Ligand field theory for pentacoordinate molecules. II. Crystal field-spin-orbit coupling treatment of the d1, d3, d6, and d8 configurations in trigonal-bipyramidal molecules and the magnetic properties of E ground terms

1969 ◽  
Vol 8 (3) ◽  
pp. 491-497 ◽  
Author(s):  
John S. Wood ◽  
Peter Townsend Greene
Keyword(s):  
Field Theory ◽  
Magnetic Properties ◽  
Crystal Field ◽  
Orbit Coupling ◽  
Ligand Field ◽  
Spin Orbit Coupling ◽  
Spin Orbit ◽  
Ligand Field Theory ◽  
Trigonal Bipyramidal ◽  
Coupling Treatment

Über die Spin-Bahn-Wechselwirkung in der Ligandenfeldtheorie

1963 ◽  
Vol 18 (3) ◽  
pp. 276-280
Author(s):  
H.-H. Schmidtke
Keyword(s):  
Field Theory ◽  
Ligand Field ◽  
Spin Orbit Coupling ◽  
Spin Orbit ◽  
Field Potentials ◽  
Coupling Energy ◽  
Ligand Field Theory ◽  
Transition Series ◽  
Low Symmetry ◽  
Made In

The spin-orbit coupling operators in ligand field theory for octahedral, tetragonal, trigonal and axial symmetry are derived from the corresponding crystal field potentials. An estimate of the coupling energy for the low symmetry part of this operator is made in the case of octahedrally symmetric complexes of the first transition series. The results are discussed and compared with other approaches to this problem.

scholarly journals Spin-Orbit Coupling Descriptions of Magnetic Excitations in Lanthanide Complexes

2020 ◽  
Author(s):  
Shashank Vittal Rao ◽  
MATTEO PICCARDO ◽  
Alessandro Soncini
Keyword(s):  
Crystal Field ◽  
Electron Spin ◽  
Single Molecule ◽  
Lanthanide Complexes ◽  
Mean Field ◽  
Orbit Coupling ◽  
Ligand Field ◽  
Spin Orbit Coupling ◽  
Spin Orbit ◽  
Magnetic Excitations

We present a number of computationally cost-effective approaches to calculate magnetic excitations (i.e. crystal field energies and magnetic anisotropies in the lowest spin-orbit multiplet) in lanthanide complexes. In particular, we focus on the representation of the spin-orbit coupling term of the molecular Hamiltonian, which has been implemented within the quantum chemistry package CERES using various approximations to the Breit-Pauli Hamiltonian. The approximations include the (i) bare one-electron approximation, (ii) atomic mean field and molecular mean field approximations of the two-electron term, (iii) full representation of the Breit-Pauli Hamiltonian. Within the framework of the CERES implementation, the spin-orbit Hamiltonian is always fully diagonalized together with the electron repulsion Hamiltonian (CASCI-SO) on the full basis of Slater determinants arising within the 4f ligand field space. For the first time, we make full use of the Cholesky decomposition of two-electron spin-orbit integrals to speed up the calculation of the two-electron spin-orbit operator. We perform an extensive comparison of the different approximations on a set of lanthanide complexes varying both the lanthanide ion and the ligands. Surprisingly, while our results confirm the need of at least a mean field approach to accurately describe the spin-orbit coupling interaction within the ground Russell-Saunders term, we find that the simple bare one-electron spin-orbit Hamiltonian performs reasonably well to describe the crystal field split energies and <sub>g</sub> tensors within the ground spin-orbit multiplet, which characterize all the magnetic excitations responsible for lanthanide-based single-molecule magnetism.<br>

scholarly journals Spin-Orbit Coupling Descriptions of Magnetic Excitations in Lanthanide Complexes

2020 ◽  
Author(s):  
Shashank Vittal Rao ◽  
MATTEO PICCARDO ◽  
Alessandro Soncini
Keyword(s):  
Crystal Field ◽  
Electron Spin ◽  
Single Molecule ◽  
Lanthanide Complexes ◽  
Mean Field ◽  
Orbit Coupling ◽  
Ligand Field ◽  
Spin Orbit Coupling ◽  
Spin Orbit ◽  
Magnetic Excitations

We present a number of computationally cost-effective approaches to calculate magnetic excitations (i.e. crystal field energies and magnetic anisotropies in the lowest spin-orbit multiplet) in lanthanide complexes. In particular, we focus on the representation of the spin-orbit coupling term of the molecular Hamiltonian, which has been implemented within the quantum chemistry package CERES using various approximations to the Breit-Pauli Hamiltonian. The approximations include the (i) bare one-electron approximation, (ii) atomic mean field and molecular mean field approximations of the two-electron term, (iii) full representation of the Breit-Pauli Hamiltonian. Within the framework of the CERES implementation, the spin-orbit Hamiltonian is always fully diagonalized together with the electron repulsion Hamiltonian (CASCI-SO) on the full basis of Slater determinants arising within the 4f ligand field space. For the first time, we make full use of the Cholesky decomposition of two-electron spin-orbit integrals to speed up the calculation of the two-electron spin-orbit operator. We perform an extensive comparison of the different approximations on a set of lanthanide complexes varying both the lanthanide ion and the ligands. Surprisingly, while our results confirm the need of at least a mean field approach to accurately describe the spin-orbit coupling interaction within the ground Russell-Saunders term, we find that the simple bare one-electron spin-orbit Hamiltonian performs reasonably well to describe the crystal field split energies and <sub>g</sub> tensors within the ground spin-orbit multiplet, which characterize all the magnetic excitations responsible for lanthanide-based single-molecule magnetism.<br>

Switchable electronic and enhanced magnetic properties of CrI3 edges

2021 ◽  
Author(s):  
Guohui Yang ◽  
Rui Wang ◽  
Mei Ge ◽  
Miaomiao Guo ◽  
Jicui Wang ◽  
...  
Keyword(s):  
Magnetic Properties ◽  
First Principles ◽  
Orbit Coupling ◽  
Ligand Field ◽  
Spin Orbit Coupling ◽  
Spin Orbit ◽  
First Principles Calculations ◽  
Electron Counting ◽  
Counting Model

The first-principles calculations with spin–orbit coupling suggest that, the thermodynamic stabilities of CrI3 nano ribbon can be understood through the octahedron ligand field and electron counting model.

Ground configuration splitting in UCl5

1977 ◽  
Vol 55 (10) ◽  
pp. 937-942 ◽  
Author(s):  
A. F. Leung ◽  
Ying-Ming Poon
Keyword(s):  
Crystal Field ◽  
Energy Levels ◽  
Orbit Coupling ◽  
Spin Orbit Coupling ◽  
Spin Orbit ◽  
Coupling Constant ◽  
Point Charge Model ◽  
X Ray Crystallography ◽  
Charge Model ◽  
Crystal Field Parameters

The absorption spectra of UCl5 single crystal were observed in the region between 0.6 and 2.4 μm at room, 77, and 4.2 K temperatures. Five pure electronic transitions were assigned at 11 665, 9772, 8950, 6643, and 4300 cm−1. The energy levels associated with these transitions were identified as the splittings of the 5f1 ground configuration under the influence of the spin–orbit coupling and a crystal field of C2v symmetry. The number of crystal field parameters was reduced by assuming the point-charge model where the positions of the ions were determined by X-ray crystallography. Then, the crystal field parameters and the spin–orbit coupling constant were calculated to be [Formula: see text],[Formula: see text], [Formula: see text], and ξ = 1760 cm−1. The vibronic analysis showed that the 90, 200, and 320 cm−1 modes were similar to the T2u(v6), T1u(v4), and T1u(v3) of an UCl6− octahedron, respectively.

Sign in / Sign up

Export Citation Format

Share Document