Collect. Czech. Chem. Commun. 2003, 68, 2335-2343

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

Zdeněk Havlasa,*, Mojmír Kývalaa and Josef Michlb

a Institute of Organic Chemistry and Biochemistry, Academy of Sciences of Czech Republic, and Centre for Complex Molecular Systems and Biomolecules, 166 10 Prague 6, Czech Republic
b J. Heyrovský Institute of Physical Chemistry, Academy of Sciences of the Czech Republic, 182 23 Prague 8, Czech Republic


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.

Keywords: Radicals; Spin-orbit coupling; EPR spectroscopy; CASSCF; Triplet states; Wave functions; Ab initio calculations.

References: 18 live references.