Nuclear Quadrupole Tensors for (35)Cl and (37)Cl in cis-1-chloro-2-fluoroethylene Obtained by Detection of Perturbation-Allowed DeltaJ = 2 and DeltaJ = 3 Transitions.
The nuclear quadrupole hyperfine structure in rotational transitions of cis-1-chloro-2-fluoroethylene was measured for both (35)Cl and (37)Cl containing isotopomers in the millimeter-wave region. Near degeneracies of the 9(3,7) and 10(2,9) levels of (35)ClHC&dbond;CFH and of the 19(9,10/11) and 17(10,7/8) levels of (37)ClHC&dbond;CFH cause strong perturbations of the hyperfine patterns and give rise to perturbation-allowed DeltaJ = 2 and DeltaJ = 3 transitions. Lamb-dip measurements of such perturbed hyperfine patterns and of forbidden DeltaJ = +2 and perturbation-enhanced DeltaJ = 0 transitions of (35)ClHC&dbond;CFH provided an accurate determination of chi(ab), the off-diagonal element of the inertial nuclear quadrupole tensor. For (37)ClHC&dbond;CFH, chi(ab) was determined for the first time thanks to the observation of perturbed hyperfine patterns and of forbidden DeltaJ = +3 and DeltaJ = -2 transitions. Additional measurements of hyperfine structures led to improved values for the diagonal elements of the chi tensor of both (35)Cl and (37)Cl. Moreover, the complete inertial nuclear quadrupole tensor was evaluated from the field gradient at the chlorine nucleus computed by using the Multi-Configuration Self-Consistent Field (MCSCF) approach and employing basis sets of triple-zeta quality: very good agreement with the experiment was obtained. Copyright 2000 Academic Press.
Dore
L
Dipartimento di Chimica "G. Ciamician,", Università di Bologna, Via Selmi 2, Bologna, I-40126, Italy
Puzzarini
C
Cazzoli
G
Gambi
A