Friday, June 20, 2008

Chemical Physics, Volume 351, Issues 1-3, 3 July 2008, Pages 83-90

Theoretical study of 14N quadrupole coupling constants in some NO-containing complexes: N2O3 and FNO

R. Polák, , and J. Fišer

The nuclear quadrupole coupling constants at nitrogen centers have been computed for N2O3 and FNO by employing the complete-active-space self-consistent field, internally contracted multireference configuration interaction and single-configuration coupled-cluster methods with correlation-consistent basis sets at the levels of attainable accuracy. To examine the overall quality of the wave functions used in our calculations, also electric dipole moments and potential energy characteristics were calculated and compared with available experimental and recent theoretical data. The effects of the choice of the basis set and reference configuration space were investigated. The robust changes in the electric field gradients occurring in the course of complex formation from isolated subunits were interpreted in terms of wave function composition. Our calculations confirm the assignment of the 14N nuclear quadrupole coupling constants to nuclear centers in N2O3 provided by the microwave measurements of Cox et al. [A.P. Cox, J. Randell, A.C. Legon, Chem. Phys. Lett. 126 (1986) 481.].

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