## Theoretical investigation of ESR parameters: H\(_2\)CN and H\(_2\)CO\(^+\)

Please always quote using this URN: urn:nbn:de:bvb:20-opus-59029

- The hyperfine structure of the two isoelectronic molecules H\(_2\)CN and H\(_2\)CO\(^+\) in their electronic ground state (X\(^2\)B\(_2\)) is studied. The influence of the atomic orbital (AO), basis sets, of the correlation treatment, and of the. equilibrium geometry on the obtained hyperfine propertles 1s - investigated. It is found that the multireference double excitation-configuration interaction (MRD-CI)/ BK treatment in which an MRD-CI wave function is corrected by a modified B\(_K\) method yields equivalent results to quadratic CIThe hyperfine structure of the two isoelectronic molecules H\(_2\)CN and H\(_2\)CO\(^+\) in their electronic ground state (X\(^2\)B\(_2\)) is studied. The influence of the atomic orbital (AO), basis sets, of the correlation treatment, and of the. equilibrium geometry on the obtained hyperfine propertles 1s - investigated. It is found that the multireference double excitation-configuration interaction (MRD-CI)/ BK treatment in which an MRD-CI wave function is corrected by a modified B\(_K\) method yields equivalent results to quadratic CI [QCISD(T)], coupled cluster single doubles [CCSD(T)), or Brueckner doubled [BD(T)]. Uncertainties in the equilibrium geometries are found to be the major source for discrepancies between theoretically and experimentally determined isotropic hyperfine coupling constants (hfccs). For the heavier centers, the calculated values of the isotropic hfccs agrees nearly perfectly with experimental values (\(\approx\) 1%-2%). The calculated values for the hydrogens are too low, but using the equilibrium structure suggested by Yamamoto and Sato [J. Chem. Phys. 96, 4157 ( 1992)], the best estimate deviates by less than 3%.…

Author: | H. U. Suter, Bernd Engels |
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URN: | urn:nbn:de:bvb:20-opus-59029 |

Document Type: | Journal article |

Faculties: | Fakultät für Chemie und Pharmazie / Institut für Organische Chemie |

Language: | English |

Year of Completion: | 1994 |

Source: | Journal of Chemical Physics (1994) 100, 2936-2942. |

Dewey Decimal Classification: | 5 Naturwissenschaften und Mathematik / 54 Chemie / 540 Chemie und zugeordnete Wissenschaften |

GND Keyword: | Organische Chemie |

Release Date: | 2011/11/04 |

Licence (German): | Deutsches Urheberrecht |