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

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Title:Spin-Orbit Coupling in Biradicals. 3. Heavy Atom Effects in Carbenes
Creators:
Havlas, Zdeněk
Michl, Josef
Journal or Publication Title:
Collection of Czechoslovak Chemical Communications, 63, 9, pp. 1485-1497
Uncontrolled Keywords:Spin-spin dipolar coupling, <i>Ab initio</i>calculations, Zero-field-splitting parameters, Spin-orbit coupling, Carbenes

Abstract

CASSCF(8,6)/cc-pVDZ calculations of electron spin-spin dipole interaction tensor in the lowest triplet state of CH<sub>2</sub>, 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.

Title:Spin-Orbit Coupling in Biradicals. 3. Heavy Atom Effects in Carbenes
Creators:
Havlas, Zdeněk
Michl, Josef
Uncontrolled Keywords:Spin-spin dipolar coupling, <i>Ab initio</i>calculations, Zero-field-splitting parameters, Spin-orbit coupling, Carbenes
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:63
Number:9
Page Range:pp. 1485-1497
ISSN:0010-0765
E-ISSN:1212-6950
Publisher:Institute of Organic Chemistry and Biochemistry
Related URLs:
URLURL Type
http://dx.doi.org/10.1135/cccc19981485UNSPECIFIED
ID Code:1395
Item Type:Article
Deposited On:06 Feb 2009 17:09
Last Modified:06 Feb 2009 16:09

Citation

Havlas, Zdeněk; Michl, Josef (1998) Spin-Orbit Coupling in Biradicals. 3. Heavy Atom Effects in Carbenes. Collection of Czechoslovak Chemical Communications, 63 (9). pp. 1485-1497. ISSN 0010-0765

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