistic Pseudopotentials: Their Development and Scope of Applications

Dolg, Michael; Cao, Xiaoyan

doi:10.1021/cr2001383

Cited by 389 publications

(389 citation statements)

References 619 publications

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“…Therefore, sooner or later we shall face the problem of evaluation of the matrix elements of the orbitorbit and spin-orbit operators with the exponential functions. For heavy atoms, where the perturbation theory breaks down, different approaches need to be considered such as Douglas-Kroll-Hess transformations [108][109][110][111] or use of effective core potentials [112,113]. Neither of the above methods can straightforwardly be combined with the STOs basis sets.…”

Section: Discussionmentioning

confidence: 99%

Reexamination of the calculation of two-center, two-electron integrals over Slater-type orbitals. III. Case study of the beryllium dimer

et al. 2015

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In this paper we present results of ab-initio calculations for the beryllium dimer with basis set of Slater-type orbitals (STOs). Nonrelativistic interaction energy of the system is determined using the frozen-core full configuration interaction calculations combined with high-level coupled cluster correction for inner-shell effects. Newly developed STOs basis sets, ranging in quality from double to sextuple zeta, are used in these computations. Principles of their construction are discussed and several atomic benchmarks are presented. Relativistic effects of order α 2 are calculated perturbatively by using the Breit-Pauli Hamiltonian and are found to be significant. We also estimate the leading-order QED effects. Influence of the adiabatic correction is found to be negligible. Finally, the interaction energy of the beryllium dimer is determined to be 929.0 ± 1.9 cm −1 , in a very good agreement with the recent experimental value. The results presented here appear to be the most accurate ab-initio calculations for the beryllium dimer available in the literature up to date and probably also one of the most accurate calculations for molecular systems containing more than four electrons.

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Section: Discussionmentioning

confidence: 99%

Reexamination of the calculation of two-center, two-electron integrals over Slater-type orbitals. III. Case study of the beryllium dimer

et al. 2015

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“…25,27 We note that scalar relativistic effects, when important, are often accounted for in quantum chemistry by using effective core potentials. 28 Incorporating the SOC Hamiltonian in the electronic Hamiltonian, 27,[29][30][31] we obtain a molecular Hamiltonian accounting for the electronic spin s,…”

Section: Theorymentioning

confidence: 99%

Communication: GAIMS—Generalized Ab Initio Multiple Spawning for both internal conversion and intersystem crossing processes

Curchod

Rauer

Marquetand

et al. 2016

The Journal of Chemical Physics

103

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A new approach to molecular dynamics with non-adiabatic and spin-orbit effects with applications to QM/MM simulations of thiophene and selenophene The Journal of Chemical Physics 146, 114101 (2017); 10.1063/1.4978289 THE JOURNAL OF CHEMICAL PHYSICS 144, 101102 (2016) Communication: GAIMS-Generalized Ab Initio Multiple Spawning for both internal conversion and intersystem crossing processes Full multiple spawning is a formally exact method to describe the excited-state dynamics of molecular systems beyond the Born-Oppenheimer approximation. However, it has been limited until now to the description of radiationless transitions taking place between electronic states with the same spin multiplicity. This Communication presents a generalization of the full and ab initio multiple spawning methods to both internal conversion (mediated by nonadiabatic coupling terms) and intersystem crossing events (triggered by spin-orbit coupling matrix elements) based on a spin-diabatic representation. The results of two numerical applications, a model system and the deactivation of thioformaldehyde, validate the presented formalism and its implementation. C 2016 AIP Publishing LLC. [http://dx

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“…In this framework, the relativistic terms are implicitly incorporated into the potential considered by parametrization with respect to suitable relativistic allelectron reference data. A detailed description of the formalism and limitations can be found in references [148][149][150]. The vast majority of electronic structure calculations on actinide species uses this simple one-component ECP method including only scalar relativistic effects.…”

Section: Some Aspects Of Relativistic Quantum Chemistrymentioning

confidence: 99%

Electronic structure theory to decipher the chemical bonding in actinide systems

Dognon

2017

Coordination Chemistry Reviews

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International audienceThe chemical bonding in actinide compounds is usually analysed by inspecting the shape and the occupation of the orbitals or by calculating bond orders which are based on orbital overlap and occupation numbers. However, this may not give a definite answer because the choice of the partitioning method may strongly influence the result possibly leading to qualitatively different answers. In this review, we summarized the state-of-the-art of methods dedicated to the theoretical characterisation of bonding including charge, orbital, quantum chemical topology and energy decomposition analyses. This review is not exhaustive but aims to highlight some of the ways opened up by recent methodological developments. Various examples have been chosen to illustrate this progress

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Relativistic Pseudopotentials: Their Development and Scope of Applications

Cited by 389 publications

References 619 publications

Reexamination of the calculation of two-center, two-electron integrals over Slater-type orbitals. III. Case study of the beryllium dimer

Reexamination of the calculation of two-center, two-electron integrals over Slater-type orbitals. III. Case study of the beryllium dimer

Communication: GAIMS—Generalized Ab Initio Multiple Spawning for both internal conversion and intersystem crossing processes

Electronic structure theory to decipher the chemical bonding in actinide systems

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