Spin-Orbit Coupling in Biradicals. 3. Heavy Atom Effects in Carbenes

1998 ◽  
Vol 63 (9) ◽  
pp. 1485-1497 ◽  
Author(s):  
Zdeněk Havlas ◽  
Josef Michl
Keyword(s):  
Triplet State ◽  
Valence Angle ◽  
Heavy Atom ◽  
Dipole Interaction ◽  
Orbit Coupling ◽  
Zero Field ◽  
Spin Orbit Coupling ◽  
Spin Orbit ◽  
Zero Field Splitting ◽  
The One

CASSCF(8,6)/cc-pVDZ calculations of electron spin-spin dipole interaction tensor in the lowest triplet state of CH2, CHF, CHCl, and CHBr, spin-orbit coupling of each of the three sublevels with the lowest singlet, and the triplet zero-field-splitting parameters are reported as a function of the valence angle, with bond lengths optimized for the triplet state at the B3LYP/cc-pVTZ level of approximation. Both the one- and the two-electron parts of the spin-orbit coupling Hamiltonian are used, and the contributions to spin-orbit coupling provided by each atom and orbital pair in Weinhold's natural hybrid orbital basis are evaluated separately. This provides intuitive insight into the origin of spin-orbit coupling in carbenes and especially, the heavy atom effect of the substituent.

Predicting phosphorescent lifetimes and zero-field splitting of organometallic complexes with time-dependent density functional theory including spin–orbit coupling

2014 ◽  
Vol 16 (28) ◽  
pp. 14523-14530 ◽  
Author(s):  
K. Mori ◽  
T. P. M. Goumans ◽  
E. van Lenthe ◽  
F. Wang
Keyword(s):  
Density Functional ◽  
Organometallic Complexes ◽  
Orbit Coupling ◽  
Zero Field ◽  
Spin Orbit Coupling ◽  
Spin Orbit ◽  
Zero Field Splitting ◽  
Solvation Model ◽  
Functional Theory ◽  
Tddft Calculations

Experimental phosphorescent lifetimes for various organometallic complexes are well reproduced by spin–orbit coupling TDDFT calculations with a continuum solvation model.

Studies of EPR Parameters and Local Structure for Cr3+ in NaInS2 Crystal

2005 ◽  
Vol 60 (1-2) ◽  
pp. 91-94
Author(s):  
Yang Mei ◽  
Wen-Chen Zheng ◽  
Xiao-Xuan Wu ◽  
Qing Zhoua
Keyword(s):  
Local Structure ◽  
Coupling Parameter ◽  
Orbit Coupling ◽  
Zero Field ◽  
Spin Orbit Coupling ◽  
Spin Orbit ◽  
Zero Field Splitting ◽  
Field Splitting ◽  
Epr Parameters ◽  
Local Angle

The EPR parameters (zero-field splitting D and g factors g‖, g⊥) of Cr3+ in a NaInS2 crystal are calculated from high-order perturbation formulas based on the two spin-orbit coupling parameter model for the EPR parameters of 3d3 ions in trigonal octahedral sites. In the calculations, both the contribution to EPR parameters from the spin-orbit coupling parameter of the central 3d3 ion and that of ligands are considered. From the calculations it is found that, to explain reasonably the EPR parameters, the local structure (in particular the local trigonal distortion angle θ ) in the vicinity of the Cr3+ impurity is different from the corresponding structure in the host crystal. The change of the local angle θ with temperature is also obtained from the temperature dependence of zero-field splitting. The results are discussed.

Studies of the Zero-Field Splitting for Mn2+ In 6H-RbMgF3 Crystal

2004 ◽  
Vol 59 (12) ◽  
pp. 961-963 ◽  
Author(s):  
Wen-Chen Zheng ◽  
Yang Mei ◽  
Xiao-Xuan Wu ◽  
Qing Zhou
Keyword(s):  
Structural Data ◽  
Orbit Coupling ◽  
Site Symmetry ◽  
Coupling Mechanism ◽  
Zero Field ◽  
Spin Orbit Coupling ◽  
Spin Orbit ◽  
Superposition Model ◽  
Zero Field Splitting ◽  
Field Splitting

By using the spin-orbit coupling mechanism and the empirical superposition model, the zero-field splittings D of Mn2+ ions on both Mg2+ sites in hexagonal 6H-RbMgF3 crystal are calculated from the structural data of both Mg2+ sites. The calculated results of both methods confirm the suggestion that Mn2+ in 6H-RbMgF3 occupies the Mg2+ (I) site (which has D3d site symmetry) and the zero-field splitting D of 6H-RbMgF3: Mn2+ is explained reasonably.

Calculations of quartet state spectra for diatomic species by INDO CI method including spin-orbit coupling perturbation

1981 ◽  
Vol 46 (1) ◽  
pp. 179-193 ◽  
Author(s):  
Boris F. Minaev ◽  
Rudolf Zahradník
Keyword(s):  
Dipole Moments ◽  
Orbit Coupling ◽  
Qualitative Description ◽  
Photoelectron Spectra ◽  
Zero Field ◽  
Spin Orbit Coupling ◽  
Spin Orbit ◽  
Zero Field Splitting ◽  
Transition Dipole ◽  
Structure Constants

Transition dipole moments for quartet-doublet transitions in diatomic species (NO, O+2 and CF) have been calculated on the basis of the INDO CI method and spin-orbit coupling (SOC) has been taken into account as a perturbation. Qualitative description of the first excited quartet and doublet states and occurrence of quartet states in photoelectron spectra are briefly discussed. The intensity and polarization of the components of the a4*P - X2*P transitions in NO and O+2 and the a4Σ- - X2*P transition in CF have been calculated. Fine structure constants (SOC constant A for 2*P and 4*P states, spin-rotation and zero-field splitting for the 4Σ- state) have been obtained and compared with experiment where possible.

Spin-Orbit Coupling in Biradicals. 4. Zero-Field Splitting in Triplet Nitrenes, Phosphinidenes, and Arsinidenes

2003 ◽  
Vol 68 (12) ◽  
pp. 2335-2343 ◽  
Author(s):  
Zdeněk Havlas ◽  
Mojmír Kývala ◽  
Josef Michl
Keyword(s):  
Orbit Coupling ◽  
Zero Field ◽  
Spin Orbit Coupling ◽  
Spin Orbit ◽  
Zero Field Splitting ◽  
Field Splitting ◽  
Zero Field Splitting Parameter ◽  
Order Of Magnitude ◽  
Splitting Parameter ◽  
A Minor

The spin dipole-spin dipole and spin-orbit coupling contributions to the zero-field splitting parameter D of CH3-N, CH3-P, CH3-As, SiH3-N, SiH3-P, and SiH3-As have been calculated from CAS(12,11)/cc-pVTZ wave functions and the Breit-Pauli Hamiltonian at T1 B3LYP/cc-pVTZ optimized geometries. The spin-orbit coupling contributions represent a minor correction for the nitrenes, and bring the value computed for methylnitrene from 1.66 to 1.84 cm-1, in good agreement with experiment (1.72 cm-1). They dominate the spin-spin terms by an order of magnitude in phosphinidenes and by more than two orders of magnitude for arsinidenes. The properties of all these perfect axial biradicals follow expectations based on the simple algebraic 2-in-2 model of biradical structure.

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