ABSTRACT
The (sub-)millimeter wave spectrum of the non-rigid CH2OH radical is investigated both experimentally and theoretically. Ab initio calculations are carried out to quantitatively characterize its potential energy surface as a function of the two large amplitude â H1COH and â H2COH dihedral angles. It is shown that the radical displays a large amplitude torsional-like motion of its CH2 group with respect to the OH group. The rotation-torsion levels computed with the help of a 4D Hamiltonian accounting for this torsional-like motion and for the overall rotation exhibit a tunneling splitting, in agreement with recent experimental investigations, and a strong rotational dependence of this tunneling splitting on the rotational quantum number Ka due to the rotation-torsion Coriolis coupling. Based on an internal axis method approach, a fitting Hamiltonian accounting for tunneling effects and for the fine and hyperfine structure is built and applied to the fitting of the new (sub)-millimeter wave transitions measured in this work along with previously available high-resolution data. 778 frequencies and wavenumbers are reproduced with a unitless standard deviation of 0.79 using 27 parameters. The N = 0 tunneling splitting, which could not be determined unambiguously in the previous high-resolution investigations, is determined based on its rotational dependence.
ABSTRACT
Age differences in the processing of contextual information were investigated using the Item, associated Context, and Ensemble (ICE) model (K. Murnane, M. P. Phelps, & K. Malmberg, 1999), a general global matching model of recognition memory. In two experiments, young and older adults studied words in environmental contexts and were tested in both the same and different contexts. Patterns of context effects for hit rate, false alarm rate, and d' suggest that older adults process associated context, but have difficulties integrating items and context into an ensemble. Thus, older adults appear to have a specific, rather than a general, deficit in processing contextual information. A deficiency in ensemble processing may be responsible for the prevalent finding that older adults show poorer recognition memory performance than young adults.
