ISSN:
1089-7690
Source:
AIP Digital Archive
Topics:
Physics
,
Chemistry and Pharmacology
Notes:
Electric field gradients (efg's) at the nitrogen nuclei in N2, NO+, NO, CN, and CN− and at the nitrogen and hydrogen nuclei in HCN, HNC, and NH3, calculated using ab initio quantum chemical methods, are reported. Employing extensive Gaussian basis sets, the efg's were computed at the self-consistent field (SCF), singles and doubles configuration interaction [CI(SD)], and coupled pair functional (CPF) levels of theory as the expectation values of the efg operator and also as the energy derivatives of the appropriate perturbed Hamiltonian using the finite field method. Corrections due to zero point vibrational motions were also calculated. The effect of basis set incompleteness on the calculated efg's, together with the experimental nuclear quadrupole coupling constants, are used to estimate the 14N and 2H nuclear quadrupole moments, and to test the quality of the correlated wave functions generated by the CI(SD) and CPF methods. The recommended values, on the basis of the present calculations, are 2.05±0.02 and 0.29±0.01 fm2, respectively, for the 14N and 2H quadrupole moments.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1063/1.452390
