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

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Title:Spin-Orbit Coupling in Biradicals. 4. Zero-Field Splitting in Triplet Nitrenes, Phosphinidenes, and Arsinidenes
Creators:
Havlas, Zdeněk
Kývala, Mojmír
Michl, Josef
Journal or Publication Title:
Collection of Czechoslovak Chemical Communications, 68, 12, pp. 2335-2343
Uncontrolled Keywords:<i>Ab initio</i> calculations, EPR spectroscopy, Radicals, Spin-orbit coupling, CASSCF, Triplet states, Wave functions

Abstract

The spin dipole-spin dipole and spin-orbit coupling contributions to the zero-field splitting parameter <i>D</i> of CH<sub>3</sub>-N, CH<sub>3</sub>-P, CH<sub>3</sub>-As, SiH<sub>3</sub>-N, SiH<sub>3</sub>-P, and SiH<sub>3</sub>-As have been calculated from CAS(12,11)/cc-pVTZ wave functions and the Breit-Pauli Hamiltonian at T<sub>1</sub> 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<sup>-1</sup>, in good agreement with experiment (1.72 cm<sup>-1</sup>). 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. <p>

Title:Spin-Orbit Coupling in Biradicals. 4. Zero-Field Splitting in Triplet Nitrenes, Phosphinidenes, and Arsinidenes
Creators:
Havlas, Zdeněk
Kývala, Mojmír
Michl, Josef
Uncontrolled Keywords:<i>Ab initio</i> calculations, EPR spectroscopy, Radicals, Spin-orbit coupling, CASSCF, Triplet states, Wave functions
Divisions:Life and Chemical Sciences > Institute of Organic Chemistry and Biochemistry > Collection of Czechoslovak Chemical Communications
Journal or Publication Title:Collection of Czechoslovak Chemical Communications
Volume:68
Number:12
Page Range:pp. 2335-2343
ISSN:0010-0765
E-ISSN:1212-6950
Publisher:Institute of Organic Chemistry and Biochemistry
Related URLs:
URLURL Type
http://dx.doi.org/10.1135/cccc20032335UNSPECIFIED
ID Code:2188
Item Type:Article
Deposited On:06 Feb 2009 17:16
Last Modified:06 Feb 2009 16:16

Citation

Havlas, Zdeněk; Kývala, Mojmír; Michl, Josef (2003) Spin-Orbit Coupling in Biradicals. 4. Zero-Field Splitting in Triplet Nitrenes, Phosphinidenes, and Arsinidenes. Collection of Czechoslovak Chemical Communications, 68 (12). pp. 2335-2343. ISSN 0010-0765

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