Structure and spectral features of H+(H2O)(7): Eigen versus Zundel forms

The two dimensional (2D) to three dimensional (3D) transition for the protonated water cluster has been controversial, in particular, for H+(H2O)(7). For H+(H2O)(7) the 3D structure is predicted to be lower in energy than the 2D structure at most levels of theory without zero-point energy (ZPE) correction. On the other hand, with ZPE correction it is predicted to be either 2D or 3D depending on the calculational levels. Although the ZPE correction favors the 3D structure at the level of coupled cluster theory with singles, doubles, and perturbative triples excitations [CCSD(T)] using the aug-cc-pVDZ basis set, the result based on the anharmonic zero-point vibrational energy correction favors the 2D structure. Therefore, the authors investigated the energies based on the complete basis set limit scheme (which we devised in an unbiased way) at the resolution of the identity approximation Moller-Plesset second order perturbation theory and CCSD(T) levels, and found that the 2D structure has the lowest energy for H+(H2O)(7) [though nearly isoenergetic to the 3D structure for D+(D2O)(7)]. This structure has the Zundel-type configuration, but it shows the quantum probabilistic distribution including some of the Eigen-type configuration. The vibrational spectra of MP2/aug-cc-pVDZ calculations and Car-Parrinello molecular dynamics simulations, taking into account the thermal and dynamic effects, show that the 2D Zundel-type form is in good agreement with experiments. (c) 2006 American Institute of Physics.open353

The effect of age on sagittal plane profile of the lumbar spine according to standing, supine, and various sitting positions

BACKGROUND: The sagittal alignment of the spine changes depending on body posture and degenerative changes. This study aimed to observe changes in sagittal alignment of the lumbar spine with different positions (standing, supine, and various sitting postures) and to verify the effect of aging on lumbar sagittal alignment. METHODS: Whole-spine lateral radiographs were obtained for young volunteers (25.4 ± 2.3 years) and elderly volunteers (66.7 ± 1.7 years). Radiographs were obtained in standing, supine, and sitting (30°, 60°, and 90°) positions respectively. We compared the radiological changes in the lordotic and segmental angles in different body positions and at different ages. Upper and lower lumbar lordosis were defined according to differences in anatomical sagittal mobility and kinematic behavior. RESULTS: Lumbar lordosis was greater in a standing position (52.79° and 53.90° in young and old groups, respectively) and tended to decrease as position changed from supine to sitting. Compared with the younger group, the older group showed significantly more lumbar lordosis in supine and 60° and 90° sitting positions (P = 0.043, 0.002, 0.011). Upper lumbar lordosis in the younger group changed dynamically in all changed positions compared with the old group (P = 0.019). Lower lumbar lordosis showed a decreasing pattern in both age groups, significantly changing as position changed from 30° to 60° (P = 0.007, 0.007). CONCLUSIONS: Lumbar lordosis decreases as position changes from standing to 90°sitting. The upper lumbar spine is more flexible in individuals in their twenties compared to those in their sixties. Changes in lumbar lordosis were concentrated in the lower lumbar region in the older group in sitting positions