Collect. Czech. Chem. Commun. 2005, 70, 923-940

Electron Affinities of BN, NO and NF: Coupled Cluster and Multireference Configuration Interaction Calculations

Jiří Fišera,* and Rudolf Polákb

a Department of Physical and Macromolecular Chemistry, Faculty of Science, Charles University, Hlavova 2030, 128 40 Prague 2, Czech Republic
b J. Heyrovský Institute of Physical Chemistry, Academy of Sciences of the Czech Republic, Dolejškova 3, 182 23 Prague 8, Czech Republic


The accurate adiabatic electron affinities (EA) of the BN, NO and NF molecules have been determined using the coupled cluster approach and multireference configuration interaction methods. By combining large doubly augmented correlation-consistent basis sets (through the sextuple zeta) and complete basis set extrapolations with corrections for core-valence correlation and relativistic effects, we find that the RCCSD(T) method gives EA(BN) = 3.153 eV in very close agreement with experiment and predicts EA(NF) = 0.247 eV. The RCCSD(T) and UCCSD(T) EA(NO) results, 0.008 and 0.031 eV, bracket the experimental value. For both the neutral and anionic ground state species the usual spectroscopic constants were derived.

Keywords: Ab initio calculations; RCCSD(T); UCCSD(T); Spectroscopic constants; Spin-orbit coupling; Electron affinity; Douglas-Kroll-Hess relativistic corrections; Complete basis set extrapolations.

References: 55 live references.