Relativistic all-electron density functional calculations

Wüllen, Christoph van

doi:10.1002/(sici)1096-987x(19990115)20:1<51::aid-jcc7>3.0.co;2-k

Cited by 77 publications

(68 citation statements)

References 66 publications

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“…The most of our calculations were performed using M06-L density functional which has been well validated for transition metals [11][12][13]. We have included the relativistic effects using two most popular ways: via Douglass-Kroll-Hess twocomponent (DKH2) Hamiltonian [14,15] or utilizing zeroorder regular approximation (ZORA) [16][17][18]. The computations with DKH2 approach were performed with ORCA 4.0.1 program [19], and the results by ZORA were obtained in ADF 2018 [20][21][22].…”

Section: Methodsmentioning

confidence: 99%

The high covalence of metal-ligand bonds as stability limiting factor: the case of Rh(IX)O4+ and Rh(IX)NO3

et al. 2020

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Rhodium, a 4d transition metal and a lighter analogue of iridium, is known to exhibit its highest VIth oxidation state in RhF 6 molecule. In this report, the stability and decomposition pathways of two species containing rhodium at a potentially formal +IX oxidation state, [RhO 4 ] + and RhNO 3 , have been investigated theoretically within the framework of the relativistic twocomponent Hamiltonian calculations. Possible rearrangement into isomers featuring lower formal oxidation numbers has been explored. We found that both species studied are metastable with respect to elimination of O 2 or NO. However, the local minima containing Rh(IX) are protected by sufficient energy barriers on the decomposition pathway, and they could in principle be prepared. The analysis of a broader set of compounds containing group 8 and 9 metals in high formal oxidation states that correspond to the group number showed that, in contrast to a standard trend, the limits of formally attainable oxidation state correlate with high level of covalent bonding character in the complexes studied.

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Section: Methodsmentioning

confidence: 99%

The high covalence of metal-ligand bonds as stability limiting factor: the case of Rh(IX)O4+ and Rh(IX)NO3

et al. 2020

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“…Among the all-electron relativistic approaches available, the family of Douglas-Kroll-Hess (DKH) transformation-based methods [59][60][61] and zero order regular approximation (ZORA) [62][63][64] are the methods most widely tested and used [65,66]. Different theoretical investigations showed that the ZORA and DKH approaches provide similar results.…”

Section: Methodsmentioning

confidence: 99%

Structure, Dynamics, and Computational Studies of Lanthanide‐Based Contrast Agents

Peters

Djanashvili

Geraldes

et al. 2013

The Chemistry of Contrast Agents in Medical Magnetic Resonance Imaging

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“…If we require to reproduce the length of magnetization instead, this is a noncollinear [' '(nc)' '] approach because the magnetization is a vector field representing a magnetic dipole moment whose direction changes with position. [135,137,139,140,141] Note that these different choices for the noninteracting reference system each implies a different definition of the noninteracting kinetic energy functional, T ðclÞ s ½q; m z and T ðncÞ s ½q; jmj , and thus also of the exchange-correlation energy, E ðclÞ xc ½q; m z and E ðncÞ xc ½q; jmj , respectively. For the choices mentioned here, where in addition to the electron density one additional quantity is reproduced by the KS system, the resulting exchangecorrelation potential has two components.…”

Section: Relativistic Spin-dftmentioning

confidence: 99%

Spin in density‐functional theory

Jacob¹,

Reiher²

2012

Int J of Quantum Chemistry

225

224

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The accurate description of open-shell molecules, in particular of transition metal complexes and clusters, is still an important challenge for quantum chemistry. Although density-functional theory (DFT) is widely applied in this area, the sometimes severe limitations of its currently available approximate realizations often preclude its application as a predictive theory. Here, we review the foundations of DFT applied to open-shell systems, both within the nonrelativistic and the relativistic framework. In particular, we provide an in-depth discussion of the exact theory, with a focus on the role of the spin density and possibilities for targeting specific spin states. It turns out that different options exist for setting up Kohn-Sham DFT schemes for open-shell systems, which imply different definitions of the exchangecorrelation energy functional and lead to different exact conditions on this functional. Finally, we suggest possible directions for future developments.

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Relativistic all-electron density functional calculations

Cited by 77 publications

References 66 publications

The high covalence of metal-ligand bonds as stability limiting factor: the case of Rh(IX)O4+ and Rh(IX)NO3

The high covalence of metal-ligand bonds as stability limiting factor: the case of Rh(IX)O4+ and Rh(IX)NO3

Structure, Dynamics, and Computational Studies of Lanthanide‐Based Contrast Agents

Spin in density‐functional theory

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