ABSTRACT
The ability of gas-surface dynamics studies to resolve the velocity distribution of the scattered species in the 2D scattering plane has been limited by technical capabilities and only a few different approaches have been explored in recent years. In comparison, gas-phase scattering studies have been transformed by the near ubiquitous use of velocity map imaging. We describe an innovative means of introducing a dielectric surface within the electric field of a typical velocity map imaging experiment. The retention of optimum velocity mapping conditions was validated by measurements of iodomethane-d3 photodissociation and SIMION calculations. To demonstrate the system's capabilities, the velocity distributions of ammonia molecules scattered from a polytetrafluoroethylene surface have been measured for multiple product rotational states.
ABSTRACT
The S1((1)ππ*) state of the (dominant) syn-conformer of 2-chlorophenol (2-ClPhOH) in the gas phase has a subpicosecond lifetime, whereas the corresponding S1 states of 3- and 4-ClPhOH have lifetimes that are, respectively, â¼2 and â¼3-orders of magnitude longer. A range of experimental techniques-electronic spectroscopy, ultrafast time-resolved photoion and photoelectron spectroscopies, H Rydberg atom photofragment translational spectroscopy, velocity map imaging, and time-resolved Fourier transform infrared emission spectroscopy-as well as electronic structure calculations (of key regions of the multidimensional ground (S0) state potential energy surface (PES) and selected cuts through the first few excited singlet PESs) have been used in the quest to explain these striking differences in excited state lifetime. The intramolecular O-H···Cl hydrogen bond specific to syn-2-ClPhOH is key. It encourages partial charge transfer and preferential stabilization of the diabatic (1)πσ* potential (relative to that of the (1)ππ* state) upon stretching the C-Cl bond, with the result that initial C-Cl bond extension on the adiabatic S1 PES offers an essentially barrierless internal conversion pathway via regions of conical intersection with the S0 PES. Intramolecular hydrogen bonding is thus seen to facilitate the type of heterolytic dissociation more typically encountered in solution studies.
ABSTRACT
OBJECTIVE: To compare the Willis dropped ovary technique with traditional spaying methods in extensive beef cattle herds in northern Australia. PROCEDURE: Three field trials were conducted simultaneously at different sites in northern Australia in 1996-97. Brahman and Brahman-Shorthorn cross heifers (n = 219, 2 years, 250 to 378 kg) and cows (n = 211, 3 to 16 years, 256 to 540 kg) were allocated by stratified randomisation to three treatments: spaying using the Willis dropped ovary technique (WDOT); spaying using traditional paralumbar and vaginal methods; and unspayed. Following these procedures, these nonpregnant, nonlactating cattle were then exposed to bulls (4 per 100 females) under extensive rangeland conditions for 12 months during which time weight, body condition, pregnancy and ovarian function were monitored and compared. RESULTS: Pregnancy rates varied from 60 to 90% for entire heifers and 80 to 100% for entire cows depending on site. The traditional spay methods were 100% successful in preventing pregnancy; the WDOT was 92 to 97% effective, depending on operator experience. The number of deaths was the same or higher in Willis spayed animals than other groups. Weight changes were similar in all groups at the three sites over the trial period. The time taken to spay using the WDOT was similar to or less than that required for the traditional methods. Uterine abnormalities were not observed in animals spayed with the WDOT, there were however 30 (12.4%) animals where excision of the ovary was incomplete; the still-attached ovarian remnant presumably accounting for the three pregnant animals in this group. CONCLUSION: The WDOT suffers from requiring a high degree of skill in transrectal ovarian manipulation. There were more deaths and more pregnancies than with traditional spay methods. More experienced operators can be expected to achieve lower mortalities, better contraception and higher processing rates. Pregnancy will occur as a consequence of ovarian remnants unless care is taken to ensure removal of the entire ovary.