ISSN:
1572-9001
Source:
Springer Online Journal Archives 1860-2000
Topics:
Chemistry and Pharmacology
Notes:
Abstract Ab initio SCF studies were performed with Cu and F basis sets of near-Hartree-Fock (HF) limit quality to obtain accurate SCF results for the molecular ground state properties of CuF+, CuF, CuF−, CuF2, and CuF2 −, as well as for the first two low-lying excited states of CuF2. A study on the effects of electron correlation was carried out by Møller-Plesset (MP) and configuration interaction (Cl) calculations. The effect of relativity on the63Cu nuclear quadrupole coupling in CuF was determined by use of a coupled HF procedure for a first-order spin-orbital-averaged Pauli operator. At the HF level the63Cu coupling constant was found to be 35.8 MHz (in e2qQ h−1), while allowing for relativity the value was reduced to 29.1 MHz, which is in better agreement with the experimental value of 22.0 MHz. The calculated molecular properties for CuF [r e = 1.737 Å,D e=4.38 eV, ωe = 562 cm−1 (MP4);r e= 1.796 Å,D e = 3.91 eV,ω e=585 cm−1 (CISD)] were in good agreement with experiment (r e = 1.745 Å,D e = 4.43 eV,ω e=623 cm−1). The adiabatic ground-state potential curve of CuF+ avoids crossing near the equilibrium distance between the two ionic potential curves Cu+-F and Cu2+-F−. At the crossing point the Cu and F electric field gradients show a sharp discontinuity.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1007/BF00671226
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