Ab initio configuration interaction calculations of the hyperfine structure in small radicals
- 1 February 1984
- journal article
- Published by AIP Publishing in The Journal of Chemical Physics
- Vol. 80 (3) , 1006-1017
- https://doi.org/10.1063/1.446826
Abstract
Extended basis set natural orbital CI wave functions have been used to compute the isotropic and anisotropic hyperfine coupling of ten small radicals for which experimental measurements exist. The configuration spaces employed in the CI’s were of two kinds: One involved all single and double excitations from the Hartree–Fock configuration plus limited triples and quadrupoles, while the other consisted of singles and doubles from a multireference set coupled with various configuration selection techniques. At the highest level of theory used in the present study, agreement with experiment was generally within 10%, but differences for the isoelectronic series H2CN, H2CO+, and H2BO as well as the related acetaldehyde radical cation H3C–CHO+ are larger than would be expected based on the data from the other six radicals.Keywords
This publication has 50 references indexed in Scilit:
- Comment on ab initio calculation of spin densities in hydrocarbon radicalsThe Journal of Chemical Physics, 1983
- An approximation to frozen natural orbitals through the use of the Hartree–Fock exchange potentialThe Journal of Chemical Physics, 1981
- Calculation of zero field splitting parameters for trimethylenemethaneThe Journal of Chemical Physics, 1981
- A theoretical study on the potential surfaces of the lower electronic states of HCOThe Journal of Chemical Physics, 1979
- Influence of spin contamination and basis set on electrostatic potential and Hfs coupling constants of organic radicalsTheoretical Chemistry Accounts, 1976
- Geometries of the methoxy radical (X 2E and A 2A1 states) and the methoxide ionJournal of the American Chemical Society, 1974
- A configuration interaction study of the spin dipole‐dipole parameters for formaldehyde and methyleneInternational Journal of Quantum Chemistry, 1973
- Hartree-fock values of energies, interaction constants, and atomic properties for the groundstates of the negative ions, neutral atoms, and first four positive ions from helium to kryptonAtomic Data and Nuclear Data Tables, 1971
- Nonempirical Calculations of the Isotropic Hyperfine Splitting Constants of 13C, 14N, and 17O in Simple RadicalsThe Journal of Chemical Physics, 1967
- The hyperfine structure of the hydrogen molecular ionProceedings of the Royal Society of London. Series A. Mathematical and Physical Sciences, 1960