Infrared spectroscopy of sodium doped water clusters: Interaction with the solvated electron

The measured vibrational OH-stretch spectra of size-selected Na(H2O)(n) clusters for n = 8, 10, 16, and 20 are compared with first-principle calculations, which account for the interaction of the sodium cation, the electron, and the water molecules with the hydrogen-bonded network. The calculated harmonic frequencies are corrected by comparing similar results obtained for pure water clusters with experiment. The experimental spectra are dominated by intensity peaks between 3350 and 3550 cm(-1), which result from the interaction of the H atoms with the delocalized electron cloud. The calculations, which are all based upon the average spectra of the four lowest-energy isomers, indicate that most of the peaks at the lower end of this range (3217 cm(-1) for n = 8) originate from the interaction of one H atom with the electron distribution in a configuration with a single hydrogen-bonding acceptor. Those at the upper end (3563 cm(-1) for n = 8) come from similar interactions with two acceptors. The doublets, which arise from the interaction of both H atoms with the electron, appear in the red-shifted part of the spectrum. They are with 3369/3443 cm(-1) quite pronounced for n = 8 but slowly vanish for the larger clusters where they mix with the other spectral interactions of the hydrogen-bonded network, namely, the fingerprints of the free, the double, and the single donor OH positions known from pure water cluster spectroscopy. For all investigated sizes, the electron is sitting at the surface of the clusters

Face and construct validation of a virtual peg transfer simulator

International audienceBackground The Fundamentals of Laparoscopic Surgery (FLS) trainer box is now established as a standard for evaluating minimally invasive surgical skills. A particularly simple task in this trainer box is the peg transfer task which is aimed at testing the surgeon's bimanual dexterity, hand-eye coordination, speed, and precision. The Virtual Basic Laparoscopic Skill Trainer (VBLaST©) is a virtual version of the FLS tasks which allows automatic scoring and real-time, subjective quantification of performance without the need of a human proctor. In this article we report validation studies of the VBLaST© peg transfer (VBLaST-PT©) simulator. Methods Thirty-five subjects with medical background were divided into two groups: experts (PGY 4-5, fellows, and practicing surgeons) and novices (PGY 1-3). The subjects were asked to perform the peg transfer task on both the FLS trainer box and the VBLaST-PT© simulator; their performance was evaluated based on established metrics of error and time. A new length of trajectory (LOT) metric has also been introduced for offline analysis. A questionnaire was used to rate the realism of the virtual system on a 5-point Likert scale. Results Preliminary face validation of the VBLaST-PT© with 34 subjects rated on a 5-point Likert scale questionnaire revealed high scores for all aspects of simulation, with 3.53 being the lowest mean score across all questions. A two-tailed Mann-Whitney test performed on the total scores showed significant (p = 0.001) difference between the groups. A similar test performed on the task time (p = 0.002) and the LOT (p = 0.004) separately showed statistically significant differences between the experts and the novices (p < 0.05). The experts appear to be traversing shorter overall trajectories in less time than the novices. Conclusion VBLaST-PT© showed both face and construct validity and has promise as a substitute for the FLS for training peg transfer skills