ISSN:
1089-7690
Source:
AIP Digital Archive
Topics:
Physics
,
Chemistry and Pharmacology
Notes:
The electric field gradient (EFG) at the deuterium nucleus of the bifluoride ion, a linear symmetrically H-bonded system, has been calculated using ab initio Hartree–Fock SCF, singles and doubles CI, and coupled pair functional methods using basis sets ranging from double zeta to the [7,5,2,1;5,4,2] contracted Gaussian set. For the free DF−2 ion, the EFG and the resulting nuclear quadrupole coupling constant (nqcc) are found to be very low and positive in sign, and to display marked dependences on basis set, and the effects of electron correlation and vibrational averaging. In particular, we note a peculiarly extreme basis-set limit problem for deuterium EFGs in symmetric H-bonded molecules. The effects of the crystal lattice on the nqcc have been calculated for the sodium, potassium, and ammonium bifluorides taking into account: the direct contribution of the lattice to the EFG as modeled by a point-charge distribution; its polarizing effect on an individual DF−2 ion using two different methods; and also the effects of librational averaging. The predicted deuterium nqccs and asymmetry parameters (η) in the bifluoride salts are compared with the free-ion values (η necessarily zero). While our predicted nqcc in KDF2 of 55±3 kHz is consistent with the only reported experimental value of 58±10 kHz [R. Blinc et al., Chem. Phys. Lett. 48, 596 (1977)], the calculated η value of 0.07±0.01 is at serious variance with the experimental value of 0.4±0.1. As our treatment of the crystal lattice effects is quite comprehensive this disagreement requires further investigation. We have predicted a significantly higher nqcc for NaDF2 of 83±3 kHz, but, again, with a very small η value of 0.04±0.01.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1063/1.454031
